CN107760091A - Wear-resisting fluorine silicon substrate super-amphiphobic coating of a kind of bottom surface integration and preparation method and application - Google Patents

Wear-resisting fluorine silicon substrate super-amphiphobic coating of a kind of bottom surface integration and preparation method and application Download PDF

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CN107760091A
CN107760091A CN201710867187.9A CN201710867187A CN107760091A CN 107760091 A CN107760091 A CN 107760091A CN 201710867187 A CN201710867187 A CN 201710867187A CN 107760091 A CN107760091 A CN 107760091A
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coupling agent
particle
super
fluorine silicon
nano
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CN107760091B (en
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宗立君
吴亚平
李辛庚
米春旭
王晓明
郭凯
张振岳
李文静
闫风洁
王蝶
樊志彬
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State Grid Corp of China SGCC
Electric Power Research Institute of State Grid Shandong Electric Power Co Ltd
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State Grid Corp of China SGCC
Electric Power Research Institute of State Grid Shandong Electric Power Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

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  • Wood Science & Technology (AREA)
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  • Paints Or Removers (AREA)
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Abstract

The invention discloses wear-resisting fluorine silicon substrate super-amphiphobic coating of a kind of bottom surface integration and preparation method and application, comprise the following steps：1) the modified synergic processing of two or more nano-particles, modified blending particle is obtained；2) blend modified Nano particle is added in dispersion solvent, the 2h of ultrasonic disperse 1, rear mechanical agitation；3) fluorine silicon resin is added into a certain amount of tert-butyl acetate, carries out shearing and disperse, obtain base material emulsion；4) the blend modified Nano particle suspension of step 2 and the base material emulsion of step 3 are mixed, adds coupling agent, heating stirring is disperseed, then disperseed using high speed shear dispersion machine, you can obtains super-amphiphobic coating；5) super-amphiphobic coating is stirred, is sprayed at body surface, drying at room temperature can successfully prepare wear-resisting integrated super-amphiphobic coating in 10 30 minutes.The mill ultra-amphosphobic organic inorganic hybridization coating that the present invention is formed by connecting by fluorine silicon base and blending and modifying particle using chemical graft copolyreaction.

Description

Wear-resisting fluorine silicon substrate super-amphiphobic coating of a kind of bottom surface integration and preparation method and application
Technical field
The invention belongs to super-amphiphobic coating preparation field, and in particular to a kind of wear-resisting fluorine silicon substrate super-amphiphobic of bottom surface integration applies Layer and preparation method and application.
Background technology
Super-hydrophobic coat refers to coat one or more layers super hydrophobic material in the surface of solids, with high water contact angle (> 150 °) and low roll angle (<10 °), realize its anticorrosion, waterproof and the function such as ice-covering-proof.Super-hydrophobic coat is due to excellent Good hydrophobicity, coated in outside hardware, reduce aqueous vapor and surround, anti-corrosion function can be realized；In sleet Snowfall In the case of, super hydrophobic surface keeps not icing condition or reduces the adhesive force of ice sheet, prevents or delays powerline ice-covering, is leading Line surface prepares the super-hydrophobic coat with durability anti-icing performance, is to realize actively ice-covering-proof economically viable technology.With Gradually stepping up for exploitation requirement of the people to new material, the material only with single super-hydrophobicity can not meet people's Demand, therefore multi-functional super-amphiphobic material is arisen at the historic moment.The design of super-double-hydrophobic surface is based primarily upon following two principles:When Migrated by fluorine atom to surface, make surface that there is extremely low surface energy, greasy dirt is not easy to bond on its surface；Second, urged by light Change degradation, make organic oil stain decomposition.The key for preparing super-double-hydrophobic surface is low-surface energy substance and surface roughness.It is super Double open coats can realize super-hydrophobic and superoleophobic function simultaneously, can significantly reduce the surface free energy of solid, have antifouling The characteristic such as dye, automatically cleaning, hydrophobic, oleophobic, lower resistance, low friction, super-amphiphobic coating is coated on power transmission and transforming equipment insulator, energy It is enough effectively to reduce filthy attachment and keep drying not wetted state, reinforced insulation performance, prevent pollution flashover accident.Due to most of Pollutant is all oil-soluble, therefore, has the self-cleaning surface of super-double-thinning property, the surface than only having super-hydrophobic effect has more Big market application foreground.
