CN107312198A - Super-hydrophobic cavernous body and preparation method thereof - Google Patents
Super-hydrophobic cavernous body and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of super-hydrophobic cavernous body and preparation method thereof, the problem of existing adsorption recovery material hydrophobic effect is poor is mainly solved.The present invention is by using a kind of super-hydrophobic cavernous body, including cavernous body and nano modifier, the cavernous body is melamine sponge or polyurethane sponge, the nano modifier is by the way that nano material is dissolved in hydrophobic silicones compound ingredients, the technical scheme that stirring is obtained and preparation method thereof to after being completely dissolved preferably solves above mentioned problem, in being prepared available for super-hydrophobic cavernous body.
Description
Technical field
The present invention relates to a kind of super-hydrophobic cavernous body and preparation method thereof.
Background technology
With economic rapid growth, the petroleum consumption cumulative year after year of China, external dependence degree also expands year by year, in order to
Reduce dependence of China's economic development to oil exporting country, in recent years, China more payes attention to the exploitation of offshore oil, but therewith
What is come is increasing sea oil spill accident, causes serious energy waste, environmental pollution or even potential safety hazard.According to statistics,
The spilling oil mass of China littoral sea ship and offshore drilling platform oil spill accident in recent years is up to 37000 tons or so, wherein 50 tons
Major oil spill accident above has 69, about 8000 tons of an oil spillage of most serious.Moreover, by artificial origin and nature
The oil leak that the factors such as corrosion are caused shows ascendant trend year by year.These all further exacerbate China's oil shortage of resources
Situation, seriously constrains domestic economy sustainable development, causes serious ecological environment disaster.Therefore, in order to ensure China
The sustainable stable development of Petroleum Industry, is oil in the urgent need to researching and developing the oil loss control technology with independent intellectual property right
The engineering that gas is reclaimed and oil leak Emergency recovery is equipped smoothly is implemented to lay the foundation.
In spill response control operation process, the larger heavy oil of commercial oil skimmer processing viscosity is highly effective but right
In the less oil of viscosity, because the oily collection mode that encloses for the features such as its diffusion area is big, oil reservoir is thin, being difficult with traditional comes clear
Reason.Secondary destruction or pollution are not only brought to ecological environment using means such as dispersant, microorganism eutrophication and burnings, and
Waste the energy oil product of worsening shortages.Adsorption separation technology is as a kind of principle is ripe and the oil loss of economical and efficient the most
Control device, it is considered to be one of main flow direction of oil spilling control technology development.This technology it is crucial with adsorbing separation material
The exploitation of material, traditional oil spilling handles sorbing material based on activated carbon, asphalt felt and a variety of natural plants, goes out again in recent years
Macroporous absorption material (CN 103951843A, the 2014.07.30, full text using macromolecule sponge as substrate are showed；CN
102989414 B, 2014.09.10, in full；Zhang,Z.；Sèbe,G.；Rentsch,D.；Zimmermann,T.；
Tingaut,P.Chemistry of Materials 2014,26,2659；Si,Y.；Yu,J.；Tang,X.；Ge,J.；Ding,
B.Nat Commun 2014,5；Yang,Y.；Yi,H.；Wang,C.ACS Sustainable Chemistry&
Engineering 2015,3,3012.).These material generally existings protect oil cut rate reduction after being used for a long time, using effect is deteriorated,
It is difficult to processing thin layer oil slick and oil-water emulsion, adds the complex operation, with high costs that the later stage reclaims oil product, seriously hinder many
The commercial applications process of hole oleophilic oil material.Therefore we are using the reconstruct of surface and interface asperity and hydrophobic functional group branch
Modification is connect, the water-oil separating nanoscale interfacial materials with special wellability are formed, develops the water-oil separating material that can be mass-produced
The technical method of material, overcomes many defects of existing oil absorption material, fast and effectively realizes that water-oil separating is reclaimed.
