CN110479218A - A method of super-hydrophobic super-oleophylic aerogel material is prepared using nano-cellulose and nanoparticle as raw material - Google Patents

Abstract

A method of super-hydrophobic super-oleophylic aerogel material being prepared using nano-cellulose and nanoparticle as raw material, it is related to a kind of method for preparing super-hydrophobic super-oleophylic aerogel material.The present invention solves the problem of that existing nano-cellulose aerogel uses fluorine-containing toxic modifying agent and volatile organic solvent to need particular device and complex process during the preparation process.Preparation method: one, modified nanometer cellulose solution is prepared；Two, improved silica solution is prepared；Three, it mixes；Four, it is pre-chilled；Five, it freezes.The present invention is used to prepare super-hydrophobic super-oleophylic aerogel material using nano-cellulose and nanoparticle as raw material.

Description

A kind of superhydrophobic superoleophilic air condensation prepared by using nanocellulose and nanoparticles as raw materials glue material method

technical field

The invention relates to a method for preparing superhydrophobic and superoleophilic airgel materials.

Background technique

Oil spills have caused enormous economic and ecological burdens. For catastrophic oil spills, there are several rescue measures such as filtration, mechanical extraction, chemical degradation, bioremediation and adsorbent materials. Among these methods, the adsorbent material stands out for its ease of handling, excellent oil trapping capacity and economical cost-effectiveness. This adsorption material can not only be used in large-scale oil spill accidents, but also has broad application prospects in chemical laboratories, production bases, and even households. Nanocellulose-based aerogels have attracted attention for oil-water separation. Compared with other polymer aerogels, abundant and sustainably produced nanocellulose aerogels are of greater value due to their environmental protection and biocompatibility. However, the inherent hydrophilicity of cellulose poses an obstacle to its application in oil-water separation. At present, a variety of surface modification methods have been developed for the preparation of cellulose-based aerogels with special wettability, such as chemical vapor deposition technology is widely used in the hydrophobic modification of cellulose-based aerogels, Atomic layer deposition, sol-gel and cold plasma techniques prepared nano-cellulose aerogels with special wettability. These methods use fluorine-containing toxic modifiers and use volatile organic solvents in the process, as well as require specific equipment and complicated processes, making it difficult to prepare nano-airgel superhydrophobic aerogels on a large scale.

Contents of the invention

The present invention aims to solve the problem that the existing nanocellulose airgel uses fluorine-containing toxic modifiers and volatile organic solvents in the preparation process, requiring specific equipment and complicated processes, and provides a nanocellulose and nanoparticle A method for preparing a superhydrophobic superoleophilic airgel material as a raw material.

A method for preparing superhydrophobic and superoleophilic airgel materials with nanocellulose and nanoparticles as raw materials, which is carried out according to the following steps:

1. Under the condition of rotating speed of 1000r/min～100000r/min, disperse nanocellulose into deionized water through a high-speed homogenizer, and disperse evenly. Under the condition of 10mL/h～20mL/h, add γ-aminopropyltriethoxysilane, and then add fluorine-free modifier under the magnetic stirring at a speed of 50r/min～1000r/min to obtain a modified Nanocellulose solution;

The mass ratio of the nanocellulose to deionized water is 1g:(50～600)mL; the mass ratio of the nanocellulose to γ-aminopropyltriethoxysilane is 1:(0.2 ～8); The mass ratio of described nanocellulose and fluorine-free modifier is 1:(0.33～1);

2. Add nanoparticles into deionized water, and then under the condition of power of 800W ~ 1500W, ultrasonically disperse evenly, and add hexadecyl trimethoxy Silane and formic acid with a mass percentage of 10% to 88% obtain a modified silicon dioxide solution;

The volume ratio of the mass of the nanoparticles to deionized water is 1g:(15-800)mL; the mass ratio of the nanoparticles to hexadecyltrimethoxysilane is 1:(0.22-15.6); The mass ratio of the nanoparticles to 10%-88% formic acid is 1:(0.5-8);

