CN107974089A - The super-hydrophobic superoleophobic regular porous silicone rubber of isotropism is prepared by anisotropic structure - Google Patents
The super-hydrophobic superoleophobic regular porous silicone rubber of isotropism is prepared by anisotropic structure Download PDFInfo
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
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Abstract
The super-hydrophobic superoleophobic silastic material method of isotropism is prepared by anisotropic structure the invention discloses one kind, is comprised the following steps：（1）The silicone oil of the double bond containing C=C, inorganic nano-filler, catalyst, inhibitor mixed is uniform, the first mixture is obtained,（2）The first mixture prepared to step 1 adds containing hydrogen silicone oil, silicon rubber auxiliary agent, is uniformly mixed, and obtains the second mixture, deaeration, obtains printing and use " ink "；（3）" ink " is loaded into 3D printer, is printed according to anisotropy loose structure feature, the silicon rubber of loose structure is prepared；（4）Precuring processing is carried out, then, cleaning is taken out after superthermal hydrogen processing is carried out after dip-coating, drying in handling agent solution, dries again, obtain the super-hydrophobic superoleophobic silastic material of isotropism.The present invention combines silicon rubber and inorganic nano-filler, realizes that physical arrangement and material property organically combine using 3D printing, prepares the super-hydrophobic superoleophobic silicon rubber of isotropism.
Description
Technical field
The invention belongs to super-hydrophobic superoleophobic porous silicone rubber field, especially relates to one kind by 3D printing respectively to different
Property structure and the super-hydrophobic superoleophobic silastic material of isotropism being directly prepared.Meanwhile above-mentioned silastic material has
The superoleophobic characteristic of excellent mechanical stability, porous super hydrophobic, and the silicon rubber preparation method is provided.
Background technology
Material surface wetability is typically to be determined by the physical arrangement and chemical composition of material surface, according to physical arrangement
And/or whether chemical composition is consistent in different directions, the wetability of material surface can be divided into isotropism wetability and each
Anisotropy wetability.Wherein, isotropism wetability refers to the wetability all same of material surface different directions, it usually needs each
Physical arrangement and isotropic chemical composition to the same sex could realize isotropism wetability, if physical arrangement and chemistry
Any one or two in composition are that then to normally result in surface be anisotropy wetability to anisotropic character.Anisotropy
Wetability is that there are different wetabilitys, this phenomenon many natural plants or animal in nature for material surface different directions
Organ surface all there are such specificity.For example, butterfly's wing surface water droplet is easily rolled to edge from root and slides,
But it is not easy backscrolling, this is primarily due to caused by the anisotropy of the physical arrangement on its surface.Meanwhile by table
The chemical composition in face carries out anisotropic moditied processing without changing surface physics structure, can also realize that surface anisotropy moistens
Moist design and preparation.
Anisotropic physical arrangement subtracts in miniature fluid devices, liquid pattern device, condensing heat-exchange equipment, fluid
The fields such as resistance, cell directional culture, organizational project application are with a wide range of applications, but these anisotropic physical arrangements
Surface often needs isotropism wetability again, to meet the function such as the waterproof on surface, antifouling, automatically cleaning, and this with it is traditional
Anisotropy physics structure causes the basic concept of anisotropy wetability to contradict, therefore common anisotropy physics structure
It is difficult to meet the needs of isotropism wetability.Thus need to carry out accuracy controlling to anisotropy physics structure, it is right to reduce its
The influence of surface wettability, so that the isotropism chemistry composition of mating surface realizes anisotropy physics body structure surface respectively to same
The design and preparation of property wetability.The construction method of usual anisotropy physics structure includes：Ferrofluid template
(Adv.Funct.Mater.2015,25,2670-2676), stretching corrugation method (Adv.Funct.Mater.2013,23,547-
553), template stamped method (Adv.Mater.2013,25,5756-5761), femtosecond laser (Soft Matter, 2011,7,
8337-8342) etc. (Adv.Mater.2012,24,1287-1302).But these methods, which exist, needs anisotropic template, mould
Plate fixes the shortcomings of then structure fixation causes to be difficult to accuracy controlling surface anisotropy physical arrangement, and prepares different anisotropy
The template of physical arrangement then needs special method, and there are complex process, of high cost, template to be easily destroyed the deficiencies of loss is big.
3D printing technique, can be carried out by computer needed for pattern design, be then output to printing device, straight forming
Various complicated architectural features, print procedure can also be controlled and obtained conveniently by computer program without template, architectural feature
Design (the CN 103854844A of preferable various labyrinths；CN 104441091A).(the CN in the work of our early periods
Desk study 105818378A) has been carried out to anisotropic silicon foam structure, solve traditional silicon rubber foam product its
The structure of abscess, the problem of size and uniformity are poor.Therefore, prepared by the 3D printing to silicon rubber, can be fine
The design and preparation of surface anisotropy physical arrangement are realized in ground, but the related work before us mainly realize still more
Anisotropy wetability caused by traditional anisotropy physics structure regulates and controls, therefore the present invention is by silicon rubber marking ink
The surface chemistry composition regulation and control of the design of material, the optimization design of printing technology and later stage are it is achieved thereby that anisotropy physics knot
The design and preparation of structure surface isotropism wetability.
The content of the invention
Present invention aims to overcome that prior art anisotropic structure surface is anisotropy wetability, no
Further improve beneficial to material property and limit reinforcing material application range deficiency, there is provided a kind of anisotropy physics knot
Structure but there is the super-hydrophobic superoleophobic silastic material of isotropic.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
A kind of method that the super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure, including it is following
Step：
(1) it is the silicone oil of the double bond containing C=C, inorganic nano-filler, catalyst, inhibitor mixed is uniform, obtain the first mixing
Material, mixed process use the one or more in ball milling, grinding or mechanical agitation.
(2) containing hydrogen silicone oil, silicon rubber auxiliary agent are added to the first mixture prepared by step 1, be uniformly mixed, it is mixed to obtain second
Close material.By the second mixture deaeration, obtain printing and use " ink ".
(3) " ink " for preparing step 2 loads 3D printer, is printed according to anisotropy loose structure feature,
The silicon rubber of loose structure is prepared.
(4) silicon rubber for the loose structure for preparing step 3 carries out precuring processing.Then, porous silicone rubber is being located
Cleaning is taken out after carrying out superthermal hydrogen processing after dip-coating, drying in reason agent solution, dries again, it is super-hydrophobic super thin to obtain isotropism
Oily silastic material.
The super-hydrophobic superoleophobic silastic material preparation method of isotropism of the present invention is using 3D printer according to anisotropy
Architectural feature is printed, and microstructure has anisotropic physical arrangement, in combination with the enhancing of upper inorganic nano-filler
Precuring processing realizes that anisotropic structure surface microroughnessization changes after the completion of effect and printing, is finally reached each to same
The super-hydrophobic superoleophobic characteristic of property.Inorganic nano-filler is evenly mixed in silicon rubber in advance, in silicon rubber in procuring process
Surface conversion forms micro-rough shape, and strong bonded is realized after last curing process, thus resulting materials are abundant
The double grading of inorganic nano-filler and silicon rubber is played, and coordinates the micro-roughening characteristic of silastic surface, is realized each to same
Property it is super-hydrophobic superoleophobic.Due to preparing anisotropic structure using 3D printing, so the overall structure of material is with regular more
Hole feature, material have pliability, so as to excellent mechanical resistant damage capability.