The content of the invention
One of technical problems to be solved by the invention be the problem of existing adsorption recovery material hydrophobic effect is poor there is provided
A kind of new super-hydrophobic cavernous body, the super-hydrophobic cavernous body has the preferable advantage of hydrophobic effect.Skill to be solved by this invention
The two of art problem are to provide a kind of preparation method with the corresponding super-hydrophobic cavernous body of one of technical problem that is solving.
One of to solve the above problems, the technical solution adopted by the present invention is as follows：A kind of super-hydrophobic cavernous body, the nanometer
Modifying agent is by the way that nano material is dissolved in hydrophobic silicones compound ingredients, and stirring is obtained to after being completely dissolved；Wherein,
The nano material is selected from carbon-based, copper race Metal Substrate, the nano particle of copper family metal oxide or silica, nano wire or received
Rice band；The hydrophobic silicones compound ingredients is being selected from dimethyl silicone polymer and octamethylcy-clotetrasiloxane curing agent just
Hexane or ethyl acetate mixture, or fluorine containing silane ethanol solution.
In above-mentioned technical proposal, it is preferable that the cavernous body is melamine sponge or polyurethane sponge, carbon-based nano material
Material particle is CNT, carbon nano-fiber, graphene；Copper race metal-based nano particle is nano silver wire/rod, silver nanoparticle
Grain, copper nano-wire, copper nano particles；Copper family metal oxide is nano wire, the nanobelt of cuprous oxide or cupric oxide.
In above-mentioned technical proposal, it is preferable that the mass ratio of nano material and hydrophobic silicones compound ingredients is 0.05
~0.2；The mass ratio of dimethyl silicone polymer and octamethylcy-clotetrasiloxane curing agent is 5~10；Dimethyl silicone polymer with
The compound proportion of nano material is 1~6；Silicon fluoride and the mass ratio of nano material are 0.25~1；Fluorine containing silane ethanol solution
Concentration is 3mg/mL~8mg/mL；Mixing time>4 hours.
For solve the above problems two, the technical solution adopted by the present invention is as follows：A kind of preparation side of super-hydrophobic cavernous body
Method, comprises the following steps：
(1) by the cavernous body supersound washing in deionized water, absolute ethyl alcohol respectively, then it is impregnated in acid solution quarter
Erosion, drains and is placed in the dry for standby in drying box；
(2) nano modifier is prepared；
(3) the dried cavernous body for obtaining step (1) is immersed in the nano modifier in step (2), at least
Drying is taken out after 30min；
(4) hardened at a temperature of dried cavernous body sample being placed in into 120~200 DEG C, obtain super-hydrophobic sponge material.
In above-mentioned technical proposal, it is preferable that acid solution is hydrochloric acid solution, chromic acid solution or chromic acid/sulfuric acid mixed liquor.
In above-mentioned technical proposal, it is preferable that the supersound washing time in step (1)>15 minutes；Etching is with acid strength
1M, etch period is 10~30 minutes, cavernous body drying time ＞ 1 hour after etching, and drying temperature is 60~80 DEG C.
In above-mentioned technical proposal, it is preferable that step is dried at room temperature in (3), drying time>3 hours.
In above-mentioned technical proposal, it is preferable that firm time is>2 hours.