3. Mix the modified nano-cellulose solution and the modified silica solution, and ultrasonically treat it for 2 minutes to 60 minutes under the condition of a power of 800W to 1500W, and then stir it under a magnetic stirring speed of 50r/min to 1000r/min , mixed evenly to obtain a mixed solution;

The volume ratio of the modified nanocellulose solution to the modified silicon dioxide solution is 1:(0.5～5);

4. Freeze the mixed solution at a temperature of -12°C to -5°C for 2h to 12h to obtain a pre-frozen solution;

5. Place the pre-frozen solution in a vacuum freeze dryer, and freeze it for 2 hours to 12 hours at a temperature of -50°C to -5°C to obtain a superhydrophobic and superoleophilic airgel material.

The beneficial effects of the present invention are:

1. Using nanocellulose as raw material, it is a naturally degradable biomass material with abundant reserves and environmental friendliness.

2. The superhydrophobic and superoleophilic airgel material prepared by the present invention has high strength, can withstand the pressure of 200g weight and maintain a stable structure, and during the contact angle test process, water droplets cannot stay on the airgel surface, Therefore, the airgel has a good hydrophobic effect.

3. As a new type of oil-absorbing material, the hydrophobic super-oleophilic airgel material prepared by the present invention has fast adsorption speed, can reach adsorption equilibrium in 10s, and has a large adsorption capacity. The maximum adsorption capacity for carbon tetrachloride can reach 32.95g /g, the maximum adsorption capacity of n-hexane can reach 13.01g/g, the method is simple, green and environmentally friendly, and can be applied to the treatment of oily wastewater, and with the assistance of the suction filter pump, it can complete the continuous and efficient separation of oil-water mixture. For suction filtration The pressure range used by the pump is -0.01MPa～0.02MPa.

4. The superhydrophobic nanocellulose airgel prepared by the present invention is prepared by using water as the environment and modified by a fluorine-free modifier, which meets the requirements of environmental protection and non-toxicity, and the preparation process is simple, reducing the cost of solvent replacement. link.

5. The experimental scheme of the present invention has high feasibility, simple operation process, less capital investment, short preparation cycle, mild reaction conditions, no need for large-scale equipment, large-scale industrial production and processing can be realized, and it has a very wide application prospect.

The invention is used for a method for preparing super-hydrophobic and super-oleophilic airgel materials by using nano-cellulose and nano-particles as raw materials.

Description of drawings

Fig. 1 is the scanning electron microscope picture of the superhydrophobic superoleophilic airgel material prepared in Example 1 under the condition that the scale is 2 μm;

Fig. 2 is the scanning electron micrograph of the superhydrophobic superoleophilic airgel material prepared in Example 1 under the condition that the scale is 1 μm;

Fig. 3 is the scanning electron microscope picture under the condition of 100nm for the superhydrophobic superoleophilic airgel material prepared in embodiment one;

Fig. 4 is the actual figure that the superhydrophobic superoleophilic airgel material prepared in embodiment one is placed in water;

Fig. 5 is the physical figure of the superhydrophobic superoleophilic airgel material prepared in Example 1 under 200g weight pressure;

Fig. 6 is the physical figure that the water surface contains light oil;

Fig. 7 is the physical diagram of the adsorption process of light oil on the water surface by the superhydrophobic superoleophilic airgel material prepared in embodiment one;

Fig. 8 is the physical figure of the process taken out after the superhydrophobic superoleophilic airgel material prepared in Example 1 completes the adsorption of light oil on the water surface;

Fig. 9 is the physical figure containing heavy oil at the bottom of the water;

Fig. 10 is the actual figure of the adsorption process of the heavy oil at the bottom of the water by the superhydrophobic superoleophilic airgel material prepared in Example 1;

Fig. 11 is the physical figure of the process taken out after the superhydrophobic superoleophilic airgel material prepared in Example 1 has completed the adsorption of heavy oil at the bottom of the water;

Fig. 12 is a real picture of water droplets moving downward during the contact angle test of the superhydrophobic and superoleophilic airgel material prepared in Example 1;

Fig. 13 is a physical picture of water droplets pressing down during the contact angle test of the superhydrophobic and superoleophilic airgel material prepared in Example 1;

Fig. 14 is a physical diagram of the upward movement of water droplets after being pressed during the contact angle test of the superhydrophobic and superoleophilic airgel material prepared in Example 1;

Fig. 15 is a physical picture of the superhydrophobic superoleophilic airgel material prepared in Example 1 during the contact angle test, and the water droplet does not stay on the surface.

