CN107974089B

CN107974089B - Preparation of isotropic super-hydrophobic super-oleophobic regular porous silicone rubber through anisotropic structure

Info

Publication number: CN107974089B
Application number: CN201711375447.7A
Authority: CN
Inventors: 何周坤; 喻永连; 杨建�; 唐昶宇; 梅军; 李秀云
Original assignee: Chengdu Science and Technology Development Center of CAEP
Current assignee: Chengdu Science and Technology Development Center of CAEP
Priority date: 2017-12-19
Filing date: 2017-12-19
Publication date: 2020-08-25
Anticipated expiration: 2037-12-19
Also published as: CN107974089A

Abstract

The invention discloses a method for preparing an isotropic super-hydrophobic and super-oleophobic silicone rubber material through an anisotropic structure, which comprises the following steps: (1) uniformly mixing silicone oil containing C = C double bonds, inorganic nano filler, catalyst and inhibitor to obtain a first mixture, (2) adding hydrogen-containing silicone oil and silicone rubber additive into the first mixture prepared in the step 1, uniformly mixing to obtain a second mixture, and defoaming to obtain printing ink; (3) filling the ink into a 3D printer, and printing according to the anisotropic porous structure characteristics to prepare the porous silicon rubber; (4) and (3) carrying out pre-curing treatment, then carrying out dip-coating and drying in a treating agent solution, then carrying out super-thermal hydrogen treatment, taking out and cleaning, and drying again to obtain the isotropic super-hydrophobic and super-oleophobic silicone rubber material. According to the invention, the silicon rubber and the inorganic nano filler are combined, and 3D printing is utilized to realize organic combination of physical structure and material characteristics, so that the isotropic super-hydrophobic super-oleophobic silicon rubber is prepared.

Description

Preparation of isotropic super-hydrophobic super-oleophobic regular porous silicone rubber through anisotropic structure

Technical Field

The invention belongs to the field of super-hydrophobic and super-oleophobic porous silicon rubber, and particularly relates to an isotropic super-hydrophobic and super-oleophobic silicon rubber material directly prepared by 3D printing of an anisotropic structure. Meanwhile, the silicon rubber material has excellent mechanical stability and porous super-hydrophobic and super-oleophobic characteristics, and the silicon rubber preparation method is provided.

Background

The wettability of a material surface is generally determined by the physical structure and chemical composition of the material surface, and can be divided into isotropic wettability and anisotropic wettability according to whether the physical structure and/or chemical composition are consistent in different directions. Here, isotropic wettability means that wettability of a material surface in different directions is the same, and usually an isotropic physical structure and an isotropic chemical composition are required to achieve isotropic wettability, and if either or both of the physical structure and the chemical composition are anisotropic characteristics, the surface is usually caused to be anisotropic wettability. Anisotropic wettability is the wettability of the material surface which is different in different directions, and the phenomenon has such specificity on the organ surfaces of many natural plants or animals in nature. For example, a water droplet on the surface of a butterfly wing easily rolls from the root to the edge and slides off, but does not easily roll backwards, mainly because of the anisotropy of the physical structure of the surface. Meanwhile, the design and preparation of the anisotropic wettability of the surface can be realized by carrying out anisotropic modification treatment on the chemical composition of the surface without changing the physical structure of the surface.

The anisotropic physical structure has wide application prospects in the fields of micro fluid equipment, liquid patterning devices, condensation heat exchange equipment, fluid drag reduction, cell oriented culture, tissue engineering application and the like, but the surfaces of the anisotropic physical structures often need isotropic wettability to meet the functions of water resistance, pollution resistance, self cleaning and the like of the surfaces, and the basic concept of the anisotropic wettability caused by the traditional anisotropic physical structure is contradictory, so that the common anisotropic physical structure is difficult to meet the requirement of the isotropic wettability. Therefore, the anisotropic physical structure needs to be precisely regulated and controlled, and the influence of the anisotropic physical structure on the surface wettability is reduced, so that the design and the preparation of the isotropic wettability of the surface of the anisotropic physical structure are realized by combining the isotropic chemical composition of the surface. The general construction method of anisotropic physical structures comprises: ferrofluid templating (adv. funct. mater.2015,25, 2670-. However, these methods have the disadvantages that it is difficult to precisely control the surface anisotropic physical structure due to the fact that the template needs anisotropic template and the structure is fixed by the template fixing, and the like, and the preparation of templates with different anisotropic physical structures needs special methods, and has the disadvantages of complex process, high cost, easy damage and large loss of the template, and the like.

The 3D printing technology can design required patterns through a computer and then output the patterns to printing equipment to directly form various complex structural characteristics, a template is not needed in the printing process, and the structural characteristics can be conveniently controlled through a computer program to obtain ideal designs of various complex structures (CN 103854844A; CN 104441091A). In our previous work (CN105818378A), we have conducted a preliminary search for anisotropic silicone foam structure, and solved the problem of poor structure, size and uniformity of cells in the conventional silicone rubber foam products. Therefore, the design and preparation of the surface anisotropic physical structure can be well realized through 3D printing preparation of the silicon rubber, but related work in the prior art mainly realizes the control of the anisotropic wettability caused by the more traditional anisotropic physical structure, so that the design and preparation of the surface isotropic wettability of the anisotropic physical structure are realized through the design of the silicon rubber printing ink material, the optimized design of the printing process and the surface chemical composition control in the later period.

Disclosure of Invention

The invention aims to overcome the defects that the surface of the surface material with the anisotropic structure in the prior art is anisotropic wettability, is not beneficial to further improving the material performance and limits the application range of a reinforcing material, and provides a silicon rubber material with an anisotropic physical structure but isotropic super-hydrophobic and super-oleophobic properties.

In order to achieve the above purpose, the invention provides the following technical scheme:

a method for preparing an isotropic super-hydrophobic and super-oleophobic silicon rubber material through an anisotropic structure comprises the following steps:

(1) uniformly mixing silicone oil containing C ═ C double bonds, inorganic nano filler, catalyst and inhibitor to obtain a first mixture, wherein one or more of ball milling, grinding or mechanical stirring is adopted in the mixing process.

(2) And (3) adding hydrogen-containing silicone oil and a silicone rubber auxiliary agent into the first mixture prepared in the step (1), and uniformly mixing to obtain a second mixture. And defoaming the second mixed material to obtain the printing ink.

(3) And (3) filling the 'ink' prepared in the step (2) into a 3D printer, and printing according to the anisotropic porous structure characteristics to prepare the silicon rubber with the porous structure.

(4) And (4) carrying out pre-curing treatment on the silicon rubber with the porous structure prepared in the step (3). And then, dip-coating the porous silicon rubber in a treating agent solution, drying, carrying out super-thermal hydrogen treatment, taking out, cleaning and drying again to obtain the isotropic super-hydrophobic and super-oleophobic silicon rubber material.