On the one hand the purpose of the present invention is a kind of based on super-hydrophobic oleophylic nanometer surface and interface to obtain, available for spill response
The material of control, is on the other hand that, to solve the technological problemses that commercial oil absorption material synthetic method complexity, cost are high, proposition is a kind of
Simple infusion process is only needed to produce hydrophobic, high oil absorption multiplying power cavernous body modification method for preparing.It is proposed by the present invention extra large based on commercialization
The preparation method of continuous (melamine sponge, polyurethane sponge etc.), using commercial sponge block as substrate, is etched by acidic liquid,
Applying the self-control modifiers such as n-hexane (or ethyl acetate) solution of leaching containing nano particle or nano wire and obtaining has nanometer table circle
Face and the sponge material of special wetting characteristics.The hydrophobic carbon adsorbing material preparation method that this patent is proposed is simple, and product is dredged
Aqueous, recycling performance and demulsification ability are excellent, and are easy to reclaim Reusability, can be mass-produced, contribute to production
Product prepare the conversion to commercial Application from laboratory.Modified sponge body material produced by the invention has good ultra-hydrophobicity
(angle of wetting>153 °), by acid etching and the micro-roughened surface produced by the load of nano material, can there is air
In in nanometer channel, air film blocks the contact between drop and the surface of solids, produces super-hydrophobic effect.At the same time, by institute
Prepared material can greatly reduce the radial distance of cavernous body free internal space via simple compression, produce excellent breaking
Can, achieve preferable technique effect.
Brief description of the drawings
Fig. 1 be the gained sponge material surface of embodiment 1 before modified after SEM (SEM) characterization result；
Fig. 2 is modified cavernous body product and water drop contact photo in embodiment 1；
Fig. 3 is the experimental result that the products obtained therefrom of embodiment 1 is positioned in water body；
Fig. 4 is that the product that embodiment 1 is obtained is combined the reality that the quick adsorption in 25 seconds reclaims oil slick with self priming pump
Passport control examination of passports piece；
Fig. 5 is to be immersed in water body that good water-resisting ability can be kept after the made sample of embodiment 1 is combined with self priming pump
Experiment photo；
Fig. 6 removes the stereoscopic aobvious of situation for micron order oil droplet in water body before and after product treatment oil-water emulsion in embodiment 1
Micro mirror observes result.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Embodiment
【Embodiment 1】
(1) first, by melamine sponge supersound washing 15 minutes in deionized water and absolute ethyl alcohol respectively, it is placed on
It is placed in being cut into 4 × 4 × 4cm after drying 1 hour in 80 DEG C of baking ovens in stainless steel pallet3Fritter is standby；
(2) then cavernous body is impregnated in 1M hydrochloric acid solution 30 minutes, then cleaned with deionized water to washing lotion pH
=7, taking-up is placed in 80 DEG C of baking ovens and dried 3 hours；
(3) 2 grams of hydrophobicity aerosil nano particles are weighed, 7 grams of PDMS, 1.2 grams of OMCTS curing agent are dissolved in
In 200 milliliters of n-hexanes, it is positioned over single-necked flask and is extremely dissolved within 6 hours with puddler mechanical agitation；
(4) take out the solution prepared to pour into beaker, sponge fritter is impregnated wherein 30 minutes；
(5) sponge fritter is put in stainless steel pallet, at room temperature aeration-drying 3 hours；
(6) the sponge fritter obtained after drying is placed in 120 DEG C of baking ovens and heats 6 hours, finally gives product hydrophobicity sea
It is continuous.
Fig. 1 be the gained sponge material surface of embodiment 1 before modified after SEM (SEM) characterize, by right
Than the two internal three-dimensional porous structure all for crosslinking net of display, wherein macropore diameter scope is 50~400 μm.But without
The fiber surface of modified sample is smooth, and the concavo-convex fold constituted by modified sample surfaces by a large amount of nano particles
Covered, cause roughness to be substantially improved；
Fig. 2 is modified cavernous body product and water drop contact photo in embodiment 1, shows its surface and the infiltration angle of water>
150 °, with very strong hydrophobic property；
Fig. 3 shows that the products obtained therefrom of embodiment 1 is positioned in water body and can swum on the water surface, is immersed in surface in water body and shows
Existing glittering air film, it was demonstrated that the air film of the nanometer channel entrainment of material body surface and interface formation can effectively obstruct water body and enter sea
In continuous body space；
Fig. 4 is that the product that embodiment 1 is obtained is combined the reality that the quick adsorption in 25 seconds reclaims oil slick with self priming pump
Passport control examination of passports piece, it was demonstrated that resulting materials have stronger oil-wet behavior；
Fig. 5 is to be immersed in water body that good water-resisting ability can be kept after the made sample of embodiment 1 is combined with self priming pump
Experiment photo, further testimonial material has good hydrophobicity；
Fig. 6 removes the stereoscopic aobvious of situation for micron order oil droplet in water body before and after product treatment oil-water emulsion in embodiment 1
Micro mirror observes result, it was demonstrated that material has excellent demulsification ability.