But super-hydrophobic or super-amphiphobic coating is extended in practical application, still suffer from larger obstacle：(1) prepare at present Super-double-hydrophobic surface coarse structure is unstable, resistance and fingerprint resistance or wears no resistance, can be so that hydrophobic phenomenon disappears when being worn, and this is Because surface abrasion can cause microstructure to be destroyed, surface roughness can reduce；Furthermore surface abrasion may result in table The chemical composition of the low-surface energy substance in face changes, and causes the performance of super-double-hydrophobic surface to reduce or lose.But surface is thick Rough structural unstable basic reason is between micro-rough structure and substrate, the binding strength that micro-rough structure is mutual Low, coarse structure is easily destroyed.In consideration of it, there is not the super-amphiphobic coating for obtaining broad practice also at present；(2) super-amphiphobic Coating usually requires the plant equipment of costliness, and preparation technology is complicated, and production cost is higher, significantly limit super-hydrophobic coat Using；(3) super-amphiphobic coating usually requires being applied in combination, it is necessary to special complete curing agent is used in combination of two layers of bottom surface paint, It is difficult in actual applications so that repairing maintenance；(4) coating needs thermally treated, and crosslinking curing temperature is higher, actually should Carried out curing of coatings with middle using high temperature and undoubtedly added difficulty of construction.
In summary, super-amphiphobic coating existing a series of problems in practical application, still shortage are effective in the prior art Solution.
The content of the invention
For being worn no resistance existing for above-mentioned super-amphiphobic coating in the prior art, preparation technology is complicated, cost is high and dimension The problems such as nurse's skill is cumbersome, there is provided the preparation method of particle is blended in a kind of modified synergic for fluorine silicon substrate super-amphiphobic coating, no Nano-particle of the same race is added in resin in a manner of nano modification particle is blended, be capable of balanced various nano-particles it is unfavorable because Element, and the respective advantage of nano-particle can be played, while the addition of nano-particle can be increased substantially, it is microcosmic thick to improve coating Rough structure, improve the performances such as hydrophobicity, oleophobic property, chemical stability, weatherability, corrosion resistance and the inoxidizability of coating.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
The preparation method of particle is blended in a kind of modified synergic for fluorine silicon substrate super-amphiphobic coating, comprises the following steps：
1) weigh selected from micron silica, nanometer grade silica, Nano titanium dioxide, nanoscale alchlor Two or more particles, be well mixed after, ball-milling treatment, be made blending ball-milled powder；
2) blending ball-milled powder is added in organic solvent, shearing mixes, and adds surfactant thereto, and mixing is equal It is even；
3) coupling agent of prehydrolysis is added in the pre-dispersed blending ball-milled powder solution prepared in step 2), heating, Generation graft reaction, obtain modified synergic blending particle.
Blending nano modification particle is cooperateed with by surfactant with coupling agent to be modified, it is possible to increase inorganic nanometer-powder The degree of modification of body, fully change its surface nature, strengthen its compatibility with organic matrix.
Preferably, in step 1), the ball mill that ball milling uses is planetary ball mill, Ball-milling Time 1-3h.
Preferably, in step 2), the organic solvent is absolute ethyl alcohol.
Preferably, in step 2), the rotating speed for shearing mixing is 6krpm-10krpm, and the time of shearing is 10-30min.
It is further preferred that in step 2), the mixing speed added after surfactant is 500-800rpm.