Further, the silicone oil of the double bond containing C=C for vinyl silicone oil, divinyl silicone oil, methyl vinyl silicon oil,
Hydroxyvinyl silicone oil, phenyl-vinyl silicon oil, Tolyl-vinyl silicone oil, benzylidene vinyl silicone oil, aminomethyl phenyl second
One or more in alkenyl silicone oil, methyl ethylene trifluoro propyl silicone oil.Material has natural hydrophobic based on silicone oil
Property, and there is pliability, extraneous destruction offset by that can be deformed during mechanism, so as to preferably strengthen it is each to
The super-hydrophobic superoleophobic characteristic of synthesis of material after anisotropic approach shaping.
Preferably, it is 20.0~40.0% that the silicone oil of the double bond containing C=C, which is added to mass fraction in silicon rubber,.According to
The mass fraction of silicon rubber preparing raw material component calculates, and determines the silicone oil adding proportion of the double bond containing C=C in raw material.
Further, the inorganic nano-filler for silica, calcium silicates, calcium carbonate, titanium dioxide, carbon black, graphene,
One or more in carbon nanotubes, montmorillonite, zinc oxide.
Preferably, the inorganic nano-filler grain size is 1~5000nm, preferably Nano filling particle diameter for 5~
500nm。
Preferably, it is 1.0~50.0% that the inorganic nano-filler, which is added to mass fraction in silicon rubber,.According to silicon rubber
Inorganic nano-filler mass ratio is calculated in the quality and raw material of finished product, inorganic nano-filler rule after silicon rubber formed
Draw and be attached among silicon rubber, form stable bond state.
Preferably, the inorganic nano-filler is as follows by pretreatment, preprocessing process：Use mass concentration for 0.1~
5.0% coupling agent first soaks 5~60min, then dry 5~60min at a temperature of 20~90 DEG C.Pre-processed by coupling agent
So that the enhancing of inorganic nano-filler surface nature improves, enable preferably and silastic material mixing is scattered, formed uniform
The mixed material combined is distributed, and the surface of silicon rubber lines can be distributed to during 3D printing, easy to follow-up precuring
Promote the realization of the micro-roughening structure of 3D printing body structure surface when processing.
Preferably, the coupling agent is alkane coupling agent or titanate coupling agent.
Preferably, the coupling agent is 3- aminopropyl triethoxysilanes, 3- glycydoxy trimethoxies
Silane, 3- (methacryloxypropyl) propyl trimethoxy silicane, Di(dioctylpyrophosphato) ethylene titanate and isopropyl
One or more in base three (dioctylphyrophosphoric acid acyloxy) titanate esters.It is good with compatibility using above-mentioned coupling agent, can
It is more preferable to be implemented in combination with inorganic nano-filler and the dispersed effect of silicon rubber, and meet to lift silastic material isotropic
Advantage.
Further, the catalyst is platinum catalyst.
Preferably, the catalyst is DOW CORNING RD27 platinum catalysts, Guangzhou great Xi chemical raw materials Co., Ltd
DX-3080 platinum catalysts, the MC-999 platinum catalysts of Dongguan City Magotan rubber-plastics material Co., Ltd, Dongguan City are many prosperous organic
One or more in the platinum catalyst of silicon materials Co., Ltd, the PT-50 of Dongguan City Tian An silica gel Science and Technology Ltd..
Preferably, it is 0.001~0.5% that the catalyst, which is added to mass fraction in silicon rubber,.
Further, the inhibitor is inhibitor containing alkynyl.
Preferably, the inhibitor is 1- acetenyl -1- cyclohexanol, 2- methyl -3- butyne-2-alcohols, propargyl alcohol, 3- fourths
One or more in alkynes -1- alcohol, 3,5- dimethyl -1- hexin -3- alcohol, 3,7,11- trimethyl dodecyne -3- alcohol.
Preferably, it is 0.001~0.5% that the inhibitor, which is added to mass fraction in silicon rubber,.
Further, step 1, mixed process realizes that specific technological parameter is such as using one of ball milling, grinding or mechanical agitation
Under：
The parameter of ball milling mixing is 50~400r/min of revolution, and 100~800r/min of rotation, the time is 20~60min.
The parameter of ground and mixed is 30~3000r/min, and the time is 30~60min.
Churned mechanically parameter is 100~3000r/min, and the time is 30~60min.
Parameter Conditions in optimal design-aside mixed process so that mutual mixed of silicone rubber material and inorganic nano-filler
It is more preferable to close effect, accomplishes to be sufficiently mixed, and avoid excessive ball milling, grinding or the unfavorable shadow of silicon rubber property caused by mechanical agitation
Ring.
Further, the containing hydrogen silicone oil is the silicone oil containing Si -- H, its hydrogen content mass fraction is 0.1~2.0%.
Preferably, it is 20.0~40.0% that the silicone oil containing Si -- H, which is added to mass fraction in silicon rubber,.It is hydrogeneous
The dosage of silicone oil is calculated with the mass ratio of the quality of the silicone oil containing Si -- H and silicon rubber finished product in raw material.
Further, the silicon rubber auxiliary agent for polytetrafluoroethylene (PTFE), polyvinylidene fluoride, 1H, 1H, 2H, 2H- perfluoro capryls three
Methoxy silane, 1H, 1H, 2H, 2H- perfluoro capryls triethoxysilane, 1H, 1H, 2H, 2H- perfluoro decyls trimethoxy silane,
One or more in 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilane.Can be effective using suitable silicon rubber auxiliary agent
Transfer efficiency and release property of the silicon rubber during 3D printing are lifted, is conducive to print the control of pattern.In silicon rubber
After printing shaping, the wearability of silicon rubber foam material can also be strengthened, be allowed to keep under severe mechanical wear environment
Good structural stability.
Preferably, it is 5.0~20.0% that the silicon rubber auxiliary agent, which is added to mass fraction in silicon rubber,.
Further, step 2, mixed process uses the one or more in ball milling, grinding or mechanical agitation.
Preferably, step 2, mixed process is directly added into material and is carried out using step 1 mixing arrangement or equipment with step 1
Mixing.For example, step 1 uses ball milling mixing, then step 2 adds containing hydrogen silicone oil, silicon rubber auxiliary agent directly into ball-milling device, so
After continue ball-milling treatment, obtain the second uniformly mixed mixture.
Further, step 2, mixed process process control parameter is as follows：
The parameter of ball milling mixing is 50~400r/min of revolution, and 100~800r/min of rotation, the time is 20~60min；
The parameter of ground and mixed is 30~3000r/min, and the time is 30~60min；
Churned mechanically experiment condition is 100~3000r/min, and the time is 30~60min.
Step 2 mixed process process parameter control and step 1 are basically identical, convenient control, while are also beneficial to addition and contain
Hydrogen silicone oil, silicon rubber auxiliary agent it is dispersed, it is ensured that add reagent the effect of can giving full play to its expection.