Detailed ways

Specific embodiment one: present embodiment a kind of method that prepares superhydrophobic superoleophilic airgel material with nanocellulose and nanoparticle as raw material, it is carried out according to the following steps:

1. Under the condition of rotating speed of 1000r/min～100000r/min, disperse nanocellulose into deionized water through a high-speed homogenizer, and disperse evenly. Under the condition of 10mL/h～20mL/h, add γ-aminopropyltriethoxysilane, and then add fluorine-free modifier under the magnetic stirring at a speed of 50r/min～1000r/min to obtain a modified Nanocellulose solution;

The mass ratio of the nanocellulose to deionized water is 1g:(50～600)mL; the mass ratio of the nanocellulose to γ-aminopropyltriethoxysilane is 1:(0.2 ～8); The mass ratio of described nanocellulose and fluorine-free modifier is 1:(0.33～1);

2. Add nanoparticles into deionized water, and then under the condition of power of 800W ~ 1500W, ultrasonically disperse evenly, and add hexadecyl trimethoxy Silane and formic acid with a mass percentage of 10% to 88% obtain a modified silicon dioxide solution;

The volume ratio of the mass of the nanoparticles to deionized water is 1g:(15-800)mL; the mass ratio of the nanoparticles to hexadecyltrimethoxysilane is 1:(0.22-15.6); The mass ratio of the nanoparticles to 10%-88% formic acid is 1:(0.5-8);

3. Mix the modified nano-cellulose solution and the modified silica solution, and ultrasonically treat it for 2 minutes to 60 minutes under the condition of a power of 800W to 1500W, and then stir it under a magnetic stirring speed of 50r/min to 1000r/min , mixed evenly to obtain a mixed solution;

The volume ratio of the modified nanocellulose solution to the modified silicon dioxide solution is 1:(0.5～5);

4. Freeze the mixed solution at a temperature of -12°C to -5°C for 2h to 12h to obtain a pre-frozen solution;

5. Place the pre-frozen solution in a vacuum freeze dryer, and freeze it for 2 hours to 12 hours at a temperature of -50°C to -5°C to obtain a superhydrophobic and superoleophilic airgel material.

The beneficial effects of this embodiment are: 1. Nanocellulose is used as a raw material, which is a natural and degradable biomass material with abundant reserves and environmental friendliness.

2. The superhydrophobic and superoleophilic airgel material prepared in this embodiment has high strength, can withstand the pressure of 200g weight and maintain a stable structure, and during the contact angle test process, water droplets cannot stay on the surface of the airgel , so the airgel has a good hydrophobic effect.

3. As a new type of oil-absorbing material, the hydrophobic super-oleophilic airgel material prepared in this embodiment has a fast adsorption speed, can reach adsorption equilibrium in 10 seconds, and has a large adsorption capacity. The maximum adsorption capacity for carbon tetrachloride can reach 32.95 g/g, the maximum adsorption capacity of n-hexane can reach 13.01g/g, the method is simple, green and environmentally friendly, and can be applied to the treatment of oily wastewater, and with the assistance of the suction filter pump, it can complete the continuous and efficient separation of oil-water mixture. The pressure range used by the filter pump is -0.01MPa～0.02MPa.

4. The superhydrophobic nanocellulose airgel prepared in this embodiment is prepared by using water as the environment and modified by a fluorine-free modifier, which meets the requirements of environmental protection and non-toxicity, and the preparation process is simple, reducing solvent replacement link.