For ensure the modified effect in later stage, it is necessary to the particle with tendency of reuniting is carried out it is pre-dispersed, it is scattered using shearing Agglomerated particles can be made to obtain fine dispersion, and netted inorganic particulate is cut into short and small chain, then in stirring at low speed shape Surfactant is added under state, surfactant can effectively be coated on micro-nano particle surface, and due to surfactant chain Space steric effect so that the particulate of absorption surface activating agent is not easy close each other, therefore can effectively prevent particle aggregation；Adopt It is to avoid the effect of high shear weakening surfactant with stirring at low speed.
Still more preferably, in step 2), the surfactant is anion surfactant-allyloxy nonyl Phenol polyethenoxy ether ichthyodin (DNS-86).This kind of surfactant is easily adsorbed to micro-nano powder surface.
Preferably, in step 3), the pre-hydrolysis method of the coupling agent of prehydrolysis is that it is 3-4's that coupling agent is dissolved in into pH value In ethanol water, ultrasonic disperse 5-10min, it is fully hydrolyzed coupling agent.
It is further preferred that in step 3), in the ethanol water, the volume ratio of ethanol and deionized water is 9:1- 19:1。
Preferably, in step 3), the coupling agent is silane coupler or silicon fluoride coupling agent, and the silane coupler is VTES, glycidoxypropyltrimethoxysilane alkane, (methacryloxy) propyl trimethoxy Silane or mercaptopropyltriethoxysilane；The silicon fluoride coupling agent is ten difluoro heptyl propyl trimethoxy silicanes, ten trifluoros Octyltri-ethoxysilane or perfluoro decyl triethoxysilane.
It is further preferred that the concentration of the coupling agent of the prehydrolysis is 3%-6%.Concentration herein is mass fraction.
Because silane coupler or the hydrolysis of silicon fluoride coupling agent need a certain amount of water, if moisture deficit, hydrolyze not Fully；If water is excessive, the silanol of silane coupler or the hydrolysis generation of silicon fluoride coupling agent can be sent out in the presence of enough water Raw dehydrating condensation, ultimately generates the netted polysiloxanes of build, loses the modifying function to inorganic micro-nano particle.The coupling agent Concentration is 3%-6%, and silane coupler or silicon fluoride coupling agent are configured into alcohol-water solution, can make silane coupler or fluorine silicon Alkane coupling agent is uniform in inorganic micro nano powder surface distributed, and can reach again reduces silane coupler or silicon fluoride coupling agent usage amount Purpose, and suitable concentration may be such that inorganic micro-nano particle surface coats the silane coupler or silicon fluoride to form suitable thickness Coupling agent molecule layer, efficient coupling can be carried out with organic polymer.
Preferably, in step 3), the temperature of graft reaction is 70 DEG C -100 DEG C, reaction time 6-12h, and stir speed (S.S.) is 600-1000r/min。
Preferably, in step 3), the feed postition of the coupling agent of the prehydrolysis is dropwise addition.It can make idol using technique is added dropwise Connection agent is fully dispersed, and coupling agent fully contacts with micro-nano particle, realizes good modified effect.
Preferably, the preparation method also includes carrying out the modified synergic blending particle being prepared separation of solid and liquid, clear The step of washing and drying.
It is further preferred that the cleaning step is that centrifugation is cleaned into 10-30min using supersonic wave cleaning machine, weight It is multiple to carry out three times.
It is further preferred that the temperature of drying is 80-105 DEG C, the time of drying is 12-24h.
Modified synergic blending particle preparating mechanism is that, by carrying out ball-milling treatment to a variety of micro-nano particles, can change micro-nano The surface physics activated state of particle, is adsorbed each other, so that two kinds of micro-nano particles of different nature are fully mixed Close uniform.Such as, lightweight Nano-meter SiO_2 can be made2The larger TiO with density2It is sufficiently mixed, you can realize that density difference is larger The mixing of particle.Blending micro-nano particle is carried out it is pre-dispersed break the micro-nano particle agglomerating force of itself, before ensureing modified-reaction Micro-nano particle has preferably dispersiveness.The blend modified Nano particle being prepared is by using coupling agent to nanoparticle sublist Face is modified, and eliminates the hydroxyl of nanoparticle surface, weakens its hydrophily, it is often more important that silane coupler or silicon fluoride Different nano-particles is attached by coupling agent by the chemical bond of itself, and it is scattered uneven because density is different to change it The problem of, it drastically reduce the area the agglomeration of nano-particle in itself.