Further, step 2, de-aeration uses vacuum defoamation.The second mixture being mixed to get is because in mixed process
The process characteristics such as the ball milling of use, grinding, mechanical agitation, the easy air entrainment in mixture, influences the quality of 3D printing, with
And the injection and printing of material.Preferably, the vacuum defoamation time is 30~240min.By inventor's experimental study vacuum
Inclined heated plate can ensure the quality of deaeration within this range, and not increase deaeration technique cost excessively.
Further, step 3, evacuation and centrifugal degassing is carried out before the second mixture adds 3D printer.By evacuation and centrifugal degassing into
The abundant removing bubble of one step, centrifugal process high speed high pressure can quickly slough micro bubble in mixture, be conducive to 3D and beat
It is continuous to print structure.Preferably, the evacuation and centrifugal degassing rotating speed is 2000~10000r/min, and the time is 5~60min.
Preferably, step 3, " ink " is subjected to tubulature, is then printed using 3D printer.Preferably, before printing,
" ink " of tubulature is subjected to centrifugal treating, deaerate deaeration.Centrifuged using the tubulature of 3D printer, can both centrifuge removing
Remaining bubble during vacuum defoamation, and emerging bubble during tubulature can be sloughed, 3D printing " ink is effectively ensured
The continuity of water ", lifts print quality.
Further, step 3, carrying out printing according to anisotropic structure feature is：Set printing sandwich construction, each layer by
The a plurality of lines that are parallel to each other are formed, the lines of adjacent layer there are certain angle, angular range (0~90] °, right closed zone is opened on a left side
Between, angle can not be with for 0 °, but can be 90 °.It is preferred that 90 ° of adjacent layer lines angle, i.e. adjacent layer lines are mutually perpendicular to.It is each
Angle between a adjacent layer may be the same or different.Preferably, angular range [30~90] °.Most preferred situation is
The lines of odd-level and even level are mutually perpendicular to.Progress in print procedure in layer continuously prints, and is beaten inside same layer
The lines of print are parallel to each other, and are adjusted the angle after printed one layer and then proceed to print next layer.
Preferably, the spacing of each layer of internal lines is 0.5~3.0mm.Found by the research of inventor, when printing
Inner wire stripe pitch within this range when, stereoeffect can be given full play to for the super-hydrophobic superoleophobic property of material
Facilitation, realize super-hydrophobic superoleophobic characteristic.
Preferably, step 3, printed according to anisotropic structure feature, the printing number of plies is 4-20 layers, is preferably 4-10
Layer.Pass through the good anisotropic structure silicon rubber composite material of sandwich construction component.
Further, the diameter control of syringe needle is printed in 0.1~2.0mm.Cooperate, realize good more with lines spacing
Pore structure, keeps silicon rubber print structure stable and has certain elasticity.Preferably, each layer of lines diameter can phase
Together, can not also be same.
Preferably, interplanar spacing where lines is each layer in plane where controlling the lines of each layer of printing and adjacent layer
The scope of inner wire stripe pitch be (0~50%], interval closed at the right is opened on a left side.Preferably, the lines of the lines of odd-level and even level
Be mutually perpendicular to, the mutual level interval of lines of first layer and third layer be for foregoing lines spacing range (0~50%], remaining phase
The adjacent same scope of odd number interlamellar spacing be (0~50%], at the same the second layer with the 4th layer of the mutual level interval of lines also to be foregoing
Lines spacing range be (0~50%], remaining same scope of neighbouring even-numbered interlamellar spacing be (0~50%].
Preferably, each Rotating fields face is considered as horizontal plane, then the vertical range between wall is each layer of inner wire
Stripe pitch (0~50%].
Further, step 3, during 3D printing, lines printing speed is 0.2~25.0mm/s.
Further, step 4, precuring processing procedure is：The silicon rubber that step 3 is printed to gained loose structure is placed in constant temperature
Precuring is carried out in constant humidity environment, such as can be that the silicon rubber of loose structure is put into climatic chamber to be cured, so
Cleaning is taken out after porous silicone rubber is carried out superthermal hydrogen processing after dip-coating, drying in handling agent solution afterwards, dries, obtains again
The super-hydrophobic superoleophobic silastic material of isotropism.
Preferably, step 4, precuring processing procedure is as follows：Silicon rubber is 20~90 DEG C in temperature and relative humidity is 20
30-180min is handled under the conditions of~100%.After printing obtains the silastic material of loose structure, constant-temperature constant-humidity environment is utilized
Small water droplet further constructs the coarse structure of about several microns of smaller scale in printing lines body structure surface in air, improves table
The super-hydrophobic superoleophobic ability in face and the isotropism of final products.
Preferably, step 4, the mass fraction for handling agent solution is 5.0~20.0%；Inorganic agent, which is selected from, gathers inclined difluoro second
Alkene, methyl ethylene trifluoro propyl silicon rubber, 1H, 1H, 2H, 2H- perfluoro capryls trimethoxy silane, 1H, 1H, 2H, 2H- perfluors
Octyltri-ethoxysilane, 1H, 1H, 2H, 2H- perfluoro decyls trimethoxy silane, 1H, 1H, 2H, three ethoxy of 2H- perfluoro decyls
One or more in base silane.Coating and super hot stressing by using inorganic agent, can make up the multilayer due to printing
The structure small harmful effect such as compression to fabric under the effect of gravity, it is overall from top to bottom so as to fulfill porous silicone rubber
And wetting uniformity and stability from outside to inside, while further anisotropy caused by reduction anisotropy physics structure
Sex differernce is soaked, so as to fulfill the purpose for the isotropism degree for improving super-hydrophobic superoleophobic regular porous silicone rubber.
Preferably, step 4, it is dimethylacetylamide, toluene, dimethylbenzene, methanol, second to handle the solvent used in agent solution
One or more in alcohol.
Preferably, step 4, after the silicon rubber of loose structure carries out precuring processing, the time of immersion in agent solution is handled
For 5-3600s, the dry 5-120min at a temperature of 20~90 DEG C, be then 100~300V in voltage, vacuum is 0.05~
Taking-up soaks 5-60min with ethanol after 5~120s is handled in the superthermal hydrogen storage equipment of 0.15Pa, is then done at a temperature of 20~90 DEG C
Dry 5-60min；Then 5-60min is soaked with deionized water, then dry 5-60min is prepared at a temperature of 20~90 DEG C
The super-hydrophobic superoleophobic silastic material of isotropism.
Further, step 4, the silastic material being prepared has following characteristic：Water droplet or water-soluble drop or oil droplet
Liquid-drop contact angle on porous silicone rubber reaches more than 150 °, and drop connecing in porous silicone rubber surface any two direction
Feeler difference is respectively less than 5 °, and the roll angle of drop in any direction be below 10 ° show as it is isotropic super-hydrophobic super
Oleophobic characteristic.
Preferably, the water-soluble drop includes but not limited to water paint, water-based ink, the acid-alkali salt that pH is 1~13
Aqueous solution, sweat, blood, urine, oil-in-water emulsion, or oil droplet include but not limited to vegetable oil, animal oil, gasoline, diiodo- first
Alkane drop, hexamethylene drop, single n-heptane droplet, water-in-oil emulsion.