According to the preparation method of the isotropic super-hydrophobic and super-oleophobic silicone rubber material, a 3D printer is adopted to print according to anisotropic structure characteristics, a microstructure has an anisotropic physical structure, and the surface micro-roughening change of the anisotropic structure is realized by combining the reinforcing effect of the inorganic nano filler and the pre-curing treatment after the printing is finished, so that the isotropic super-hydrophobic and super-oleophobic characteristic is finally achieved. The inorganic nano filler is uniformly mixed in the silicon rubber in advance, a microcosmic rough shape is formed on the surface of the silicon rubber in a pre-curing process, and firm combination is realized after final curing treatment, so that the obtained material fully exerts the dual characteristics of the inorganic nano filler and the silicon rubber and is matched with the microcosmic rough characteristic on the surface of the silicon rubber to realize isotropic super-hydrophobic and super-oleophobic property. Due to the fact that the anisotropic structure is prepared through 3D printing, the overall structure of the material has the characteristics of regularity and porosity, and the material has flexibility, so that the material has excellent mechanical damage resistance.

Further, the silicone oil containing a double bond of C ═ C is one or more of vinyl silicone oil, divinyl silicone oil, methyl vinyl silicone oil, hydroxy vinyl silicone oil, phenyl vinyl silicone oil, tolyl vinyl silicone oil, benzylidene vinyl silicone oil, methylphenyl vinyl silicone oil, and methyl vinyl trifluoropropyl silicone oil. The silicone oil has natural hydrophobicity and flexibility as a base material, and can deform to offset the external destructive effect under the mechanical action, so that the comprehensive super-hydrophobic and super-oleophobic property of the material after the anisotropic structure is formed can be better enhanced.

Preferably, the mass fraction of the silicone oil containing C ═ C double bonds added into the silicone rubber is 20.0-40.0%. And (3) determining the addition proportion of the silicone oil containing C-C double bonds in the raw material according to the mass fraction calculation of the raw material components for preparing the silicone rubber.

Further, the inorganic nano filler is one or more of silicon dioxide, calcium silicate, calcium carbonate, titanium dioxide, carbon black, graphene, carbon nano tube, montmorillonite and zinc oxide.

Preferably, the particle size of the inorganic nano filler is 1-5000 nm, and the particle size of the nano filler is 5-500 nm.

Preferably, the mass fraction of the inorganic nano filler added into the silicone rubber is 1.0-50.0%. The mass ratio of the finished product of the silicon rubber to the inorganic nano-filler in the raw material is calculated, and the inorganic nano-filler is planned and combined into the silicon rubber after the silicon rubber is formed to form a stable combination state.

Preferably, the inorganic nanofiller is pretreated as follows: the coupling agent with the mass concentration of 0.1-5.0% is adopted to be soaked for 5-60min, and then the drying is carried out for 5-60min at the temperature of 20-90 ℃. The surface property of the inorganic nano filler is enhanced and improved through the pretreatment of the coupling agent, so that the inorganic nano filler can be better mixed and dispersed with the silicon rubber material to form a uniformly distributed and combined mixed material, and can be dispersed to the surface of a silicon rubber line in the 3D printing process, thereby facilitating the realization of a micro roughened structure on the surface of a 3D printing structure in the subsequent pre-curing treatment.

Preferably, the coupling agent is an alkane coupling agent or a titanate coupling agent.

Preferably, the coupling agent is one or more of 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, bis (dioctyloxypyrophosphate) ethylene titanate and isopropyltris (dioctylpyrophosphate) titanate. The coupling agent has good affinity, can better combine and realize the effect of uniformly dispersing the inorganic nano filler and the silicon rubber, and meets the advantage of improving the isotropy of the silicon rubber material.

Further, the catalyst is a platinum catalyst.

Preferably, the catalyst is one or more of Dow Corning RD27 platinum catalyst, DX-3080 platinum catalyst of Guangzhou Daxi chemical raw material Co., Ltd, MC-999 platinum catalyst of Miteng rubber and plastic material Co., Ltd, platinum catalyst of Zhongxin organic silicon material Co., Ltd, Dongguan city, and PT-50 of Tian Eucalypti silica gel technology Co., Ltd, Dongguan city.

Preferably, the mass fraction of the catalyst added into the silicone rubber is 0.001-0.5%.

Further, the inhibitor is an alkynyl-containing inhibitor.

Preferably, the inhibitor is one or more of 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 3-butyn-1-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3,7, 11-trimethyldodecyn-3-ol.

Preferably, the mass fraction of the inhibitor added into the silicone rubber is 0.001-0.5%.

Further, in step 1, the mixing process is realized by one of ball milling, grinding or mechanical stirring, and the specific process parameters are as follows:

the parameters of ball milling and mixing are that the revolution is 50-400 r/min, the rotation is 100-800 r/min, and the time is 20-60 min.

The parameters of grinding and mixing are 30-3000 r/min, and the time is 30-60 min.

The mechanical stirring parameter is 100-3000 r/min, and the time is 30-60 min.

The parameter conditions in the mixing process are optimized, so that the mixing effect of the silicon rubber raw material and the inorganic nano filler is better, the silicon rubber raw material and the inorganic nano filler are fully mixed, and the adverse effect of the silicon rubber property caused by excessive ball milling, grinding or mechanical stirring is avoided.

Further, the hydrogen-containing silicone oil is silicone oil containing Si-H groups, and the mass fraction of hydrogen content is 0.1-2.0%.

Preferably, the silicone oil containing Si-H groups is added into the silicone rubber at a mass fraction of 20.0-40.0%. The dosage of the hydrogen-containing silicone oil is calculated according to the mass ratio of the silicone oil containing Si-H groups in the raw material to the finished silicone rubber product.

Further, the silicon rubber auxiliary agent is one or more of polytetrafluoroethylene, polyvinylidene fluoride, 1H,2H, 2H-perfluorooctyltrimethoxysilane, 1H,2H, 2H-perfluorooctyltriethoxysilane, 1H,2H, 2H-perfluorodecyltrimethoxysilane and 1H,1H,2H, 2H-perfluorodecyltriethoxysilane. The suitable silicone rubber additive can effectively improve the conveying efficiency and the demolding property of the silicone rubber in the 3D printing process, and is favorable for controlling the printing morphology. After the silicone rubber is printed and formed, the wear resistance of the silicone rubber foam material can be enhanced, so that the silicone rubber foam material can keep good structural stability in a severe mechanical wear environment.

Preferably, the mass fraction of the silicone rubber auxiliary agent added into the silicone rubber is 5.0-20.0%.

Further, in the step 2, one or more of ball milling, grinding or mechanical stirring is adopted in the mixing process.

Preferably, step 2, the mixing process is the same as step 1, and the materials are directly added and mixed by using the mixing device or equipment in step 1. For example, ball milling and mixing are adopted in the step 1, then hydrogen-containing silicone oil and silicone rubber auxiliary agents are directly added into the ball milling device in the step 2, and then ball milling treatment is continued to obtain a second uniformly mixed material.

Further, step 2, the process control parameters of the mixing process are as follows:

the parameters of ball milling and mixing are that the revolution is 50-400 r/min, the rotation is 100-800 r/min, and the time is 20-60 min;

the grinding and mixing parameters are 30-3000 r/min, and the time is 30-60 min;

the experimental condition of mechanical stirring is 100-3000 r/min, and the time is 30-60 min.

And 2, the control of the technological parameters of the mixing process in the step 1 is basically consistent, the control is convenient, the uniform dispersion of the hydrogen-containing silicone oil and the silicone rubber additive is facilitated, and the reagent can be ensured to be added to fully exert the expected effect.