In addition, using silane coupler or the hydrophilic radical on silicon fluoride coupling agent surface, the hydroxyl on surface is with receiving after hydrolysis Dehydration condensation occurs for the hydroxyl on rice corpuscles surface, and two or more inorganic particles are connected, and solves it due to density not The problem of scattered uneven together, and lipophilic group is grafted to inorganic particle surfaces, inorganic particle hydrophily feature is improved, and The compatibility of inorganic particle and organic environment is improved, effectively eliminates the reunion between inorganic nanoparticles, is improved point Dissipate property.
By taking the blending and modifying of particle 1 and particle 2 as an example, its mechanism of modification is as follows：
First, using ball-milling treatment, the surface-active state of particle 1 and the nano particle of particle 2 is changed so that mutually Mutually depend on, be sufficiently mixed so that the different two kinds of nano-particles of property are realized.
In addition, using silane coupler to the two progress modified synergic processing, hydrolysis occurs for silane coupler, as follows Shown in formula：
Wherein, R is the lipophilic group of silane coupler, and X is hydrolyzable groups.
Then, multistep dehydration condensation occurs between the hydroxyl and inorganic particle of particle surface, ultimately forms blending and changes Property particle, is shown below：
By ball-milling treatment, the two can be sufficiently mixed, and there is certain absorption affinity.Therefore, ball milling powder is entirely blended The particle that may have in opisthosoma system has the stuff and other stuff of cladding formation of the modified small particles to big particle, particle 1 to change with particle 2 Learn the stuff and other stuff that grafting is formed.
Second object of the present invention is to provide the above-mentioned modified synergic for fluorine silicon substrate super-amphiphobic coating and particle is blended The modified synergic blending particle that preparation method is prepared.
Third object of the present invention is to provide a kind of fluorine silicon substrate super-amphiphobic coating, by above-mentioned modified synergic be blended particle, Fluorine silicon resin is prepared with coupling agent reaction.
Preferably, the coupling agent is KH550, KH792, KH560 or KH570.
It is further preferred that the mass ratio of the coupling agent and fluorine silicon resin is 1:20-1:15.
Preferably, the mass ratio of the modified synergic blending particle and fluorine silicon resin is 1:1-1:3.
Fourth object of the present invention is to provide the preparation method of above-mentioned fluorine silicon substrate super-amphiphobic coating, comprises the following steps：
1) modified synergic blending particle is added in dispersion solvent, and adds dispersant thereto, shearing is scattered, obtains To suspension；
2) tert-butyl acetate is added into fluorine silicon resin, shearing is scattered, obtains base material emulsion；
3) suspension and base material emulsion are mixed, coupling agent is added into mixed liquor, and it is scattered in shearing During add defoamer, produce fluorine silicon substrate super-amphiphobic coating.
Preferably, in step 1), the weight ratio of the modified synergic blending particle and dispersion solvent is 1:5-1:3.
It is further preferred that the dispersion solvent is butyl acetate, tert-butyl acetate, propylene glycol methyl ether acetate and acetic acid The mixed solution of ethyl ester, the weight ratio of each component are followed successively by 1:1-1.5:1.5-2:1.5-2.
Preferably, in step 1), the weight ratio of the modified synergic blending particle and dispersant is 15:1-20:1.
It is further preferred that the dispersant is BYK-163.
Preferably, in step 2), the weight ratio of fluorine silicon resin and tert-butyl acetate is 10:1-4:1.
Preferably, in step 2), it is 4000-7000r/min, time 0.5-1h to shear scattered speed, adjusts viscosity For 15-30s.