Further, step 4, the porous silicone rubber material being prepared has following characteristic：By 120min ultrasound strengths
Destroy, after one or more of destructions in 10000 mechanical bends destructions or 10000 mechanical friction, liquid-drop contact angle remains to
Reach more than 150 °, and contact angle difference of the drop in porous silicone rubber surface any two direction is respectively less than 5 °, and drop exists
The roll angle of any direction is below 10 °.Preferably, including water droplet or water-soluble drop or oil droplet on it, contact angle reaches
More than 150 °, and contact angle difference of the drop in porous silicone rubber surface any two direction is respectively less than 5 °, and drop is any
The roll angle in direction is below 10 °.
Compared with prior art, beneficial effects of the present invention：
1. the method that the present invention prepares super-hydrophobic superoleophobic porous silicone rubber, is combined using silicon rubber and inorganic nano-filler
Mode, the combination of physical arrangement and material property is realized using 3D printing anisotropic structure, reaches isotropism and surpasses
Hydrophobic superoleophobic characteristic.
2. the super-hydrophobic superoleophobic porous silicone rubber material of isotropism that preparation method of the present invention is processed has resistance to height
Temperature, foam porosity, have stable structure reliable, the characteristics of being hardly damaged, meet that the function silastic material long-life uses
Requirement.
3. the method for the present invention prepare super-hydrophobic superoleophobic regular porous silicone rubber with high temperature resistant, foam structure is controllable, table
The advantages that face is super-hydrophobic superoleophobic state, soft stretchable deformation, mechanical resistant friction, capability is strong, light.
4. the present invention prepare function silicon rubber process without template, without surface breakdown, it is reproducible, can obtain easily structure rule
The super-hydrophobic superoleophobic surface of whole large area, preparation method have that universality is strong, technique is simply easy to actual production, production cost
Low advantage.
5. the present invention super-hydrophobic superoleophobic silastic material can meet building, ship, aerospace, microfluid preparation,
The practical application requests such as the surface waterproofing/anti-pollution in the fields such as bio-medical, automatically cleaning, the polymer patterning template of low cost.
Brief description of the drawings：
Fig. 1：30 ° sides of the hydrochloride aqueous solution drop that pH is 2 in sample surfaces after 120min ultrasound strong destructions
To when contact angle 154 ° (embodiments 2)
Fig. 2：90 ° sides of the sodium-chloride water solution drop that pH is 7 in sample surfaces after 10000 mechanical bends are destroyed
To when drop rolling behavior (embodiment 3)
Fig. 3：Surface topography optical photograph (embodiment 5) of the sample surfaces after 10000 mechanical bends are destroyed
Fig. 4：Single n-heptane droplet sample surfaces by 10000 mechanical friction destruction after 45 ° of directions when drop rolling
Dynamic behavior (embodiment 7)
Fig. 5：(digitized representation page order is from the 1st layer to the 10th layer in figure for porous silicone rubber printing path planning schematic diagram
Arrangement change, embodiment 8)
Fig. 6：PH be 12 sodium hydrate aqueous solution drop sample surfaces by 10000 mechanical friction destruction after 0 °
Contact angle 151 ° (embodiments 10) during direction
Embodiment
Make specific be described in detail to the present invention below by embodiment, it is necessary to which indicated herein to be, following embodiments are only used for
The present invention is made and is further illustrated by, it is impossible to is interpreted as limiting the scope of the invention, the technology in the field
Personnel's some nonessential modifications and adaptations that content makes this according to the present invention, are regarded as protection scope of the present invention.
Embodiment 1：
Prepare the inorganic nano-particle of coupling agent pretreatment
Inorganic nano-particle uses mass concentration to carry out immersion 5-60min in advance for 0.1~5.0% coupling agent, then
The dry 5-60min at a temperature of 20~90 DEG C, is prepared the inorganic nano-particle of coupling agent treatment.Specific preparing raw material and
Parameter is as follows：
Embodiment 2：
The super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure
(1) numbering for preparing the embodiment 1 that vinyl silicone oil that mass fraction is 40.0%, mass fraction are 14.0%
The 1- acetenyls that the DOW CORNING RD27 platinum catalysts and mass fraction that filler, mass fraction for 101 are 0.5% are 0.5%-
1- cyclohexanol inhibitor mixeds are uniform, obtain the first mixture.Mixed process uses the parameter of ball milling mixing as the 50r/ that revolves round the sun
Min, rotation 100r/min, time 40min.
(2) it is 2.0% to add the hydrogen content mass fraction that mass fraction is 40.0% to the first mixture prepared by step 1
Silicone oil containing Si -- H and polyvinylidene fluoride silicon rubber auxiliary agent that mass fraction is 5.0%, continue to be uniformly mixed, use
The parameter of ball milling mixing is revolution 50r/min, and rotation 100r/min, time 60min, obtains the second mixture.Second is mixed
Material vacuum defoamation 60min is closed, printing is obtained and uses " ink ".Note：Mass fraction is the matter calculated according to the gross mass of preparing raw material
Fraction is measured, all material composition mass fraction sums are 100%, are calculated according to the gross mass for preparing silastic material former
Material quality is simultaneously taken, similarly hereinafter.
(3) " ink " for preparing step 2 loads 3D printer, 5000r/min evacuation and centrifugal degassing 10min, according to each to different
Property loose structure feature printed layer by layer, lines printing speed be 25.0mm/s.The printing a diameter of 0.3mm of syringe needle is set, often
The parallel printing of one layer line bar, lines spacing 0.6mm.Printing adjusts the angle after completing one layer, makes 90 ° of adjacent layer angle, each
Angle between a adjacent layer is identical, and interplanar spacing where lines is each layer in plane where each layer of lines and adjacent layer
The scope of inner wire stripe pitch is 50%.19 layers are printed altogether, and the silicon rubber of loose structure is prepared.
(4) silicon rubber for the loose structure for preparing step 3 is pre- under the conditions of temperature is 30 DEG C and relative humidity is 90%
Cure 180min.Then, the dimethylacetamide by porous silicone rubber in mass fraction for 5.0% polyvinylidene fluoride inorganic agent
Dip-coating 3600s in amine aqueous solution, the dry 10min at a temperature of 90 DEG C, are then 100V in voltage, vacuum is the superthermal of 0.05Pa
Taking-up soaks 10min with ethanol after 120s is handled in hydrogen storage equipment, then the dry 10min at a temperature of 90 DEG C；Then deionization is used
Water soaks 10min, and then the super-hydrophobic superoleophobic silicon rubber material of isotropism is prepared in dry 10min at a temperature of 90 DEG C
Material.
Embodiment 3：
The super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure
(1) volume for preparing the embodiment 1 that divinyl silicone oil that mass fraction is 35.0%, mass fraction are 14.0%
Number for 102 filler, mass fraction be 0.5% Guangzhou great Xi chemical raw materials Co., Ltd DX-3080 platinum catalysts
It is uniform for 0.5% 2- methyl -3- butyne-2-alcohol inhibitor mixeds with mass fraction, obtain the first mixture.Mixed process is adopted
It is 100r/min, time 60min with the parameter of ground and mixed.