【Embodiment 2】
(1) first, by melamine sponge supersound washing 20 minutes in deionized water and absolute ethyl alcohol respectively, it is placed on
It is placed in being cut into 1 × 1 × 1cm after drying 1 hour in 60 DEG C of baking ovens in stainless steel pallet3Fritter is standby；
(2) then cavernous body is impregnated in 1M chromic acid solution 30 minutes, then cleaned with deionized water to washing lotion pH
=7, taking-up is placed in 80 DEG C of baking ovens and dried 3 hours；
(3) 0.4 gram of nanometer silica line is weighed, 2 grams of PDMS, 0.4 gram of curing agent is dissolved in 60 milliliters of ethyl acetate,
It is positioned over single-necked flask and is extremely dissolved within 4 hours with puddler mechanical agitation；
(4) sponge fritter is impregnated in modified solution 2 hours, while being placed in ultrasonic disperse in ultrasonic cleaning machine；
(5) sponge fritter is put in stainless steel pallet, at room temperature aeration-drying 3 hours；
(6) the sponge fritter obtained after drying is placed in 150 DEG C of baking ovens and hardens 4 hours, finally gives product hydrophobicity sea
It is continuous.
The surface and interface microtexture of gained sample has close coarse structure with sample in embodiment 1, its hydrophobic test
As a result show same excellent hydrophobic property, with reference to same model self priming pump formed the oil-water separation of system also with reality
The products obtained therefrom of example 1 is similar.
【Embodiment 3】
(1) first, by polyurethane sponge supersound washing 15 minutes in deionized water and absolute ethyl alcohol respectively, it is placed on not
It is placed in being cut into 4 × 4 × 4cm after drying 1 hour in 70 DEG C of baking ovens in rust steel tray3Fritter is standby；
(2) then cavernous body is impregnated in 1M chromic acid/sulfuric acid solution 1 hour, then cleaned with deionized water to washing
Liquid pH=7, taking-up is placed in 80 DEG C of baking ovens and dried 3 hours；
(3) 2 grams of hydrophobicity aerosil nano particles, 12 grams of PDMS are weighed, 1.2 grams of curing agent are dissolved in 200 millis
Rise in n-hexane, be positioned over single-necked flask and extremely dissolved within 5 hours with puddler mechanical agitation；
(4) take out the solution prepared to pour into beaker, sponge fritter is impregnated wherein 30 minutes, taking-up is placed at room temperature
Drying 3 hours, the process is repeated 3 times；
(5) the sponge fritter that last time is infiltrated after being modified and drying is placed in 120 DEG C of baking ovens and heats 6 hours, finally
Obtain product hydrophobicity sponge.
Gained sample hydrophobicity, oil and water separation capability etc. are similar with the products obtained therefrom of example 1.
【Embodiment 4】
(1) first, by melamine sponge, supersound washing removes table in 15 minutes in deionized water and absolute ethyl alcohol respectively
Face pollutant that may be present, be placed in stainless steel pallet be placed in 80 DEG C of baking ovens dry 1 hour after be cut into 4 × 4 × 4cm3
Fritter is standby；
(2) then cavernous body is impregnated in 1M hydrochloric acid solution 1 hour, then cleaned with deionized water to washing lotion pH=
7, taking-up is placed in 80 DEG C of baking ovens and dried 3 hours；
(3) 10 grams of PDMS are weighed, 1 gram of curing agent is dissolved in 200 milliliters of n-hexanes, be positioned over single-necked flask and with stirring
Bar mechanical agitation 4 hours；
(4) take out the solution prepared to pour into beaker, sponge fritter is impregnated wherein 12 hours, taking-up is placed at room temperature
Ventilation 5 hours；
(5) modified sponge fritter is placed in 200 DEG C of baking ovens and heats 2 hours, finally give product hydrophobicity sponge.