Preferably, in step 3), the weight ratio of modified synergic blending particle and fluorine silicon resin is 1:3-1:1.
Preferably, in step 3), the coupling agent is KH550, KH792, KH560 or KH570.
Preferably, in step 3), the defoamer is the defoamer of organosilicon 100.
Preferably, in step 3), after adding coupling agent into mixed liquor, 1-3h is dispersed with stirring at 40 DEG C -60 DEG C, then Disperse 0.5h-1.5h under 7000-10000rpm shear rates.
Nonionic surfactant is added because modified synergic is blended in particle preparation process, it is subsequently preparing coating mistake Effective emulsifying agent is may act as in journey, F-Si emulsion particles surface can be made to carry electric charge, can be led between micro-nano particle and organic polymer It is mutually compound to cross electrostatic interaction；And the lipophilic group of silane coupler can be connected with F-Si resins by chemical graft copolyreaction Connect.
1-3h is dispersed with stirring at 40 DEG C -60 DEG C, can effectively promote the performance of action of coupling agents, and cause system scattered It is more homogeneous.
The 5th purpose of the present invention is to provide a kind of preparation method of the wear-resisting fluorine silicon substrate super-amphiphobic coating of bottom surface integration, Comprise the following steps：After the super-amphiphobic coating is stirred, body surface is sprayed at, is produced after drying.
Preferably, the pressure of the spraying is 0.3MPa-0.6MPa, spray gun and coating of objects distance 10-30cm.
The 6th purpose of the present invention is to provide the bottom surface wear-resisting fluorine silicon substrate of integration that above-mentioned preparation method is prepared and surpassed Double open coats.
The present invention the 7th purpose be to provide above-mentioned super-amphiphobic coating and above-mentioned super-amphiphobic coating anticorrosion, waterproof, Automatically cleaning or it is ice-covering-proof in application.
The beneficial effects of the present invention are：
(1) blending nano modification particle is modified by using silane coupler to nanoparticle surface, eliminates nanometer The hydroxyl of particle surface, weaken its hydrophily, it is often more important that silane coupler is received different by the chemical bond of itself Rice corpuscles is attached, and is changed it and is disperseed the problem of uneven because density is different, drastically reduce the area nano-particle in itself Agglomeration.And the powder coating of blending nano modification particle just has preferable hydrophobic effect on the glass sheet.
(2) added in the emulsion of resin by the way that nano modification particle mode is blended, rather than mixed using follow-up mechanicalness Close, be capable of the unfavorable factor of balanced various nano-particles, and play respective advantage, increase substantially the addition of nano-particle Amount, improve filming performance of the formation of its micro-rough structure without influenceing resin.
(3) blending nano modification particle is cooperateed with by surfactant with silane coupler is modified, it is possible to increase nothing The degree of modification of machine nano-powder, fully change its surface nature, strengthen its compatibility with organic matrix.And micro-nano particle with Be present cross-linking polymerization in fluorine silicon base, connected by chemical graft copolyreaction so that have more between organic and inorganic materials Good compatibility, the use of silane coupler improves the adhesive property between coating and base material, therefore changes fluorine silicon coating The shortcomings that adhesion difference, adhesion is up to 1-2 levels between super-amphiphobic coating and substrate；
(4) super-amphiphobic coating prepared has excellent super-amphiphobic characteristic, and water contact angle can reach 155 ° -160 °, roll 1 ° -5 ° or so of angle, and for the alcohol water blend that concentration is 20%, contact angle is dredged up to more than 100 °, thus with good Oiliness, the advantages of being effectively combined micro nano structure and low surface energy fluorine silicon, so as to significantly improve the hydrophobicity of coating, oleophobic The performance such as property, chemical stability, weatherability, corrosion resistance, inoxidizability.
(5) super-amphiphobic coating wearability be improved significantly, nano modification particle has hydrophobicity in itself, passes through fluorine silicon tree Stacking turns into multiple nano composite structure between the chemical bonding of fat and non-single nano-particle is mutual, ensure that the wear-resisting of coating Property and long-term effect.