(2) it is 1.5% to add the hydrogen content mass fraction that mass fraction is 40.0% to the first mixture prepared by step 1
Silicone oil containing Si -- H and 1H, 1H, 2H that mass fraction is 10.0%, 2H- perfluoro capryl trimethoxy silane silicon rubber
Auxiliary agent, continues to be uniformly mixed, and using the parameter of ground and mixed, time 60min, obtains the second mixture for 100r/min.Will
Second mixture vacuum defoamation 60min, obtains printing and uses " ink ".
(3) " ink " for preparing step 2 loads 3D printer, 2000r/min evacuation and centrifugal degassing 30min, according to each to different
Property loose structure feature printed layer by layer, lines printing speed be 15.0mm/s.The printing a diameter of 0.5mm of syringe needle is set, often
The parallel printing of one layer line bar, lines spacing 1.0mm.Printing adjusts the angle after completing one layer, makes 45 ° of adjacent layer angle, each
Angle between a adjacent layer is identical, and interplanar spacing where lines is each layer in plane where each layer of lines and adjacent layer
The scope of inner wire stripe pitch is 40%.13 layers are printed altogether, and the silicon rubber of loose structure is prepared.
(4) silicon rubber for the loose structure for preparing step 3 is pre- under the conditions of temperature is 40 DEG C and relative humidity is 80%
Cure 120min.Then, by porous silicone rubber in the methyl ethylene trifluoro propyl silicon rubber inorganic agent that mass fraction is 8.0%
Toluene solution in dip-coating 2400s, the dry 30min at a temperature of 80 DEG C, be then 100V in voltage, vacuum is 0.1Pa's
Taking-up soaks 20min with ethanol after 60s is handled in superthermal hydrogen storage equipment, then the dry 30min at a temperature of 80 DEG C；Then spend from
Sub- water soaks 20min, and then the super-hydrophobic superoleophobic silicon rubber material of isotropism is prepared in dry 30min at a temperature of 80 DEG C
Material.
Embodiment 4：
The super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure
(1) prepared by the embodiment 1 that methyl vinyl silicon oil that mass fraction is 35.0%, mass fraction are 15.0%
The MC-999 platinums catalysis for the Dongguan City Magotan rubber-plastics material Co., Ltd that filler that numbering is 103, mass fraction are 0.25%
Agent and the propargyl alcohol inhibitor mixed that mass fraction is 0.25% are uniform, obtain the first mixture.Mixed process is stirred using machinery
The parameter mixed is 500r/min, time 50min.
(2) it is 1.5% to add the hydrogen content mass fraction that mass fraction is 35.0% to the first mixture prepared by step 1
Silicone oil containing Si -- H and polytetrafluoroethylene (PTFE) silicon rubber auxiliary agent that mass fraction is 14.5%.Continue to be uniformly mixed, use
Churned mechanically parameter is 500r/min, and time 60min, obtains the second mixture.By the second mixture vacuum defoamation
60min, obtains printing and uses " ink ".
(3) " ink " for preparing step 2 loads 3D printer, 8000r/min evacuation and centrifugal degassing 20min, according to each to different
Property loose structure feature printed layer by layer, lines printing speed be 10.0mm/s.The printing a diameter of 0.8mm of syringe needle is set, often
The parallel printing of one layer line bar, lines spacing 1.5mm.Printing adjusts the angle after completing one layer, makes 60 ° of adjacent layer angle, each
Angle between a adjacent layer is identical, and interplanar spacing where lines is each layer in plane where each layer of lines and adjacent layer
The scope of inner wire stripe pitch is 30%.9 layers are printed altogether, and the silicon rubber of loose structure is prepared.
(4) silicon rubber for the loose structure for preparing step 3 is pre- under the conditions of temperature is 50 DEG C and relative humidity is 70%
Cure 90min.Then, by porous silicone rubber in 1H, 1H, 2H that mass fraction is 10.0%, 2H- perfluoro capryl trimethoxy silicon
Dip-coating 1200s in the methanol solution of alkane inorganic agent, dry 60min, is then 100V in voltage, vacuum is at a temperature of 70 DEG C
Taking-up soaks 30min with ethanol after 30s is handled in the superthermal hydrogen storage equipment of 0.15Pa, then the dry 30min at a temperature of 70 DEG C；So
30min is soaked with deionized water afterwards, then that isotropism is prepared is super-hydrophobic superoleophobic by dry 30min at a temperature of 70 DEG C
Silastic material.
Embodiment 5：
The super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure
(1) prepared by the embodiment 1 that hydroxyvinyl silicone oil that mass fraction is 30.0%, mass fraction are 14.5%
The platinum catalyst for the Dongguan City Zhong Xin organosilicon materials Co., Ltd that filler that numbering is 104, mass fraction are 0.25% and
The 3- butyne-1-ol inhibitor mixeds that mass fraction is 0.25% are uniform, obtain the first mixture.Mixed process is mixed using ball milling
The parameter of conjunction is revolution 200r/min, rotation 500r/min, time 30min.
(2) it is 1.0% to add the hydrogen content mass fraction that mass fraction is 35.0% to the first mixture prepared by step 1
Silicone oil containing Si -- H and 1H, 1H, 2H that mass fraction is 20.0%, 2H- perfluoro capryl triethoxysilane silicon rubber
Auxiliary agent, continues to be uniformly mixed, and uses the parameter of ball milling mixing as 200r/min, rotation 500r/min, the time 60min of revolving round the sun,
Obtain the second mixture.By the second mixture vacuum defoamation 120min, obtain printing and use " ink ".
(3) " ink " for preparing step 2 loads 3D printer, 5000r/min evacuation and centrifugal degassing 30min, according to each to different
Property loose structure feature printed layer by layer, lines printing speed be 5.0mm/s.Printing syringe needle a diameter of 0.4mm is set, it is each
The parallel printing of layer line bar, lines spacing 0.8mm.Printing adjusts the angle after completing one layer, makes 90 ° of adjacent layer angle, each
Angle between adjacent layer is identical, and interplanar spacing where lines is in each layer in plane where each layer of lines and adjacent layer
The scope of portion's lines spacing is 20%.4 layers are printed altogether, and the silicon rubber of loose structure is prepared.
(4) silicon rubber for the loose structure for preparing step 3 is pre- under the conditions of temperature is 60 DEG C and relative humidity is 60%
Cure 60min.Then, by porous silicone rubber in 1H, 1H, 2H that mass fraction is 15.0%, 2H- perfluoro capryl triethoxysilicanes
Dip-coating 600s in the ethanol solution of alkane inorganic agent, dry 90min, is then 200V in voltage, vacuum is at a temperature of 60 DEG C
Taking-up soaks 50min with ethanol after 100s is handled in the superthermal hydrogen storage equipment of 0.05Pa, then the dry 50min at a temperature of 60 DEG C；
Then 50min is soaked with deionized water, then that isotropism is prepared is super-hydrophobic super thin by dry 50min at a temperature of 60 DEG C
Oily silastic material.
Embodiment 6：
The super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure
(1) prepared by the embodiment 1 that phenyl-vinyl silicon oil that mass fraction is 25.0%, mass fraction are 24.8%
The PT-50 catalyst and matter for the Dongguan City Tian An silica gel Science and Technology Ltd. that filler that numbering is 105, mass fraction are 0.1%
It is uniform to measure 3, the 5- dimethyl -1- hexin -3- alcohol inhibitor mixeds that fraction is 0.1%, obtains the first mixture.Mixed process is adopted
It is 1500r/min, time 40min with the parameter of ground and mixed.