Further, step 2, vacuum defoaming is adopted in the defoaming process. The second mixture obtained by mixing is easy to mix with air in the mixture due to the process characteristics of ball milling, grinding, mechanical stirring and the like adopted in the mixing process, so that the quality of 3D printing is influenced, and the materials are injected and printed. Preferably, the vacuum defoaming time is 30-240 min. The vacuum defoaming time in the range can ensure the defoaming quality and does not increase the cost of the defoaming process too much through the experimental study of the inventor.

Further, step 3, performing centrifugal deaeration before the second mixture is added into the 3D printer. Through further abundant desorption bubble of centrifugal deaeration, the high-speed high pressure can take off the micro-bubble in the mixture fast among the centrifugal process, is favorable to 3D to print the structure and is continuous. Preferably, the centrifugal defoaming rotating speed is 2000-10000 r/min, and the time is 5-60 min.

Preferably, step 3, tubing the "ink" and then printing with a 3D printer. Preferably, the "ink" contained in the tube is centrifuged, degassed and defoamed before printing. The tubulation that utilizes the 3D printer is centrifuged, both can centrifuge desorption vacuum defoamation in-process remaining bubble, can take off the bubble that the tubulation in-process newly appeared again, effectively guarantees the continuity that 3D printed "ink", promotes and prints the quality.

Further, step 3, the printing according to the anisotropic structure features is: the printing method comprises the steps of setting a printing multilayer structure, wherein each layer is formed by a plurality of mutually parallel lines, the lines of adjacent layers have a certain included angle, the included angle range is (0-90 degrees), the left-open and right-close interval is opened, the included angle cannot be 0 degrees but can be 90 degrees, the included angle of the lines of the adjacent layers is preferably 90 degrees, namely the lines of the adjacent layers are mutually perpendicular, the included angle between every two adjacent layers can be the same or different, preferably, the included angle range is [ 30-90 ] °, the lines of the odd layers and the lines of the even layers are mutually perpendicular in the most preferred condition, the lines printed in one layer are mutually parallel in the printing process, the angles are adjusted after the lines are printed, and then the next layer is printed.

Preferably, the distance between the inner lines of each layer is 0.5-3.0 mm. Through research of the inventor, when the printed internal line spacing is within the range, the promotion effect of the spatial three-dimensional structure on the super-hydrophobic and super-oleophobic property of the material can be fully exerted, and the super-hydrophobic and super-oleophobic property is realized.

Preferably, step 3, printing is performed according to the anisotropic structure characteristics, with the number of printing layers being 4-20, preferably 4-10. A silicone rubber composite material with good anisotropic structure by a multi-layer structural member.

Furthermore, the diameter of the printing needle head is controlled to be 0.1-2.0 mm. The silicon rubber printing structure is matched with the line space, a good porous structure is realized, and the silicon rubber printing structure is kept stable and has certain elasticity. Preferably, the line diameter of each layer may be the same or different.

Preferably, the distance between the plane where the lines of each layer are printed and the plane where the lines of the adjacent layer are positioned is controlled to be within the range of (0-50% ]) of the distance between the lines of each layer and the inner part of each layer, and the distance between the lines of the odd layer and the lines of the even layer are perpendicular to each other, the horizontal distance between the lines of the first layer and the third layer is within the range of the distance between the lines, and the distance between the lines of the other adjacent odd layer is within the same range of (0-50% ], and the horizontal distance between the lines of the second layer and the fourth layer is within the range of the distance between the lines, and the distance between the lines of the other adjacent even layer is within the same range of (0-50% ]).

Preferably, the vertical distance between the spacing layers is (0-50%) of the interval of the inner lines of each layer by regarding the structural surface of each layer as a horizontal plane.

Further, in the 3D printing process, the line printing speed is 0.2-25.0 mm/s.

Further, in step 4, the pre-curing process is as follows: and (3) placing the silicon rubber with the porous structure printed in the step (3) in a constant temperature and humidity environment for pre-curing, for example, placing the silicon rubber with the porous structure in a constant temperature and humidity box for curing, then carrying out dip-coating and drying on the porous silicon rubber in a treating agent solution, then carrying out super-thermal hydrogen treatment, taking out and cleaning, and drying again to obtain the isotropic super-hydrophobic and super-oleophobic silicon rubber material.

Preferably, in step 4, the pre-curing process is as follows: the silicon rubber is treated for 30-180min under the conditions that the temperature is 20-90 ℃ and the relative humidity is 20-100%. After the silicone rubber material with a porous structure is obtained by printing, a coarse structure with a smaller size of about several micrometers is further constructed on the surface of the printed line structure by utilizing micro water drops in the air of a constant-temperature and constant-humidity environment, so that the super-hydrophobic and super-oleophobic capability of the surface and the isotropy of a final product are improved.

Preferably, in the step 4, the mass fraction of the treating agent solution is 5.0-20.0%; the treating agent is one or more selected from polyvinylidene fluoride, methyl vinyl trifluoropropyl silicone rubber, 1H,2H, 2H-perfluorooctyl trimethoxy silane, 1H,2H, 2H-perfluorooctyl triethoxy silane, 1H,2H, 2H-perfluorodecyl trimethoxy silane and 1H,1H,2H, 2H-perfluorodecyl triethoxy silane. By adopting the coating of the treating agent and the super-thermal hydrogen treatment, the micro adverse effects of the printed multilayer structure on the compression of the bottom layer structure and the like under the action of gravity can be compensated, so that the wetting uniformity and stability of the whole porous silicon rubber from top to bottom and from outside to inside are realized, the anisotropic wettability difference caused by the anisotropic physical structure is further reduced, and the aim of improving the isotropy of the super-hydrophobic and super-oleophobic regular porous silicon rubber is fulfilled.

Preferably, in step 4, the solvent used in the treating agent solution is one or more of dimethylacetamide, toluene, xylene, methanol and ethanol.

Preferably, step 4, after the silicone rubber with the porous structure is subjected to pre-curing treatment, dip-coating the silicone rubber in a treating agent solution for 5-3600s, drying the silicone rubber at the temperature of 20-90 ℃ for 5-120min, then treating the silicone rubber in a super-thermal hydrogen device with the voltage of 100-300V and the vacuum degree of 0.05-0.15 Pa for 5-120 s, taking out the silicone rubber, soaking the silicone rubber in ethanol for 5-60min, and then drying the silicone rubber at the temperature of 20-90 ℃ for 5-60 min; and then soaking the mixture in deionized water for 5-60min, and then drying the mixture at the temperature of 20-90 ℃ for 5-60min to obtain the isotropic super-hydrophobic and super-oleophobic silicone rubber material.

Further, in step 4, the prepared silicone rubber material has the following characteristics: the contact angle of the water drops or the water-soluble liquid drops or the liquid drops on the porous silicon rubber reaches more than 150 degrees, the difference of the contact angles of the liquid drops on the surface of the porous silicon rubber in any two directions is less than 5 degrees, and the rolling angle of the liquid drops in any direction is less than 10 degrees, so that the super-hydrophobic and super-oleophobic characteristic is represented as isotropy.