(6) the inventive method realizes bottom covering integration, and preparation technology is simple, safeguards and repairs simple possible, greatly The application cost of super-amphiphobic coating is reduced, super-amphiphobic coating can be effectively formed on a variety of matrixes, application method is simple, is not required to Exacting terms is wanted, is adapted to large-scale industrial production.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing further understanding of the present application, and the application's shows Meaning property embodiment and its illustrate be used for explain the application, do not form the improper restriction to the application.
Fig. 1 be for fluorine silicon substrate super-amphiphobic coating AFM patterns of the present invention, wherein, (a) is plan, and (b) is 3D shape appearance figures, It can be seen that micron order and nanoscale projection.
Fig. 2 is the hydrophobic effect figure of modified blending ball milling micro-nano powder.
Fig. 3 is fluorine silicon substrate super-amphiphobic coating surface of the present invention to the contact angle picture between water and 20% alcohol, wherein 1- Water droplet, 2-20% alcohol drops.
Fig. 4 is the water contact angle of fluorine silicon substrate super-amphiphobic coating of the present invention.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
Embodiment 1：The wear-resisting fluorine silicon substrate-micro-nano SiO of bottom surface integration2Super-amphiphobic coating preparation technology
1. the modified synergic of micron silica and nano silicon is handled, modified blending micro-nano SiO is obtained2Particle.
(1) preparation of ball milling micro-nano powder is blended：Weigh a certain amount of micron order SiO2With nanoscale SiO2Two kinds of particles, It is placed in batch mixer and is well mixed, be subsequently placed in planetary ball mill ball-milling treatment 2h, blending ball milling micro-nano powder is made.
(2) the pre-dispersed of micro-nano particle is blended：Blending ball milling micro-nano powder is dissolved in absolute ethyl alcohol, 6krpm speed The scattered 20min of shearing, it is 500rpm to switch to low-speed machinery stir speed (S.S.), adds a small amount of surfactant D NS-86, stirring 20min。
(3) prehydrolysis of coupling agent：Ten difluoro heptyl propyl trimethoxy silicanes are dissolved in ethanol and deionized water ratio For 9:It is 3 using acetic acid adjustment pH value in 1 mixed solution, ultrasonic disperse 5min so that coupling agent is fully hydrolyzed.
(4) preparation of modified synergic blending particle：Ten difluoro heptyl propyl trimethoxy silicanes of prehydrolysis are added dropwise to In pre-dispersed blending micro-nano particle, the two graft reaction of agitating and heating promotion, 80 DEG C, speed 600r/min of heating-up temperature, when Between 6h.
(5) centrifugal treating, drying：The suspension that step (4) is obtained carries out centrifugal treating, and is repeatedly rushed with absolute ethyl alcohol Centrifugal treating again after washing, is finally placed in the dry 20h of 80 DEG C of drying box.
What is be prepared is modified the hydrophobic effect figure that ball milling micro-nano powder is blended as shown in Fig. 2 water droplet is dropped on powder, The effect for balling-up of dripping is presented, illustrates powder after modification, there is preferable hydrophobic effect.
2. blending and modifying micro-nano silicon dioxide granule is added in dispersion solvent, weight ratio is 1:5, and add dispersant B YK- 163 carry out ultrasonic disperse 1.5h, rear to carry out mechanical agitation 1h.Dispersion solvent is butyl acetate, tert-butyl acetate, propylene glycol monomethyl ether The mixed solution of acetate and ethyl acetate, weight ratio are 1:1:2:1.5.Blend modified Nano particle and dispersant B YK-163 Weight ratio be 15:1.
3. fluorine silicon resin is added into a certain amount of tert-butyl acetate, weight ratio is 10:1, carry out shearing and disperse, shear rate 7000r/min, time 1h, regulation viscosity are 30s, obtain base material emulsion.