(2) it is 0.5% to add the hydrogen content mass fraction that mass fraction is 35.0% to the first mixture prepared by step 1
Silicone oil containing Si -- H and 1H, 1H, 2H that mass fraction is 15.0%, 2H- perfluoro decyl trimethoxy silane silicon rubber
Auxiliary agent, continues to be uniformly mixed, and using the parameter of ground and mixed, time 60min, obtains the second mixture for 1500r/min.Will
Second mixture vacuum defoamation 120min, obtains printing and uses " ink ".
(3) " ink " for preparing step 2 loads 3D printer, 10000r/min evacuation and centrifugal degassing 10min, according to each to different
Property loose structure feature printed layer by layer, lines printing speed be 2.0mm/s.Printing syringe needle a diameter of 1.0mm is set, it is each
The parallel printing of layer line bar, lines spacing 2.0mm.Printing adjusts the angle after completing one layer, makes the 30 ° and 60 ° friendships of adjacent layer angle
For appearance, interplanar spacing where lines is the model of each layer of inner wire stripe pitch in plane where each layer of lines and adjacent layer
Enclose is 10%.12 layers are printed altogether, and the silicon rubber of loose structure is prepared.
(4) silicon rubber for the loose structure for preparing step 3 is pre- under the conditions of temperature is 70 DEG C and relative humidity is 50%
Cure 60min.Then, by porous silicone rubber in 1H, 1H, 2H that mass fraction is 20.0%, 2H- perfluoro decyl trimethoxy silicon
Dip-coating 90s in the methanol solution of alkane inorganic agent, dry 90min, is then 200V in voltage, vacuum is at a temperature of 50 DEG C
Taking-up soaks 60min with ethanol after 60s is handled in the superthermal hydrogen storage equipment of 0.1Pa, then the dry 60min at a temperature of 50 DEG C；So
60min is soaked with deionized water afterwards, then that isotropism is prepared is super-hydrophobic superoleophobic by dry 60min at a temperature of 50 DEG C
Silastic material.
Embodiment 7：
The super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure
(1) prepared by the embodiment 1 that Tolyl-vinyl silicone oil that mass fraction is 20.0%, mass fraction are 24.9%
Numbering be 106 filler, mass fraction be 0.05% DOW CORNING RD27 platinum catalysts and mass fraction be 0.05%
3,7,11- trimethyl dodecyne -3- alcohol inhibitor mixeds are uniform, obtain the first mixture.Mixed process is using churned mechanically
Parameter is 2000r/min, time 50min.
(2) it is 0.1% to add the hydrogen content mass fraction that mass fraction is 35.0% to the first mixture prepared by step 1
Silicone oil containing Si -- H and 1H, 1H, 2H that mass fraction is 20.0%, 2H- perfluoro decyl triethoxysilane silicon rubber
Auxiliary agent, continues to be uniformly mixed, and using churned mechanically parameter, time 60min, obtains the second mixture for 2000r/min.Will
Second mixture vacuum defoamation 120min, obtains printing and uses " ink ".
(3) " ink " for preparing step 2 loads 3D printer, 8000r/min evacuation and centrifugal degassing 20min, according to each to different
Property loose structure feature printed layer by layer, lines printing speed be 1.0mm/s.Printing syringe needle a diameter of 1.5mm is set, it is each
The parallel printing of layer line bar, lines spacing 2.0mm.Printing adjusts the angle after completing one layer, makes the 45 ° and 90 ° friendships of adjacent layer angle
For appearance, interplanar spacing where lines is the model of each layer of inner wire stripe pitch in plane where each layer of lines and adjacent layer
Enclose is 50%.7 layers are printed altogether, and the silicon rubber of loose structure is prepared.
(4) silicon rubber for the loose structure for preparing step 3 is pre- under the conditions of temperature is 80 DEG C and relative humidity is 40%
Cure 30min.Then, by porous silicone rubber in 1H, 1H, 2H that mass fraction is 20.0%, 2H- perfluoro decyl triethoxysilicanes
Dip-coating 10s in the ethanol solution of alkane inorganic agent, dry 5-120min, is then 200V in voltage, very at a temperature of 20~90 DEG C
Taking-up ethanol soaks 5-60min after 120s is handled in the superthermal hydrogen storage equipment that reciprocal of duty cycle is 0.15Pa, then in 20~90 DEG C of temperature
Lower dry 5-60min；Then 5-60min is soaked with deionized water, then dry 5-60min is prepared at a temperature of 20~90 DEG C
Obtain the super-hydrophobic superoleophobic silastic material of isotropism.
Embodiment 8：
The super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure
(1) embodiment 1 that benzylidene vinyl silicone oil that mass fraction is 25.0%, mass fraction are 29.9% is made
The DX-3080 platinums for the Guangzhou great Xi chemical raw materials Co., Ltd that filler that standby numbering is 105, mass fraction are 0.05%
Catalyst and the 2- methyl -3- butyne-2-alcohol inhibitor mixeds that mass fraction is 0.05% are uniform, obtain the first mixture.It is mixed
Conjunction process uses the parameter of ball milling mixing as the 400r/min, rotation 800r/min, time 20min of revolving round the sun.
(2) it is 0.1% to add the hydrogen content mass fraction that mass fraction is 30.0% to the first mixture prepared by step 1
Silicone oil containing Si -- H and polyvinylidene fluoride silicon rubber auxiliary agent that mass fraction is 15.0%, continue to be uniformly mixed, adopt
It is revolution 400r/min with the parameter of ball milling mixing, rotation 800r/min, time 60min, obtains the second mixture.By second
Mixture vacuum defoamation 120min, obtains printing and uses " ink ".
(3) " ink " for preparing step 2 loads 3D printer, 5000r/min evacuation and centrifugal degassing 20min, according to each to different
Property loose structure feature printed layer by layer, lines printing speed be 0.5mm/s.Printing syringe needle a diameter of 1.5mm is set, it is each
The parallel printing of layer line bar, lines spacing 2.0mm.Printing complete one layer after adjust the angle, make 30 °, 60 ° of adjacent layer angle and
90 ° are alternately present, and interplanar spacing where lines is between each layer of internal lines in plane where each layer of lines and adjacent layer
Away from scope be 40%.10 layers are printed altogether, and the silicon rubber of loose structure is prepared.
(4) silicon rubber for the loose structure for preparing step 3 is pre- under the conditions of temperature is 90 DEG C and relative humidity is 30%
Cure 30min.Then, the dimethylacetamide by porous silicone rubber in mass fraction for 5.0% polyvinylidene fluoride inorganic agent
Dip-coating 900s in amine aqueous solution, the dry 120min at a temperature of 40 DEG C, are then 300V in voltage, vacuum is the superthermal of 0.05Pa
Taking-up soaks 40min with ethanol after 20s is handled in hydrogen storage equipment, then the dry 60min at a temperature of 40 DEG C；Then deionized water is used
40min is soaked, then the super-hydrophobic superoleophobic silastic material of isotropism is prepared in dry 60min at a temperature of 40 DEG C.