5. The experimental scheme of this embodiment has high feasibility, simple operation process, less capital investment, short preparation cycle, mild reaction conditions, no need for large-scale equipment, large-scale industrial production and processing can be realized, and it has a very wide application prospect.

Embodiment 2: This embodiment is different from Embodiment 1 in that: the particle size of the nanoparticles described in Step 2 is 7nm-40nm. Others are the same as in the first embodiment.

Specific embodiment three: This embodiment differs from specific embodiment one or two in that the nanoparticles described in step two are nano-silicon dioxide, nano-titanium dioxide, nano-ferric oxide, nano-calcium carbonate, nano-kaolin or nano- alumina. Others are the same as in the first or second embodiment.

Embodiment 4: This embodiment is different from Embodiment 1 to Embodiment 3 in that: in step 1, the fluorine-free modifier is hexadecyltrimethoxysilane. Others are the same as the specific embodiments 1 to 3.

Specific embodiment five: the difference between this embodiment and one of specific embodiments one to four is: the volume ratio of the quality of nanocellulose described in step one to deionized water is 1g: (100～600) mL; step one The mass ratio of nanocellulose described in and γ-aminopropyltriethoxysilane is 1:(0.5～8); the mass ratio of nanocellulose described in step 1 and fluorine-free modifier is 1 :(1.3～1). Others are the same as the specific embodiments 1 to 4.

Embodiment 6: The difference between this embodiment and one of Embodiments 1 to 5 is that in step 1, the nanocellulose is dispersed into the deionized Disperse evenly in water, add γ-aminopropyltriethoxysilane under the conditions of magnetic stirring at a rotating speed of 100r/min to 1000r/min and an adding speed of 15mL/h to 20mL/h, and then add γ-aminopropyltriethoxysilane at a rotating speed of 100r/min Under the magnetic stirring of /min～1000r/min, the fluorine-free modifier is added to obtain the modified nanocellulose solution. Others are the same as those in Embodiments 1 to 5.

Specific embodiment seven: this embodiment is different from one of specific embodiments one to six in that: the volume ratio of the quality of the nanoparticles described in step two to deionized water is 1g:(15-500) mL; in step two The mass ratio of the nanoparticles and hexadecyltrimethoxysilane is 1:(1.2～15.6); the mass ratio of the nanoparticles and the mass percent of formic acid described in step 2 is 1 :(1.1～8). Others are the same as those in Embodiments 1 to 6.

Embodiment 8: The difference between this embodiment and one of Embodiments 1 to 7 is that in step 2, nanoparticles are added to deionized water, and then under the condition of power of 1000W to 1500W, ultrasonic dispersion is uniform, and the Under 100r/min-1000r/min magnetic stirring, cetyltrimethoxysilane and formic acid with a mass percentage of 50%-88% are sequentially added to obtain a modified silicon dioxide solution. Others are the same as those in Embodiments 1 to 7.

Embodiment 9: This embodiment differs from Embodiment 1 to Embodiment 8 in that the volume ratio of the modified nanocellulose solution to the modified silica solution described in step 3 is 1: (2-5). Others are the same as those in Embodiments 1 to 8.

Embodiment 10: The difference between this embodiment and one of Embodiments 1 to 9 is that in step 5, the pre-frozen solution is placed in a vacuum freeze dryer at a temperature of -50°C to -10°C. , frozen for 8h ~ 12h. Others are the same as the specific embodiments 1 to 9.

Adopt the following examples to verify the beneficial effects of the present invention:

Embodiment one:

A method for preparing superhydrophobic and superoleophilic airgel materials with nanocellulose and nanoparticles as raw materials, characterized in that it is carried out in the following steps:

1. Under the condition of rotating speed of 100000r/min, disperse nanocellulose into deionized water through a high-speed homogenizer, and disperse evenly. Adding γ-aminopropyltriethoxysilane, and then adding hexadecyltrimethoxysilane under a magnetic stirring speed of 1000r/min to obtain a modified nanocellulose solution;

The mass ratio of the nanocellulose to deionized water is 1g:100mL; the mass ratio of the nanocellulose to γ-aminopropyltriethoxysilane is 1:0.5; the nanofiber The mass ratio of prime and hexadecyltrimethoxysilane is 1:1.3;