Preferably, the water-soluble droplets include, but are not limited to, water-based paints, water-based inks, aqueous acid, base and salt solutions with a pH of 1-13, sweat, blood, urine, oil-in-water emulsions, or oil droplets include, but are not limited to, vegetable oils, animal oils, gasoline, diiodomethane droplets, cyclohexane droplets, n-heptane droplets, water-in-oil emulsions.

Further, in step 4, the prepared porous silicon rubber material has the following characteristics: after one or more of ultrasonic strong damage, 10000 mechanical bending damage or 10000 mechanical friction damage for 120min, the contact angle of the liquid drop can still reach more than 150 degrees, the difference of the contact angles of the liquid drop in any two directions on the surface of the porous silicon rubber is less than 5 degrees, and the rolling angle of the liquid drop in any direction is less than 10 degrees. Preferably, the contact angle of the water drop or the water-soluble liquid drop or the oil drop on the porous silicon rubber surface reaches more than 150 degrees, the difference of the contact angles of the liquid drop in any two directions on the porous silicon rubber surface is less than 5 degrees, and the rolling angle of the liquid drop in any direction is less than 10 degrees.

Compared with the prior art, the invention has the beneficial effects that:

1. the method for preparing the super-hydrophobic and super-oleophobic porous silicon rubber adopts a mode of combining the silicon rubber and the inorganic nano filler, and utilizes a 3D printing anisotropic structure to realize organic combination of a physical structure and material characteristics so as to achieve isotropic super-hydrophobic and super-oleophobic characteristics.

2. The isotropic super-hydrophobic and super-oleophobic porous silicon rubber material processed by the preparation method has the characteristics of high temperature resistance, foam porous structure, stable and reliable structure and difficult damage, and meets the requirement of long service life of the functional silicon rubber material.

3. The super-hydrophobic and super-oleophobic regular porous silicone rubber prepared by the method has the advantages of high temperature resistance, controllable cell structure, super-hydrophobic and super-oleophobic surface, flexibility, tensile deformation, strong mechanical friction resistance, light weight and the like.

4. The preparation method has the advantages of no template, no surface damage, good repeatability, easy obtainment of a large-area super-hydrophobic and super-oleophobic surface with a regular structure, strong universality, simple process, easy actual production, low production cost and the like.

5. The super-hydrophobic and super-oleophobic silicon rubber material can meet the practical application requirements of surface waterproof/anti-fouling, self-cleaning, low-cost polymer patterning templates and the like in the fields of buildings, ships, aerospace, microfluid preparation, biomedicine and the like.

Description of the drawings:

FIG. 1: contact angle of a droplet of aqueous hydrogen chloride solution having pH 2 in the 30 ℃ direction after 120min ultrasonic strong destruction of the sample surface was 154 ° (example 2)

FIG. 2: rolling behavior of aqueous sodium chloride solution droplet having pH 7 in 90 ℃ direction after 10000 mechanical bending failures on sample surface (example 3)

FIG. 3: optical photograph of surface morphology of sample surface after 10000 times mechanical bending failure (example 5)

FIG. 4: rolling behavior of n-heptane droplets in the 45 ℃ direction after 10000 mechanical abrasion failures on the sample surface (example 7)

FIG. 5: porous Silicone rubber print Path planning schematic (figures show the variation of the print sequence from layer 1 to layer 10, example 8)

FIG. 6: contact angle 151 ℃ in the 0 ℃ direction of a droplet of aqueous sodium hydroxide solution having a pH of 12 on the surface of a sample after 10000 mechanical disruptions (example 10)

Detailed Description

The present invention is described in detail below by way of examples, and it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.

Example 1:

preparation of coupling agent pretreated inorganic nanoparticles

The inorganic nanoparticles are pre-soaked for 5-60min by adopting a coupling agent with the mass concentration of 0.1-5.0%, and then dried for 5-60min at the temperature of 20-90 ℃ to prepare the coupling agent-treated inorganic nanoparticles. The specific preparation raw materials and parameters are as follows:

example 2:

preparation of isotropic super-hydrophobic and super-oleophobic silicone rubber material through anisotropic structure

(1) A first mixture was obtained by uniformly mixing 40.0 mass% vinyl silicone oil, 14.0 mass% filler No. 101 prepared in example 1, 0.5 mass% dow corning RD27 platinum catalyst, and 0.5 mass% 1-ethynyl-1-cyclohexanol inhibitor. The mixing process adopts the parameters of ball milling and mixing as revolution of 50r/min and rotation of 100r/min, and the time is 40 min.

(2) Adding 40.0 mass percent of silicon oil containing 2.0 mass percent of hydrogen and containing Si-H groups and 5.0 mass percent of polyvinylidene fluoride silicon rubber auxiliary agent into the first mixture prepared in the step 1, continuously and uniformly mixing, wherein the parameters of ball milling mixing are revolution of 50r/min, rotation of 100r/min and time of 60min, and thus obtaining a second mixture. And (4) defoaming the second mixed material in vacuum for 60min to obtain the printing ink. Note: the mass fraction is calculated according to the total mass of the preparation raw materials, the sum of the mass fractions of all the raw material components is 100%, the mass of the raw materials is calculated according to the total mass of the preparation silicon rubber material and is taken, and the following steps are carried out.

(3) And (3) loading the 'ink' prepared in the step (2) into a 3D printer, centrifuging and defoaming at 5000r/min for 10min, and printing layer by layer according to the anisotropic porous structure characteristics, wherein the line printing speed is 25.0 mm/s. The diameter of the printing needle head is set to be 0.3mm, each layer of lines are printed in parallel, and the line spacing is 0.6 mm. And after printing one layer, adjusting the angle to ensure that the included angle between every two adjacent layers is 90 degrees, wherein the included angle between every two adjacent layers is the same, and the distance between the plane where the lines of each layer are located and the plane where the lines of the adjacent layers are located is 50 percent of the distance between the lines inside each layer. A total of 19 layers were printed to prepare a silicone rubber having a porous structure.

(4) And (3) pre-curing the silicon rubber with the porous structure prepared in the step (3) for 180min under the conditions that the temperature is 30 ℃ and the relative humidity is 90%. Then dipping porous silicon rubber in a dimethylacetamide solution of a polyvinylidene fluoride treating agent with the mass fraction of 5.0% for 3600s, drying at the temperature of 90 ℃ for 10min, then treating in an hyperthermia hydrogen device with the voltage of 100V and the vacuum degree of 0.05Pa for 120s, taking out, soaking in ethanol for 10min, and then drying at the temperature of 90 ℃ for 10 min; then soaking the mixture in deionized water for 10min, and then drying the mixture for 10min at the temperature of 90 ℃ to prepare the isotropic super-hydrophobic and super-oleophobic silicone rubber material.

Example 3:

(1) The first mixture was obtained by uniformly mixing 35.0 mass% of divinyl silicone oil, 14.0 mass% of the filler No. 102 prepared in example 1, 0.5 mass% of DX-3080 platinum catalyst from Guangzhou large-sized chemical raw material Co., Ltd, and 0.5 mass% of 2-methyl-3-butyn-2-ol inhibitor. The mixing process adopts grinding mixing parameters of 100r/min and 60 min.