Embodiment 9：
The super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure
(1) embodiment 1 that methyl phenyl vinyl silicone oil that mass fraction is 20.0%, mass fraction are 44.9% is made
The MC-999 platinums for the Dongguan City Magotan rubber-plastics material Co., Ltd that filler that standby numbering is 103, mass fraction are 0.05%
Catalyst and the 3- butyne-1-ol inhibitor mixeds that mass fraction is 0.05% are uniform, obtain the first mixture.Mixed process is adopted
It is 3000r/min, time 60min with the parameter of ground and mixed.
(2) it is 2.0% to add the hydrogen content mass fraction that mass fraction is 20.0% to the first mixture prepared by step 1
Silicone oil containing Si -- H and 1H, 1H, 2H that mass fraction is 15.0%, 2H- perfluoro capryl triethoxysilane silicon rubber
Auxiliary agent, continues to be uniformly mixed, and using the parameter of ground and mixed, time 60min, obtains the second mixture for 3000r/min.Will
Second mixture vacuum defoamation 120min, obtains printing and uses " ink ".
(3) " ink " for preparing step 2 loads 3D printer, 10000r/min evacuation and centrifugal degassing 30min, according to each to different
Property loose structure feature printed layer by layer, lines printing speed be 0.2mm/s.Printing syringe needle a diameter of 2.0mm is set, it is each
The parallel printing of layer line bar, lines spacing 3.0mm.Printing adjusts the angle after completing one layer, makes the 60 ° and 90 ° friendships of adjacent layer angle
For appearance, interplanar spacing where lines is the model of each layer of inner wire stripe pitch in plane where each layer of lines and adjacent layer
Enclose is 30%.9 layers are printed altogether, and the silicon rubber of loose structure is prepared.
(4) silicon rubber for the loose structure for preparing step 3 is pre- under the conditions of temperature is 70 DEG C and relative humidity is 50%
Cure 90min.Then, by porous silicone rubber in the methyl ethylene trifluoro propyl silicon rubber inorganic agent that mass fraction is 5.0%
Xylene solution in dip-coating 2400s, dry 120min, is then 300V, vacuum 0.1Pa in voltage at a temperature of 30 DEG C
Superthermal hydrogen storage equipment in handle 60s after taking-up soak 30min with ethanol, the then dry 60min at a temperature of 30 DEG C；Then spend
Ionized water soaks 30min, and then the super-hydrophobic superoleophobic silicon rubber of isotropism is prepared in dry 60min at a temperature of 30 DEG C
Material.
Embodiment 10：
The super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure
(1) embodiment for being 5.0% by methyl ethylene trifluoro propyl silicone oil that mass fraction is 40.0%, mass fraction
1 prepare numbering be 101 filler, mass fraction be 0.5% Dongguan City Tian An silica gel Science and Technology Ltd. PT-50 be catalyzed
Agent and 3,7, the 11- trimethyl dodecyne -3- alcohol inhibitor mixeds that mass fraction is 0.5% are uniform, obtain the first mixture.It is mixed
Conjunction process uses churned mechanically parameter as 3000r/min, time 30min.
(2) it is 2.0% to add the hydrogen content mass fraction that mass fraction is 40.0% to the first mixture prepared by step 1
Silicone oil containing Si -- H and 1H, 1H, 2H that mass fraction is 14.0%, 2H- perfluoro decyl triethoxysilane silicon rubber
Auxiliary agent, continues to be uniformly mixed, and using churned mechanically parameter, time 50min, obtains the second mixture for 3000r/min.Will
Second mixture vacuum defoamation 90min, obtains printing and uses " ink ".
(3) " ink " for preparing step 2 loads 3D printer, 2000r/min evacuation and centrifugal degassing 30min, according to each to different
Property loose structure feature printed layer by layer, lines printing speed be 2.0mm/s.Printing syringe needle a diameter of 0.1mm is set, it is each
The parallel printing of layer line bar, lines spacing 0.5mm.Printing adjusts the angle after completing one layer, makes 90 ° of adjacent layer angle, each
Angle between adjacent layer is identical, and interplanar spacing where lines is in each layer in plane where each layer of lines and adjacent layer
The scope of portion's lines spacing is 20%.15 layers are printed altogether, and the silicon rubber of loose structure is prepared.
(4) silicon rubber for the loose structure for preparing step 3 is pre- under the conditions of temperature is 50 DEG C and relative humidity is 70%
Cure 180min.Then, by porous silicone rubber in 1H, 1H, 2H that mass fraction is 10.0%, 2H- perfluoro decyl triethoxies
Dip-coating 3600s in the ethanol solution of silane finish, the dry 120min at a temperature of 25 DEG C, are then 150V in voltage, vacuum
Spend in the superthermal hydrogen storage equipment for 0.15Pa taking-up ethanol after handling 30s and soak 50min, it is then dry at a temperature of 25 DEG C
60min；Then 50min is soaked with deionized water, then that isotropism is prepared is super thin by dry 60min at a temperature of 25 DEG C
The superoleophobic silastic material of water.
＜ tests ＞
It is being the water droplet in 0 °, 45 °, 90 ° direction, water with the angle of the superiors lines to test the silastic material that is prepared
The contact angle size of dissolubility drop, oil droplet, if liquid-drop contact angle reaches more than 150 °, and drop is any on porous silicone rubber surface
The contact angle difference of both direction is respectively less than 5 °, and roll angle of the drop in 0 °, 45 °, 90 ° direction is below 10 °, then sample quilt
Think to show as isotropic super-hydrophobic superoleophobic feature.If by 120min ultrasounds strong destruction, 10000 mechanical bends
After destruction or 10000 mechanical friction destroy, the contact angle of drop remains to reach more than 150 °, and liquid in 0 °, 45 °, 90 ° of directions
The contact angle difference in porous silicone rubber surface any two direction is dropped in still less than 5 °, and drop is in the rolling in 0 °, 45 °, 90 ° direction
Dynamic angle is below 10 °, that is, shows as the super-hydrophobic superoleophobic feature of isotropism that stable mechanical resistant is destroyed, and sample is marked at this time
Qualification is denoted as, otherwise to be unqualified, test result is as shown in following table 1-2.Table 1 distills water droplet contact angle, roll angle test result
2 peanut oil droplet contact angle of table, roll angle test result
Claims (10)
1. a kind of method that the super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure, including following step
Suddenly：
（1）The silicone oil of the double bond containing C=C, inorganic nano-filler, catalyst, inhibitor mixed is uniform, the first mixture is obtained, is mixed
Conjunction process uses the one or more in ball milling, grinding or mechanical agitation；
（2）The first mixture prepared to step 1 adds containing hydrogen silicone oil, silicon rubber auxiliary agent, is uniformly mixed, obtains the second mixing
Material；By the second mixture deaeration, obtain printing and use " ink "；
（3）" ink " that step 2 is prepared loads 3D printer, is printed according to anisotropy loose structure feature, prepares
Obtain the silicon rubber of loose structure；
（4）The silicon rubber of loose structure prepared by step 3 carries out precuring processing；Then, by porous silicone rubber in inorganic agent
Cleaning is taken out after carrying out superthermal hydrogen processing after dip-coating, drying in solution, dries again, obtains the super-hydrophobic superoleophobic silicon of isotropism
Elastomeric material.