2. Add the nanoparticles into deionized water, and then, under the condition of a power of 900W, ultrasonically disperse evenly, and under the magnetic stirring at a speed of 600r/min, add hexadecyltrimethoxysilane and 88% by mass in turn. % formic acid to obtain a modified silicon dioxide solution;

The mass ratio of described nanoparticle and deionized water is 1g:15mL; The mass ratio of described nanoparticle and hexadecyltrimethoxysilane is 1:1.2; Described nanoparticle and mass percent are The mass ratio of 88% formic acid is 1:1.1;

3. Mix the modified nanocellulose solution and the modified silicon dioxide solution, and ultrasonically treat it for 45 minutes under the condition of a power of 900W, and then mix evenly under a magnetic stirring speed of 1000r/min to obtain a mixed solution;

The volume ratio of the modified nanocellulose solution to the modified silicon dioxide solution is 1:2;

4. Freeze the mixed solution for 6 hours at a temperature of -12°C to obtain a pre-frozen solution;

5. Place the pre-frozen solution in a vacuum freeze dryer, and freeze it for 12 hours at a temperature of -50° C. to obtain a superhydrophobic and superoleophilic airgel material.

The particle size of the nanoparticles described in step 2 is 7nm-40nm;

The nanoparticles described in step 2 are nano silicon dioxide;

The total volume after mixing the modified nanocellulose solution and the modified silica solution described in Step 3 is 10 mL.

Fig. 1 is the scanning electron microscope picture of the superhydrophobic superoleophilic airgel material prepared in Example 1 under the condition of 2 μm, and Fig. 2 is the photomicrograph of the superhydrophobic superoleophilic airgel material prepared in Example 1 under the condition of 1 μm The scanning electron microscope picture shows that the surface of the super-hydrophobic and super-oleophilic airgel material is rough.

Figure 3 is a scanning electron microscope image of the superhydrophobic and superoleophilic airgel material prepared in Example 1 under the condition of a scale of 100nm. It can be seen from the figure that the average particle size of the modified nano-silica particles is about 50nm, and they are evenly distributed. .

Fig. 4 is the physical picture of the superhydrophobic superoleophilic airgel material prepared in Example 1 placed in water; As can be seen from the figure, a bright path is formed on the surface of the superhydrophobic superoleophilic airgel material, indicating that the prepared airgel has good superhydrophobicity.

Fig. 5 is the actual picture of the superhydrophobic superoleophilic airgel material prepared in Example 1 under the pressure of 200g weight. It can be seen from the figure that the superhydrophobic superoleophilic airgel material can maintain a stable structure under the pressure of 200g weight.

Using the superhydrophobic superoleophilic airgel material prepared in Example 1 to absorb light oil n-hexane in water, Figure 6 is a physical map containing light oil on the water surface; Figure 7 is the superhydrophobic superoleophilic airgel material prepared in Example 1 The physical figure of the adsorption process of light oil on the water surface; Figure 8 is the physical figure of the process taken out after the superhydrophobic superoleophilic airgel material prepared in Example 1 has completed the adsorption of light oil on the water surface; after testing 0.3681g of superhydrophobic super The lipophilic airgel material can absorb 4.79g of n-hexane (13.01g/g).

Utilize the superhydrophobic superoleophilic airgel material prepared in Example 1 to absorb heavy oil carbon tetrachloride in water, and Fig. 9 is a physical map containing heavy oil at the bottom of the water; Fig. 10 is the superhydrophobic superoleophilic airgel material prepared in Example 1 The physical picture of the adsorption process of heavy oil at the bottom of the water; Figure 11 is the physical picture of the process taken out after the superhydrophobic and super-oleophilic airgel material prepared in Example 1 has absorbed the heavy oil at the bottom of the water; after testing, 0.366g of the airgel can absorb 12.06g of carbon tetrachloride (32.95g/g).