(2) And (2) adding 40.0 mass percent of silicon oil containing 1.5 mass percent of hydrogen and containing Si-H groups and 10.0 mass percent of 1H,1H,2H, 2H-perfluorooctyltrimethoxysilane silicon rubber auxiliary agent into the first mixture prepared in the step (1), continuously and uniformly mixing, and obtaining a second mixture by adopting grinding and mixing parameters of 100r/min and 60 min. And (4) defoaming the second mixed material in vacuum for 60min to obtain the printing ink.

(3) And (3) loading the 'ink' prepared in the step (2) into a 3D printer, centrifuging and defoaming at 2000r/min for 30min, and printing layer by layer according to the anisotropic porous structure characteristics, wherein the line printing speed is 15.0 mm/s. The diameter of the printing needle head is set to be 0.5mm, each layer of lines are printed in parallel, and the line spacing is 1.0 mm. And after printing one layer, adjusting the angle to ensure that the included angle between adjacent layers is 45 degrees, wherein the included angle between every two adjacent layers is the same, and the distance between the plane where the lines of each layer are located and the plane where the lines of the adjacent layers are located is 40 percent of the distance between the lines inside each layer. A total of 13 layers were printed to prepare a silicone rubber having a porous structure.

(4) And (3) pre-curing the silicon rubber with the porous structure prepared in the step (3) for 120min under the conditions that the temperature is 40 ℃ and the relative humidity is 80%. Then, dip-coating porous silicon rubber in a toluene solution of 8.0 mass percent of methyl vinyl trifluoropropyl silicon rubber treating agent for 2400s, drying at 80 ℃ for 30min, treating in an hyperthermia hydrogen device with the voltage of 100V and the vacuum degree of 0.1Pa for 60s, taking out, soaking in ethanol for 20min, and drying at 80 ℃ for 30 min; then soaking the mixture in deionized water for 20min, and then drying the mixture for 30min at the temperature of 80 ℃ to prepare the isotropic super-hydrophobic and super-oleophobic silicone rubber material.

Example 4:

(1) Uniformly mixing 35.0 mass percent of methyl vinyl silicone oil, 15.0 mass percent of the filler which is prepared in the example 1 and is numbered as 103, 0.25 mass percent of MC-999 platinum-gold catalyst of Miteng rubber and plastic materials Co., Ltd, Dongguan city and 0.25 mass percent of propargyl alcohol inhibitor to obtain a first mixture. The mechanical stirring parameter adopted in the mixing process is 500r/min, and the time is 50 min.

(2) Adding 35.0 mass percent of silicone oil containing 1.5 mass percent of hydrogen and containing Si-H groups and 14.5 mass percent of polytetrafluoroethylene silicone rubber auxiliary agent into the first mixture prepared in the step 1. And continuously and uniformly mixing the mixture for 60min by adopting mechanical stirring parameters of 500r/min to obtain a second mixture. And (4) defoaming the second mixed material in vacuum for 60min to obtain the printing ink.

(3) And (3) loading the 'ink' prepared in the step (2) into a 3D printer, centrifuging and defoaming at 8000r/min for 20min, and printing layer by layer according to the anisotropic porous structure characteristics, wherein the line printing speed is 10.0 mm/s. The diameter of the printing needle head is set to be 0.8mm, each layer of lines are printed in parallel, and the line spacing is 1.5 mm. And after printing one layer, adjusting the angle to ensure that the included angle between adjacent layers is 60 degrees, wherein the included angle between every two adjacent layers is the same, and the distance between the plane where the lines of each layer are located and the plane where the lines of the adjacent layers are located is 30 percent of the distance between the lines inside each layer. A total of 9 layers were printed to prepare a silicone rubber having a porous structure.

(4) And (3) pre-curing the silicon rubber with the porous structure prepared in the step (3) for 90min under the conditions that the temperature is 50 ℃ and the relative humidity is 70%. Then dip-coating porous silicon rubber in a methanol solution of 10.0 mass percent of 1H,1H,2H, 2H-perfluorooctyltrimethoxysilane treating agent for 1200s, drying at 70 ℃ for 60min, treating in a super-thermal hydrogen device with the voltage of 100V and the vacuum degree of 0.15Pa for 30s, taking out, soaking in ethanol for 30min, and drying at 70 ℃ for 30 min; and then soaking the mixture in deionized water for 30min, and then drying the mixture for 30min at the temperature of 70 ℃ to prepare the isotropic super-hydrophobic and super-oleophobic silicone rubber material.

Example 5:

(1) 30.0 mass percent of hydroxy vinyl silicone oil, 14.5 mass percent of the filler No. 104 prepared in example 1, 0.25 mass percent of platinum catalyst from Zhongxin organosilicon materials Co., Ltd, Dongguan and 0.25 mass percent of 3-butyn-1-ol inhibitor are uniformly mixed to obtain a first mixture. The mixing process adopts the parameters of ball milling and mixing as revolution of 200r/min and rotation of 500r/min for 30 min.

(2) Adding 35.0 mass percent of silicone oil containing 1.0 mass percent of hydrogen and containing 1.0 mass percent of Si-H groups and 20.0 mass percent of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane silicone rubber auxiliary agent into the first mixture prepared in the step 1, continuously and uniformly mixing, and obtaining a second mixture by adopting ball milling mixing parameters of revolution of 200r/min, autorotation of 500r/min and time of 60 min. And (4) defoaming the second mixed material in vacuum for 120min to obtain the printing ink.

(3) And (3) loading the 'ink' prepared in the step (2) into a 3D printer, centrifuging and defoaming at 5000r/min for 30min, and printing layer by layer according to the anisotropic porous structure characteristics, wherein the line printing speed is 5.0 mm/s. The diameter of the printing needle head is set to be 0.4mm, each layer of lines are printed in parallel, and the line spacing is 0.8 mm. And after printing one layer, adjusting the angle to ensure that the included angle between every two adjacent layers is 90 degrees, wherein the included angle between every two adjacent layers is the same, and the distance between the plane where the lines of each layer are located and the plane where the lines of the adjacent layers are located is 20 percent of the distance between the lines inside each layer. A total of 4 layers were printed to prepare a silicone rubber having a porous structure.

(4) And (3) pre-curing the silicon rubber with the porous structure prepared in the step (3) for 60min under the conditions that the temperature is 60 ℃ and the relative humidity is 60%. Then, dip-coating porous silicon rubber in an ethanol solution of a 1H,1H,2H, 2H-perfluorooctyltriethoxysilane treating agent with the mass fraction of 15.0% for 600s, drying at 60 ℃ for 90min, treating in a super-thermal hydrogen device with the voltage of 200V and the vacuum degree of 0.05Pa for 100s, taking out, soaking in ethanol for 50min, and drying at 60 ℃ for 50 min; and then soaking the mixture in deionized water for 50min, and then drying the mixture for 50min at the temperature of 60 ℃ to prepare the isotropic super-hydrophobic and super-oleophobic silicone rubber material.

Example 6:

(1) A first mixture was obtained by uniformly mixing 25.0 mass% of phenyl vinyl silicone oil, 24.8 mass% of the filler numbered 105 prepared in example 1, 0.1 mass% of PT-50 catalyst from eucalyptus silica gel science and technology ltd, guan, and 0.1 mass% of 3, 5-dimethyl-1-hexyn-3-ol inhibitor. The mixing process adopts grinding mixing parameters of 1500r/min and 40 min.