Gained sample hydrophobicity, oil and water separation capability etc. are similar with the products obtained therefrom of example 1.
【Embodiment 5】
(1) first, by polyurethane sponge, supersound washing removes surface in 15 minutes in deionized water and absolute ethyl alcohol respectively
Pollutant that may be present, be placed in stainless steel pallet be placed in 80 DEG C of baking ovens dry 1 hour after be cut into 4 × 4 × 4cm3It is small
Block is standby；
(2) then cavernous body is impregnated in 1M hydrochloric acid solution 1 hour, then cleaned with deionized water to washing lotion pH=
7, taking-up is placed in 80 DEG C of baking ovens and dried 3 hours；
(3) 2 grams of super-hydrophobic silica nano particles are weighed, 0.6 gram of silicon fluoride is dissolved in 200 milliliters of ethanol, magneton
Stirring 4 hours；
(4) sponge fritter is impregnated in modified solution 24 hours, taking-up is placed in divulges information 5 hours at room temperature, finally obtains
Super-hydrophobic cavernous body product
Gained sample hydrophobicity, oil and water separation capability etc. are similar with the products obtained therefrom of example 1.
【Embodiment 6】
(1) first, by melamine sponge, supersound washing removes table in 15 minutes in deionized water and absolute ethyl alcohol respectively
Face pollutant that may be present, be placed in stainless steel pallet be placed in 80 DEG C of baking ovens dry 1 hour after be cut into 4 × 4 × 4cm3
Fritter is standby；
(2) then cavernous body is impregnated in 1M chromic acid solution 1 hour, then cleaned with deionized water to washing lotion pH=
7, taking-up is placed in 80 DEG C of baking ovens and dried 3 hours；
(3) 2 grams of super-hydrophobic silica nano particles are weighed, 2 grams of silicon fluorides are dissolved in 200 milliliters of ethanol, and magneton is stirred
Mix 6 hours and ultrasonically treated；
(4) sponge fritter is impregnated in modified solution 10 hours, taking-up is placed in dries 3 hours at room temperature, the process weight
It is multiple 3 times, finally give super-hydrophobic cavernous body sample.
Gained sample hydrophobicity, oil and water separation capability etc. are similar with the products obtained therefrom of example 1.
【Embodiment 7】
Under optimum controlling condition, the contact angle that modified sponge body material prepared by embodiment 1-6 enters water-filling is tested, it is determined that
Its superhydrophobic property, as shown in table 1, present invention design preparation method resulting materials are respectively provided with superhydrophobic characteristic：
Table 1
| Embodiment | The contact angle of water |
| 1 | 153.7° |
| 2 | 156.8° |
| 3 | 153.2° |
| 4 | 154.6° |
| 5 | 155.3° |
| 6 | 154.9° |
【Embodiment 8】
(1) first, by melamine sponge supersound washing 15 minutes in deionized water and absolute ethyl alcohol respectively, it is placed on
It is placed in being cut into 4 × 4 × 4cm after drying 1 hour in 80 DEG C of baking ovens in stainless steel pallet3Fritter is standby；
(2) then cavernous body is impregnated in 1M hydrochloric acid solution 30 minutes, then cleaned with deionized water to washing lotion pH
=7, taking-up is placed in 80 DEG C of baking ovens and dried 3 hours；
(3) 4 grams of fine copper nano wires are weighed, 7 grams of PDMS, 1.2 grams of OMCTS curing agent are dissolved in 200 milliliters of n-hexanes, put
It is placed in single-necked flask and is extremely dissolved within 6 hours with puddler mechanical agitation；
(4) take out the solution prepared to pour into beaker, sponge fritter is impregnated wherein 30 minutes；
(5) sponge fritter is put in stainless steel pallet, at room temperature aeration-drying 3 hours；
(6) the sponge fritter obtained after drying is placed in 120 DEG C of baking ovens and heats 6 hours, finally gives product hydrophobicity sea
It is continuous.