The superhydrophobic superoleophilic airgel material prepared in Example 1 was tested for contact angle. Since the superhydrophobic superoleophilic airgel material prepared in this example has good hydrophobicity, water droplets cannot stay on the surface of the airgel, as shown in Fig. 12 is the actual picture of the water drop moving downward during the contact angle test of the superhydrophobic and superoleophilic airgel material prepared in Example 1; FIG. 13 is the contact angle test process of the superhydrophobic and superoleophilic airgel material prepared in Example 1 14 is the actual picture of the water droplet moving upward after being pressed during the contact angle test of the superhydrophobic and superoleophilic airgel material prepared in Example 1; FIG. 15 is the superhydrophobic airgel material prepared in Example 1. During the contact angle test of the super-oleophilic airgel material, the actual picture of the water droplet not staying on the surface; through the drop and press test of the water droplet on the airgel, it can be observed that when the water droplet touches the surface of the airgel Pressing with a certain force, the droplet fails to stay on the surface of the airgel during the pull-back process, so the airgel has a good hydrophobic effect.

Use tweezers to pick up the super-hydrophobic and super-oleophilic airgel material prepared in Example 1 and put it into various organic solvents (n-hexane, acetone, toluene, xylene, carbon tetrachloride, ethyl acetate, cyclohexane, dichloromethane , gasoline, vegetable oil), and then record the quality of the superhydrophobic superoleophilic airgel material after adsorption every 2s, and it can be found that the quality of the superhydrophobic superoleophilic airgel material no longer changes after adsorption for 10s. The superhydrophobic and superoleophilic airgel material prepared in Example 1 has a fast adsorption speed, can reach adsorption equilibrium in 10 seconds, and can reach a maximum adsorption capacity of 32.95 g/g for carbon tetrachloride.

The superhydrophobic and superoleophilic airgel material prepared in Example 1 can complete the continuous and efficient separation of oil-water mixture with the assistance of the suction filter pump, and the pressure range for the suction filter pump is -0.01MPa～0.02MPa.

Claims (10)

1. a kind of method for preparing super-hydrophobic super-oleophylic aerogel material as raw material using nano-cellulose and nanoparticle, feature It is that it is carried out according to the following steps:

One, under conditions of revolving speed is 1000r/min~100000r/min, nano-cellulose is dispersed by high speed homogenization device Into deionized water, be uniformly dispersed, revolving speed be 50r/min~1000r/min magnetic agitation and be added speed be 10mL/h Under conditions of~20mL/h, gamma-aminopropyl-triethoxy-silane is added, then in the magnetic that revolving speed is 50r/min~1000r/min Under power stirring, it is added fluorine-free modified dose, obtains modified nanometer cellulose solution；

The quality of the nano-cellulose and the volume ratio of deionized water are 1g:(50~600) mL；The nano-cellulose Mass ratio with gamma-aminopropyl-triethoxy-silane is 1:(0.2~8)；The nano-cellulose and fluorine-free modified dose of matter Amount is than being 1:(0.33~1)；

Two, nano particle is add to deionized water, then under conditions of power is 800W~1500W, ultrasonic disperse is equal It is even, in the case where revolving speed is the magnetic agitation of 50r/min~1000r/min, sequentially add hexadecyl trimethoxy silane and quality The formic acid that percentage is 10%~88%, obtains improved silica solution；

The quality of the nano particle and the volume ratio of deionized water are 1g:(15~800) mL；The nano particle and ten The mass ratio of six alkyl trimethoxysilanes is 1:(0.22~15.6)；The nano particle and mass percent be 10%~ The mass ratio of 88% formic acid is 1:(0.5~8)；

Three, modified nanometer cellulose solution and improved silica solution are mixed, and in the condition that power is 800W~1500W Under, it is ultrasonically treated 2min~60min, then in the case where revolving speed is the magnetic agitation of 50r/min~1000r/min, is uniformly mixed, obtains To mixed solution；

Volume ratio 1:(0.5~5 of the modified nanometer cellulose solution and improved silica solution)；

Four, by mixed solution under conditions of temperature is -12 DEG C~-5 DEG C, 2h~12h is freezed, it is molten after being freezed in advance Liquid；

Five, the solution after preparatory freezing is placed in vacuum freeze drier, it is cold under conditions of temperature is -50 DEG C~-5 DEG C Freeze 2h~12h, obtains super-hydrophobic super-oleophylic aerogel material.