(2) Adding 35.0 mass percent of silicone oil containing 0.5 mass percent of hydrogen and containing Si-H groups and 15.0 mass percent of 1H,1H,2H, 2H-perfluorodecyl trimethoxy silane silicone rubber auxiliary agent into the first mixture prepared in the step 1, continuously and uniformly mixing, wherein the grinding and mixing parameters are 1500r/min, and the time is 60min, so as to obtain a second mixture. And (4) defoaming the second mixed material in vacuum for 120min to obtain the printing ink.

(3) And (3) filling the 'ink' prepared in the step (2) into a 3D printer, centrifuging and defoaming at 10000r/min for 10min, and printing layer by layer according to the anisotropic porous structure characteristics, wherein the line printing speed is 2.0 mm/s. The diameter of the printing needle head is set to be 1.0mm, each layer of lines are printed in parallel, and the line spacing is 2.0 mm. After printing one layer, adjusting the angle to make the included angle of 30 degrees and 60 degrees of adjacent layers appear alternately, wherein the distance between the plane where the lines of each layer are located and the plane where the lines of the adjacent layers are located is 10 percent of the distance between the lines in each layer. A total of 12 layers were printed to prepare a silicone rubber of porous structure.

(4) And (3) pre-curing the silicon rubber with the porous structure prepared in the step (3) for 60min under the conditions that the temperature is 70 ℃ and the relative humidity is 50%. Then, dip-coating porous silicon rubber in a methanol solution of 20.0 mass percent of 1H,1H,2H, 2H-perfluorodecyl trimethoxy silane treating agent for 90s, drying at 50 ℃ for 90min, treating in a super-thermal hydrogen device with the voltage of 200V and the vacuum degree of 0.1Pa for 60s, taking out, soaking in ethanol for 60min, and drying at 50 ℃ for 60 min; and then soaking the mixture in deionized water for 60min, and then drying the mixture for 60min at the temperature of 50 ℃ to prepare the isotropic super-hydrophobic and super-oleophobic silicone rubber material.

Example 7:

(1) A first blend was prepared by uniformly mixing 20.0 mass percent of tolyl vinyl silicone oil, 24.9 mass percent of the filler No. 106 prepared in example 1, 0.05 mass percent of Dow Corning RD27 platinum catalyst, and 0.05 mass percent of 3,7, 11-trimethyldodecyn-3-ol inhibitor. The mechanical stirring parameter adopted in the mixing process is 2000r/min, and the time is 50 min.

(2) Adding 35.0 mass percent of silicone oil containing 0.1 mass percent of hydrogen and containing Si-H groups and 20.0 mass percent of 1H,1H,2H, 2H-perfluorodecyl triethoxysilane silicone rubber auxiliary agent into the first mixture prepared in the step 1, continuously and uniformly mixing, wherein the mechanical stirring parameter is 2000r/min, and the time is 60min, so as to obtain a second mixture. And (4) defoaming the second mixed material in vacuum for 120min to obtain the printing ink.

(3) And (3) loading the 'ink' prepared in the step (2) into a 3D printer, centrifuging and defoaming at 8000r/min for 20min, and printing layer by layer according to the anisotropic porous structure characteristics, wherein the line printing speed is 1.0 mm/s. The diameter of the printing needle head is set to be 1.5mm, each layer of lines are printed in parallel, and the line spacing is 2.0 mm. After printing one layer, adjusting the angle to make the included angle of 45 degrees and 90 degrees of adjacent layers appear alternately, wherein the distance between the plane where the lines of each layer are located and the plane where the lines of the adjacent layers are located is 50% of the distance between the lines in each layer. A total of 7 layers were printed to prepare a silicone rubber having a porous structure.

(4) And (3) pre-curing the silicon rubber with the porous structure prepared in the step (3) for 30min under the conditions that the temperature is 80 ℃ and the relative humidity is 40%. Then, dip-coating porous silicon rubber in an ethanol solution of 20.0 mass percent of 1H,1H,2H, 2H-perfluorodecyl triethoxysilane treating agent for 10s, drying at the temperature of 20-90 ℃ for 5-120min, treating in a super-thermal hydrogen device with the voltage of 200V and the vacuum degree of 0.15Pa for 120s, taking out, soaking in ethanol for 5-60min, and drying at the temperature of 20-90 ℃ for 5-60 min; and then soaking the mixture in deionized water for 5-60min, and then drying the mixture at the temperature of 20-90 ℃ for 5-60min to obtain the isotropic super-hydrophobic and super-oleophobic silicone rubber material.

Example 8:

(1) Uniformly mixing 25.0 mass percent of benzylidene vinyl silicone oil, 29.9 mass percent of filler with the number of 105 prepared in example 1, 0.05 mass percent of DX-3080 platinum catalyst of Guangzhou large-sized and sensitive chemical raw material company Limited and 0.05 mass percent of 2-methyl-3-butyn-2-ol inhibitor to obtain a first mixture. The mixing process adopts the parameters of ball milling and mixing as revolution of 400r/min and rotation of 800r/min for 20 min.

(2) Adding 30.0 mass percent of silicon oil containing 0.1 mass percent of hydrogen and containing 0.1 mass percent of Si-H groups and 15.0 mass percent of polyvinylidene fluoride silicon rubber auxiliary agent into the first mixture prepared in the step 1, continuously and uniformly mixing, and obtaining a second mixture by adopting ball milling mixing parameters of revolution of 400r/min, rotation of 800r/min and time of 60 min. And (4) defoaming the second mixed material in vacuum for 120min to obtain the printing ink.

(3) And (3) loading the 'ink' prepared in the step (2) into a 3D printer, centrifuging and defoaming at 5000r/min for 20min, and printing layer by layer according to the anisotropic porous structure characteristics, wherein the line printing speed is 0.5 mm/s. The diameter of the printing needle head is set to be 1.5mm, each layer of lines are printed in parallel, and the line spacing is 2.0 mm. After printing one layer, adjusting the angle to make the included angles of the adjacent layers alternate at 30 degrees, 60 degrees and 90 degrees, wherein the distance between the plane where the lines of each layer are located and the plane where the lines of the adjacent layers are located is 40 percent of the distance between the lines in each layer. A total of 10 layers were printed to prepare a silicone rubber having a porous structure.

(4) And (3) pre-curing the silicon rubber with the porous structure prepared in the step (3) for 30min under the conditions that the temperature is 90 ℃ and the relative humidity is 30%. Then, dip-coating porous silicon rubber in a dimethylacetamide solution of a polyvinylidene fluoride treating agent with the mass fraction of 5.0% for 900s, drying at the temperature of 40 ℃ for 120min, treating in an hyperthermia hydrogen device with the voltage of 300V and the vacuum degree of 0.05Pa for 20s, taking out, soaking in ethanol for 40min, and drying at the temperature of 40 ℃ for 60 min; and then soaking the mixture in deionized water for 40min, and then drying the mixture for 60min at the temperature of 40 ℃ to prepare the isotropic super-hydrophobic and super-oleophobic silicone rubber material.

Example 9:

(1) A first mixture was obtained by uniformly mixing 20.0 mass% of methyl phenyl vinyl silicone oil, 44.9 mass% of the filler numbered 103 prepared in example 1, 0.05 mass% of MC-999 platinum-gold catalyst from Miteng rubber and plastic materials Co., Ltd, Dongguan, and 0.05 mass% of 3-butyn-1-ol inhibitor. The parameters of grinding and mixing adopted in the mixing process are 3000r/min, and the time is 60 min.