Copper red color is presented in gained color sample, with the hydrophobic similar temperament of gained sample of embodiment 1, can be suspended in water body and realize
The function such as oil slick adsorption recovery and water-oil separating.
【Embodiment 9】
(1) first, by polyurethane sponge, supersound washing removes surface in 15 minutes in deionized water and absolute ethyl alcohol respectively
Pollutant that may be present, be placed in stainless steel pallet be placed in 80 DEG C of baking ovens dry 1 hour after be cut into 4 × 4 × 4cm3It is small
Block is standby；
(2) then cavernous body is impregnated in 1M hydrochloric acid solution 1 hour, then cleaned with deionized water to washing lotion pH=
7, taking-up is placed in 80 DEG C of baking ovens and dried 3 hours；
(3) 2 grams of cuprous oxide over-expense nanostructured powders are weighed, 0.6 gram of silicon fluoride is dissolved in 200 milliliters of ethanol, magnetic
Son stirring 4 hours；
(4) sponge fritter is impregnated in modified solution 24 hours, taking-up is placed in divulges information 5 hours at room temperature, finally obtains
Super-hydrophobic cavernous body product.
Gained sample hydrophobicity and oil and water separation capability and embodiment 1 are similar.
【Embodiment 10】
(1) first, by polyurethane sponge, supersound washing removes surface in 15 minutes in deionized water and absolute ethyl alcohol respectively
Pollutant that may be present, be placed in stainless steel pallet be placed in 80 DEG C of baking ovens dry 1 hour after be cut into 4 × 4 × 4cm3It is small
Block is standby；
(2) then cavernous body is impregnated in 1M hydrochloric acid solution 1 hour, then cleaned with deionized water to washing lotion pH=
7, taking-up is placed in 80 DEG C of baking ovens and dried 3 hours；
(3) 2 grams of nano silver wire powders are weighed, 7 grams of PDMS, 1.2 grams of OMCTS curing agent are dissolved in 200 milliliters of ethyl acetate
In, magneton is stirred 6 hours；
(4) sponge fritter is impregnated in modified solution 24 hours, taking-up is placed in divulges information 5 hours at room temperature, then is positioned over
Hardened 6 hours in 120 DEG C of baking ovens, finally obtain super-hydrophobic cavernous body product.
Gained sample hydrophobicity and oil and water separation capability and embodiment 1 are similar.
【Embodiment 11】
(1) first, by polyurethane sponge, supersound washing removes surface in 15 minutes in deionized water and absolute ethyl alcohol respectively
Pollutant that may be present, be placed in stainless steel pallet be placed in 80 DEG C of baking ovens dry 1 hour after be cut into 4 × 4 × 4cm3It is small
Block is standby；
(2) then cavernous body is impregnated in 1M hydrochloric acid solution 1 hour, then cleaned with deionized water to washing lotion pH=
7, taking-up is placed in 80 DEG C of baking ovens and dried 3 hours；
(3) 2 grams of nano cuprous oxide wires are weighed, 0.6 gram of silicon fluoride is dissolved in 200 milliliters of ethanol, magneton stirring 4 is small
When；
(4) sponge fritter is impregnated in modified solution 24 hours, taking-up is placed in divulges information 5 hours at room temperature, finally obtains
Super-hydrophobic cavernous body product.
Gained sample hydrophobicity and oil and water separation capability and embodiment 1 are similar.