2. according to claim 1 a kind of using nano-cellulose and nanoparticle as raw material preparation super-hydrophobic super-oleophylic airsetting The method of glue material, it is characterised in that the partial size of nano particle described in step 2 is 7nm~40nm.

3. according to claim 1 a kind of using nano-cellulose and nanoparticle as raw material preparation super-hydrophobic super-oleophylic airsetting The method of glue material, it is characterised in that nano particle described in step 2 is nano silica, nano-titanium dioxide, nanometer Ferroso-ferric oxide, nanometer calcium carbonate, nano kaoline or nano aluminium oxide.

4. according to claim 1 a kind of using nano-cellulose and nanoparticle as raw material preparation super-hydrophobic super-oleophylic airsetting The method of glue material, it is characterised in that fluorine-free modified dose is hexadecyl trimethoxy silane in step 1.

5. according to claim 1 a kind of using nano-cellulose and nanoparticle as raw material preparation super-hydrophobic super-oleophylic airsetting The method of glue material, it is characterised in that the volume ratio of the quality of nano-cellulose described in step 1 and deionized water is 1g: (100~600) mL；The mass ratio of nano-cellulose and gamma-aminopropyl-triethoxy-silane described in step 1 is 1:(0.5 ~8)；Nano-cellulose described in step 1 and fluorine-free modified dose of mass ratio are 1:(1.3~1).

6. according to claim 1 a kind of using nano-cellulose and nanoparticle as raw material preparation super-hydrophobic super-oleophylic airsetting The method of glue material, it is characterised in that in step 1 under conditions of revolving speed is 5000r/min~100000r/min, by nanometer Cellulose is distributed in deionized water by high speed homogenization device, is uniformly dispersed, in the magnetic that revolving speed is 100r/min~1000r/min Under conditions of power stirring and addition speed are 15mL/h~20mL/h, gamma-aminopropyl-triethoxy-silane is added, then in revolving speed To be added fluorine-free modified dose, obtaining modified nanometer cellulose solution under the magnetic agitation of 100r/min~1000r/min.

7. according to claim 1 a kind of using nano-cellulose and nanoparticle as raw material preparation super-hydrophobic super-oleophylic airsetting The method of glue material, it is characterised in that the volume ratio of the quality of nano particle described in step 2 and deionized water is 1g:(15 ~500) mL；The mass ratio of nano particle described in step 2 and hexadecyl trimethoxy silane is 1:(1.2~15.6)； The mass ratio for the formic acid that nano particle described in step 2 and mass percent are 10%~88% is 1:(1.1~8).

8. according to claim 1 a kind of using nano-cellulose and nanoparticle as raw material preparation super-hydrophobic super-oleophylic airsetting The method of glue material, it is characterised in that nano particle is add to deionized water in step 2, then power be 1000W~ Under conditions of 1500W, ultrasonic disperse is uniform, in the case where revolving speed is the magnetic agitation of 100r/min~1000r/min, sequentially adds ten The formic acid that six alkyl trimethoxysilanes and mass percent are 50%~88%, obtains improved silica solution.

9. according to claim 1 a kind of using nano-cellulose and nanoparticle as raw material preparation super-hydrophobic super-oleophylic airsetting The method of glue material, it is characterised in that the body of modified nanometer cellulose solution and improved silica solution described in step 3 Product is than 1:(2~5).

10. according to claim 1 a kind of using nano-cellulose and nanoparticle as raw material preparation super-hydrophobic super-oleophylic gas The method of gel rubber material, it is characterised in that the solution after preparatory freezing is placed in vacuum freeze drier in step 5, in temperature Under conditions of degree is -50 DEG C~-10 DEG C, 8h~12h is freezed.