2. the side of the super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure according to claim 1
Method, it is characterised in that the silicone oil of the double bond containing C=C is vinyl silicone oil, divinyl silicone oil, methyl vinyl silicon oil, hydroxyl
Base vinyl silicone oil, phenyl-vinyl silicon oil, Tolyl-vinyl silicone oil, benzylidene vinyl silicone oil, methyl phenyl vinyl
One or more in base silicone oil, methyl ethylene trifluoro propyl silicone oil；
The inorganic nano-filler is silica, calcium silicates, calcium carbonate, titanium dioxide, carbon black, graphene, carbon nanotubes, illiteracy
One or more in de- soil, zinc oxide；
The inorganic nano-filler grain size is 1 ~ 5000 nm.
3. the side of the super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure according to claim 1
Method, it is characterised in that the inorganic nano-filler is as follows by pretreatment, preprocessing process：Use mass concentration for 0.1 ~
5.0% coupling agent first soaks 5 ~ 60 min, then dry 5 ~ 60 min at a temperature of 20 ~ 90 DEG C；
The coupling agent is alkane coupling agent or titanate coupling agent.
4. the side of the super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure according to claim 1
Method, it is characterised in that the catalyst is platinum catalyst；
The catalyst is DOW CORNING RD27 platinum catalysts, the DX-3080 platinums of Guangzhou great Xi chemical raw materials Co., Ltd
The many prosperous organosilicon materials of catalyst, the MC-999 platinum catalysts of Dongguan City Magotan rubber-plastics material Co., Ltd, Dongguan City are limited
One or more in the platinum catalyst of company, the PT-50 of Dongguan City Tian An silica gel Science and Technology Ltd.；
It is 0.001 ~ 0.5% that the catalyst, which is added to mass fraction in silicon rubber,；
The inhibitor is inhibitor containing alkynyl；
The inhibitor is 1- acetenyl -1- cyclohexanol, 2- methyl -3- butyne-2-alcohols, propargyl alcohol, 3- butyne-1-ols, 3,5-
One or more in dimethyl -1- hexin -3- alcohol, 3,7,11- trimethyl dodecyne -3- alcohol；
It is 0.001 ~ 0.5% that the inhibitor, which is added to mass fraction in silicon rubber,.
5. the side of the super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure according to claim 1
Method, it is characterised in that step 1, mixed process realizes that specific technological parameter is such as using one of ball milling, grinding or mechanical agitation
Under：
The parameter of ball milling mixing is 50 ~ 400 r/min of revolution, and 100 ~ 800 r/min of rotation, the time is 20 ~ 60 min；
The parameter of ground and mixed is 30 ~ 3000 r/min, and the time is 30 ~ 60 min；
Churned mechanically parameter is 100 ~ 3000 r/min, and the time is 30 ~ 60 min.
6. the side of the super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure according to claim 1
Method, it is characterised in that the containing hydrogen silicone oil is the silicone oil containing Si -- H, its hydrogen content mass fraction is 0.1 ~ 2.0%；
It is 20.0 ~ 40.0% that the silicone oil containing Si -- H, which is added to mass fraction in silicon rubber,；
The silicon rubber auxiliary agent for polytetrafluoroethylene (PTFE), polyvinylidene fluoride, 1H, 1H, 2H, 2H- perfluoro capryls trimethoxy silane,
1H, 1H, 2H, 2H- perfluoro capryl triethoxysilane, 1H, 1H, 2H, 2H- perfluoro decyls trimethoxy silane, 1H, 1H, 2H,
One or more in 2H- perfluoro decyl triethoxysilanes；
It is 5.0 ~ 20.0% that the silicon rubber auxiliary agent, which is added to mass fraction in silicon rubber,.
7. the side of the super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure according to claim 1
Method, it is characterised in that step 2, de-aeration uses vacuum defoamation；
Step 3, evacuation and centrifugal degassing is carried out before the second mixture adds 3D printer；
The evacuation and centrifugal degassing rotating speed is 2000 ~ 10000 r/min, and the time is 5 ~ 60 min.
8. the side of the super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure according to claim 1
Method, it is characterised in that step 3, carrying out printing according to anisotropic structure feature is：Set printing sandwich construction, each layer by
The a plurality of lines being parallel to each other are formed, and there are certain angle, angular range for the lines of adjacent layer（0~90]°；
The spacing of each layer of internal lines is 0.5 ~ 3.0 mm；
Step 3, printed according to anisotropic structure feature, the printing number of plies is 4-20 layers, is preferably 4-10 layers；
The diameter control of syringe needle is printed in 0.1 ~ 2.0 mm；
Interplanar spacing where lines is between each layer of internal lines in plane where controlling the lines of each layer of printing and adjacent layer
Away from scope be（0~50%]；
Step 3, during 3D printing, lines printing speed is 0.2 ~ 25.0 mm/s.
9. the side of the super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure according to claim 1
Method, it is characterised in that step 4, precuring processing procedure is：The silicon rubber that step 3 is printed to gained loose structure is placed in constant temperature
Precuring is carried out in constant humidity environment, porous silicone rubber is then subjected to superthermal hydrogen processing after dip-coating, drying in handling agent solution
Cleaning is taken out afterwards, is dried again, is obtained the super-hydrophobic superoleophobic silastic material of isotropism；
Step 4, precuring processing procedure is as follows：Silicon rubber is under the conditions of temperature is 20 ~ 90 DEG C and relative humidity is 20 ~ 100%
Handle 30-180 min；
Preferably, step 4, the mass fraction for handling agent solution is 5.0 ~ 20.0%；Inorganic agent is selected from polyvinylidene fluoride, methyl
Vinyl trifluoro propyl silicon rubber, 1H, 1H, 2H, 2H- perfluoro capryls trimethoxy silane, 1H, 1H, 2H, 2H- perfluoro capryls three
Ethoxysilane, 1H, 1H, 2H, 2H- perfluoro decyls trimethoxy silane, 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilanes
In one or more；
Preferably, step 4, it is dimethylacetylamide, in toluene, dimethylbenzene, methanol, ethanol to handle the solvent used in agent solution
One or more.
10. the super-hydrophobic superoleophobic silastic material of isotropism is prepared by anisotropic structure according to claim 1
Method, it is characterised in that step 4, the silastic material being prepared has following characteristic：
The liquid-drop contact angle of water droplet or water-soluble drop or oil droplet on porous silicone rubber reaches more than 150 °, and drop is porous
The contact angle difference in silastic surface any two direction is respectively less than 5 °, and the roll angle of drop in any direction is below 10 °；
It is described water solubility drop include but not limited to water paint, water-based ink, pH be 1 ~ 13 soda acid saline solution, sweat,
Blood, urine, oil-in-water emulsion,
Or oil droplet include but not limited to vegetable oil, animal oil, gasoline, diiodomethane drop, hexamethylene drop, single n-heptane droplet,
Water-in-oil emulsion；
By one kind or several in 120 min ultrasounds strong destructions, 10000 mechanical bends destructions or 10000 mechanical friction
After kind is destroyed, liquid-drop contact angle remains to reach more than 150 °, and drop is in the contact in porous silicone rubber surface any two direction
Angular difference is respectively less than 5 °, and the roll angle of drop in any direction is below 10 °.
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