【Embodiment 12】
Under optimum controlling condition, the contact angle that modified sponge body material prepared by embodiment 8-11 enters water-filling is tested, really
Its fixed superhydrophobic property, as shown in table 1, present invention design preparation method resulting materials are respectively provided with superhydrophobic characteristic：
Table 2
| Embodiment | The contact angle of water |
| 8 | 155.3° |
| 9 | 151.6° |
| 10 | 150.7° |
| 11 | 154.9° |
Obviously, above-described embodiment, just to illustrate the validity and practicality of the preparation method, is not to embodiment party
The restriction of formula, such as base material use commercial sponge in the invention, naturally it is also possible to be changed to stainless (steel) wire, copper mesh,
Other various forms of changes of filter membrane (paper), polyester textile etc., are carried out there is no need and unable to be directed to various embodiments one by one
Exhaustion, and the obvious changes or variations thus amplified is in scope of patent protection of the present invention.
Claims (8)
1. a kind of super-hydrophobic cavernous body, including cavernous body and nano modifier, the nano modifier passes through nano material is molten
Solution is in hydrophobic silicones compound ingredients, and stirring is obtained to after being completely dissolved；Wherein, the nano material be selected from it is carbon-based,
Nano particle, nano wire or the nanobelt of copper race Metal Substrate, copper family metal oxide or silica；The hydrophobic silicones
Compound ingredients is selected from dimethyl silicone polymer and n-hexane or the ethyl acetate mixing of octamethylcy-clotetrasiloxane curing agent are molten
Liquid, or fluorine containing silane ethanol solution.
2. super-hydrophobic cavernous body according to claim 1, it is characterised in that the cavernous body is melamine sponge or poly- ammonia
Ester sponge, c-based nanomaterial particle is CNT, carbon nano-fiber, graphene；Copper race metal-based nano particle is received for silver
Rice noodles/rod, silver nano-grain, copper nano-wire, copper nano particles；Copper family metal oxide is the nanometer of cuprous oxide or cupric oxide
Line, nanobelt.
3. super-hydrophobic cavernous body according to claim 1, it is characterised in that nano material is matched somebody with somebody with hydrophobic silicones compound
The mass ratio of agent is 0.05~0.2；The mass ratio of dimethyl silicone polymer and octamethylcy-clotetrasiloxane curing agent is 5~10；
Dimethyl silicone polymer and the compound proportion of nano material are 1~6；Silicon fluoride and the mass ratio of nano material are 0.25~1；Contain
The concentration of silicon fluoride ethanol solution is 3mg/mL~8mg/mL；Mixing time>4 hours.
4. the preparation method of super-hydrophobic cavernous body as claimed in claim 1, comprises the following steps：
(1) by the cavernous body supersound washing in deionized water, absolute ethyl alcohol respectively, acid solution etching is then impregnated in,
Drain and be placed in the dry for standby in drying box；
(2) nano modifier is prepared；
(3) the dried cavernous body for obtaining step (1) is immersed in the nano modifier in step (2), after at least 30min
Take out drying；
(4) hardened at a temperature of dried cavernous body sample being placed in into 120~200 DEG C, obtain super-hydrophobic sponge material.
5. the preparation method of super-hydrophobic cavernous body according to claim 1, it is characterised in that acid solution is hydrochloric acid solution, chromium
Acid solution or chromic acid/sulfuric acid mixed liquor.
6. the preparation method of super-hydrophobic cavernous body according to claim 1, it is characterised in that during supersound washing in step (1)
Between>15 minutes；Etching is 1M with acid strength, and etch period is 10~30 minutes, and cavernous body drying time ＞ 1 is small after etching
When, drying temperature is 60~80 DEG C.
7. the preparation method of super-hydrophobic cavernous body according to claim 1, it is characterised in that step is done at room temperature in (3)
It is dry, drying time>3 hours.
8. the preparation method of super-hydrophobic cavernous body according to claim 1, it is characterised in that firm time is>2 hours.
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