(2) And (2) adding 20.0 mass percent of silicon oil containing 2.0 mass percent of hydrogen and containing Si-H groups and 15.0 mass percent of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane silicon rubber auxiliary agent into the first mixture prepared in the step (1), continuously and uniformly mixing, and obtaining a second mixture by adopting grinding and mixing parameters of 3000r/min for 60 min. And (4) defoaming the second mixed material in vacuum for 120min to obtain the printing ink.

(3) And (3) filling the 'ink' prepared in the step (2) into a 3D printer, centrifuging and defoaming at 10000r/min for 30min, and printing layer by layer according to the anisotropic porous structure characteristics, wherein the line printing speed is 0.2 mm/s. The diameter of the printing needle head is set to be 2.0mm, each layer of lines are printed in parallel, and the line spacing is 3.0 mm. After printing one layer, adjusting the angle to make the included angle of 60 degrees and 90 degrees of adjacent layers appear alternately, wherein the distance between the plane where the lines of each layer are located and the plane where the lines of the adjacent layers are located is 30% of the distance between the lines in each layer. A total of 9 layers were printed to prepare a silicone rubber having a porous structure.

(4) And (3) pre-curing the silicon rubber with the porous structure prepared in the step (3) for 90min under the conditions that the temperature is 70 ℃ and the relative humidity is 50%. Then, dip-coating porous silicon rubber in xylene solution of 5.0 mass percent methyl vinyl trifluoropropyl silicon rubber treating agent for 2400s, drying at the temperature of 30 ℃ for 120min, treating in an hyperthermia hydrogen device with the voltage of 300V and the vacuum degree of 0.1Pa for 60s, taking out, soaking in ethanol for 30min, and drying at the temperature of 30 ℃ for 60 min; and then soaking the silicon rubber material in deionized water for 30min, and then drying the silicon rubber material for 60min at the temperature of 30 ℃ to prepare the isotropic super-hydrophobic and super-oleophobic silicon rubber material.

Example 10:

(1) Methyl vinyl trifluoropropyl silicone oil in a mass fraction of 40.0%, the filler numbered 101 and prepared in example 1 in a mass fraction of 5.0%, PT-50 catalyst of eucalyptus silica gel technology ltd, guan, in a mass fraction of 0.5%, and 3,7, 11-trimethyldodecyn-3-ol inhibitor in a mass fraction of 0.5% were mixed uniformly to obtain a first mixture. The mechanical stirring parameter adopted in the mixing process is 3000r/min, and the time is 30 min.

(2) Adding 40.0 mass percent of silicon oil containing 2.0 mass percent of hydrogen and containing Si-H groups and 14.0 mass percent of 1H,1H,2H, 2H-perfluorodecyl triethoxysilane silicon rubber auxiliary agent into the first mixture prepared in the step 1, continuously and uniformly mixing, wherein the mechanical stirring parameter is 3000r/min, and the time is 50min, thus obtaining a second mixture. And (4) defoaming the second mixture in vacuum for 90min to obtain the printing ink.

(3) And (3) loading the 'ink' prepared in the step (2) into a 3D printer, centrifuging and defoaming at 2000r/min for 30min, and printing layer by layer according to the anisotropic porous structure characteristics, wherein the line printing speed is 2.0 mm/s. The diameter of the printing needle head is set to be 0.1mm, each layer of lines are printed in parallel, and the line spacing is 0.5 mm. And after printing one layer, adjusting the angle to ensure that the included angle between every two adjacent layers is 90 degrees, wherein the included angle between every two adjacent layers is the same, and the distance between the plane where the lines of each layer are located and the plane where the lines of the adjacent layers are located is 20 percent of the distance between the lines inside each layer. A total of 15 layers were printed to prepare a silicone rubber having a porous structure.

(4) And (3) pre-curing the silicon rubber with the porous structure prepared in the step (3) for 180min under the conditions that the temperature is 50 ℃ and the relative humidity is 70%. Then, dip-coating the porous silicon rubber in an ethanol solution of 10.0 mass percent of 1H,1H,2H, 2H-perfluorodecyl triethoxysilane treating agent for 3600s, drying at the temperature of 25 ℃ for 120min, treating in a super-thermal hydrogen device with the voltage of 150V and the vacuum degree of 0.15Pa for 30s, taking out, soaking in ethanol for 50min, and drying at the temperature of 25 ℃ for 60 min; and then soaking the mixture in deionized water for 50min, and then drying the mixture for 60min at the temperature of 25 ℃ to prepare the isotropic super-hydrophobic and super-oleophobic silicone rubber material.

< test >

The contact angles of water drops, water-soluble liquid drops and oil drops of the prepared silicone rubber material in the directions of 0 degree, 45 degrees and 90 degrees with the uppermost line are tested, if the contact angle of the liquid drops reaches more than 150 degrees, the difference of the contact angles of the liquid drops in any two directions of the surface of the porous silicone rubber is less than 5 degrees, and the rolling angles of the liquid drops in the directions of 0 degree, 45 degrees and 90 degrees are less than 10 degrees, the sample is considered to be represented as the isotropic super-hydrophobic and super-oleophobic characteristic. If the contact angle of the liquid drop still can reach more than 150 degrees in the directions of 0 degree, 45 degrees and 90 degrees after 120min ultrasonic strong damage, 10000 times mechanical bending damage or 10000 times mechanical friction damage, the difference of the contact angles of the liquid drop in any two directions of the surface of the porous silicon rubber is still less than 5 degrees, and the rolling angles of the liquid drop in the directions of 0 degree, 45 degrees and 90 degrees are all less than 10 degrees, the stable isotropic super-hydrophobic super-oleophobic characteristic resisting the mechanical damage is shown, the sample is marked to be qualified at the moment, otherwise, the sample is unqualified, and the test result is shown in the following table 1-2. TABLE 1 test results of contact angle and rolling angle of distilled water drop

TABLE 2 peanut oil drop contact angle and rolling angle test results

Claims

1. A method for preparing an isotropic super-hydrophobic and super-oleophobic silicon rubber material through an anisotropic structure comprises the following steps:

(1) uniformly mixing silicone oil containing C = C double bonds, inorganic nano filler, catalyst and inhibitor to obtain a first mixture, wherein one or more of ball milling, grinding or mechanical stirring is adopted in the mixing process;

(2) adding hydrogen-containing silicone oil and a silicone rubber auxiliary agent into the first mixture prepared in the step (1), and uniformly mixing to obtain a second mixture; defoaming the second mixture to obtain 'ink' for printing;

(3) filling the 'ink' prepared in the step (2) into a 3D printer, and printing according to the anisotropic porous structure characteristics to prepare the silicon rubber with the porous structure;

(4) placing the silicon rubber with the porous structure prepared in the step (3) in a constant temperature and humidity environment for pre-curing treatment; then, dip-coating porous silicon rubber in a treating agent solution, drying, carrying out super-thermal hydrogen treatment, taking out, cleaning and drying again to obtain an isotropic super-hydrophobic super-oleophobic silicon rubber material;

the pre-curing process is as follows: the silicon rubber is treated for 30-180min under the conditions that the temperature is 20-90 ℃ and the relative humidity is 20-100%.

2. The method for preparing an isotropic superhydrophobic and superoleophobic silicone rubber material through anisotropic structure according to claim 1, characterized in that said silicone oil containing C = C double bonds is vinyl silicone oil;

the inorganic nano filler is one or more of silicon dioxide, calcium silicate, calcium carbonate, titanium dioxide, carbon black, graphene, carbon nano tubes, montmorillonite and zinc oxide;

the particle size of the inorganic nano filler is 1-5000 nm.

3. The method for preparing the isotropic superhydrophobic and superoleophobic silicone rubber material through anisotropic structure according to claim 2, characterized in that the vinyl silicone oil is one or more of divinyl silicone oil, methyl vinyl silicone oil, hydroxyl vinyl silicone oil, phenyl vinyl silicone oil, tolyl vinyl silicone oil, benzylidene vinyl silicone oil, methyl phenyl vinyl silicone oil, methyl vinyl trifluoropropyl silicone oil.

4. The method for preparing the isotropic super-hydrophobic and super-oleophobic silicone rubber material through the anisotropic structure according to claim 1, characterized in that the inorganic nano-filler is pretreated by the following steps: soaking the coupling agent with the mass concentration of 0.1-5.0% for 5-60min, and then drying the coupling agent at the temperature of 20-90 ℃ for 5-60 min;

the coupling agent is a silane coupling agent or a titanate coupling agent.

5. The method for preparing the isotropic superhydrophobic and superoleophobic silicone rubber material through anisotropic structure according to claim 1, characterized in that the catalyst is platinum catalyst;

the catalyst is one or more of Dow Corning RD27 platinum catalyst, DX-3080 platinum catalyst of Guangzhou Daxixi chemical raw material Co., Ltd, MC-999 platinum catalyst of Miteng rubber and plastic material Co., Ltd, platinum catalyst of Zhongxin organic silicon material Co., Ltd, Dongguan and PT-50 of Tian Eucalyptus silica gel technology Co., Ltd;

the mass fraction of the catalyst added into the silicon rubber is 0.001-0.5%;

the inhibitor is an alkynyl-containing inhibitor;

the inhibitor is one or more of 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 3-butyn-1-ol, 3, 5-dimethyl-1-hexyn-3-ol and 3,7, 11-trimethyldodecyn-3-ol;

the mass fraction of the inhibitor added into the silicone rubber is 0.001-0.5%.

6. The method for preparing the isotropic super-hydrophobic and super-oleophobic silicone rubber material through the anisotropic structure according to claim 1, wherein in step 1, the mixing process is realized by one of ball milling, grinding or mechanical stirring, and the specific process parameters are as follows:

the mechanical stirring parameter is 100-3000 r/min, and the time is 30-60 min.

7. The method for preparing the isotropic super-hydrophobic and super-oleophobic silicone rubber material through the anisotropic structure according to claim 1, characterized in that the hydrogen-containing silicone oil is silicone oil containing Si-H groups, and the mass fraction of hydrogen content of the silicone oil is 0.1-2.0%;

the silicone oil containing Si-H groups is added into the silicone rubber, and the mass fraction of the silicone oil added into the silicone rubber is 20.0-40.0%;

the silicon rubber additive is one or more of polytetrafluoroethylene, polyvinylidene fluoride, 1H,2H, 2H-perfluorooctyltrimethoxysilane, 1H,2H, 2H-perfluorooctyltriethoxysilane, 1H,2H, 2H-perfluorodecyltrimethoxysilane and 1H,1H,2H, 2H-perfluorodecyltrimethoxysilane;

the mass fraction of the silicone rubber additive added into the silicone rubber is 5.0-20.0%.

8. The method for preparing the isotropic super-hydrophobic and super-oleophobic silicone rubber material through the anisotropic structure according to claim 1, wherein in the step (2), the defoaming process adopts vacuum defoaming;

step 3, performing centrifugal deaeration before adding the second mixture into the 3D printer;

the centrifugal defoaming rotating speed is 2000-10000 r/min, and the time is 5-60 min.

9. The method for preparing the isotropic superhydrophobic and superoleophobic silicone rubber material through the anisotropic structure according to claim 1, wherein the step (3) of printing according to the anisotropic structure features is that: setting a printing multilayer structure, wherein each layer is formed by a plurality of mutually parallel lines, and the lines of adjacent layers have a certain included angle which is 0-90 degrees and does not contain 0 degree;

the distance between the inner lines of each layer is 0.5-3.0 mm;

step (3), printing according to the anisotropic structure characteristics, wherein the number of printing layers is 4-20;

the diameter of the printing needle head is controlled to be 0.1-2.0 mm;

controlling the range of the distance between the plane where the lines of each layer are printed and the plane where the lines of the adjacent layer are positioned to be 0-50% of the distance between the lines of each layer, wherein the distance does not contain 0;

and (3) in the 3D printing process, the line printing speed is 0.2-25.0 mm/s.

10. The method for preparing the isotropic superhydrophobic and superoleophobic silicone rubber material through anisotropic structure according to claim 9, wherein in step (3), the number of printing layers is 4-10.

11. The method for preparing the isotropic super-hydrophobic and super-oleophobic silicone rubber material through the anisotropic structure according to claim 1, characterized in that in the step (4), the mass fraction of the treating agent solution is 5.0-20.0%; the treating agent is one or more selected from polyvinylidene fluoride, methyl vinyl trifluoropropyl silicone rubber, 1H,2H, 2H-perfluorooctyl trimethoxy silane, 1H,2H, 2H-perfluorooctyl triethoxy silane, 1H,2H, 2H-perfluorodecyl trimethoxy silane and 1H,1H,2H, 2H-perfluorodecyl triethoxy silane.

12. The method for preparing the isotropic superhydrophobic and superoleophobic silicone rubber material through anisotropic structure according to claim 11, characterized in that in step (4), the solvent used in the treating agent solution is one or more of dimethylacetamide, toluene, xylene, methanol and ethanol.

13. The method for preparing the isotropic superhydrophobic and superoleophobic silicone rubber material through the anisotropic structure in the claim 1, wherein in the step (4), the prepared silicone rubber material has the following characteristics:

the contact angle of the water drops or the water-soluble liquid drops or the liquid drops on the porous silicon rubber reaches more than 150 degrees, the difference of the contact angles of the liquid drops on the surface of the porous silicon rubber in any two directions is less than 5 degrees, and the rolling angle of the liquid drops in any direction is less than 10 degrees;

the water-soluble liquid drop comprises one or more of water-based paint, water-based ink, acid-base salt water solution with the pH value of 1-13, sweat, blood, urine and oil-in-water emulsion,

or the oil drops comprise one or more of vegetable oil, animal oil, gasoline, diiodomethane drops, cyclohexane drops, n-heptane drops and water-in-oil emulsion;

after one or more of ultrasonic strong damage, 10000 mechanical bending damage or 10000 mechanical friction damage for 120min, the contact angle of the liquid drop can still reach more than 150 degrees, the difference of the contact angles of the liquid drop in any two directions on the surface of the porous silicon rubber is less than 5 degrees, and the rolling angle of the liquid drop in any direction is less than 10 degrees.