4. the blending and modifying micro-nano silicon dioxide granule suspension of step 2 and the base material emulsion of step 3 are mixed, Wherein the weight of blend modified Nano particle and fluorine silicon resin ratio is 1:3.Coupling agent KH792 is added, heating-up temperature is 40 DEG C, is stirred Scattered 3h is mixed, is then disperseed using high speed shear dispersion machine, speed 10000rpm, shear time 1.5h, in shear history Middle addition defoamer, you can obtain super-amphiphobic coating.Weight ratio between KH792 and resin is 1:20.The defoamer is organic The defoamer of silicon 100.
5. prepared by super-amphiphobic coating：Super-amphiphobic coating is stirred, is sprayed at body surface, drying at room temperature 30 minutes is i.e. The wear-resisting fluorine silicon substrate-micro-nano silica super-amphiphobic coating of wear-resisting bottom surface integration can successfully be prepared.The spray pressure is 0.3MPa-0.4MPa, spray gun and coating of objects distance 15cm.
The present embodiment utilizes the hydrolysis of the difluoro heptyl propyl trimethoxy silicane of silicon fluoride coupling agent ten and micro-nano SiO2Between Condensation reaction, form blending and modifying micro-nano SiO2Particle, by two kinds of various sizes of micro-nano SiO2Connection, solve its due to Density is different and disperses the problem of uneven, and lipophilic group is grafted into inorganic particle surfaces, improves inorganic particle hydrophily Feature, and the compatibility of inorganic particle and organic environment is improved, the reunion between inorganic nanoparticles is effectively eliminated, is improved Dispersiveness.Wherein blending and modifying particle such as following formula：
Wherein R is the lipophilic group of ten difluoro heptyl propyl trimethoxy silicanes.
The AFM patterns of fluorine silicon substrate super-amphiphobic coating prepared by the embodiment are as shown in figure 1, wherein, and (a) is plan, (b) For 3D shape appearance figures, it is seen that coating has regular micro-nano coarse structure, and convex-concave is orderly, is also dispersed with larger bulge-structure Small bulge-structure.The compound diadactic structure of this micro-nano just because of the surface of solids can form substantial amounts of groove, can be effective Ground entrapped air, rustic degree is provided for the formation of hydrophobic surface.
The wear-resisting fluorine silicon substrate-micro-nano silica super-amphiphobic coating of bottom surface integration manufactured in the present embodiment has excellent surpass Double thin characteristics, water contact angle can be to 152 °, 2 ° or so of roll angle, and for 20% alcoholic solution, and contact angle is up to 100 °, such as Shown in Fig. 3 and Fig. 4.Adhesion is up to 2 grades between substrate, and after finger or Sandpapering, ultra-amphosphobic can remain to continue to protect Hold.
Embodiment 2：The wear-resisting fluorine silicon substrate-nano-TiO of bottom surface integration2-SiO2Super-amphiphobic coating preparation technology
1. nano-TiO2With Nano-meter SiO_22Modified synergic processing, obtain being modified TiO2-SiO2Nano-particle
(1) preparation of ball milling micro-nano powder is blended：Weigh two kinds of a certain amount of nanometer grade silica, Nano titanium dioxide Particle, it is placed in batch mixer and is well mixed, be subsequently placed in planetary ball mill ball-milling treatment 2h, blending ball milling micro-nano powder is made End.Nanoscale TiO2With nanoscale SiO2Weight ratio between particle is 1:2.
(2) the pre-dispersed of micro-nano particle is blended：Blending ball milling micro-nano powder is scattered in absolute ethyl alcohol, 8krpm speed The scattered 30min of rate shearing, it is 600rpm to switch to low-speed machinery stir speed (S.S.), adds a small amount of surfactant D NS-86, stirring 25min。
(3) prehydrolysis of VTES coupling agent：VTES coupling agent is dissolved in second Alcohol is 19 with deionized water:In 1 mixed solution, using acetic acid by pH value be 4, ultrasonic disperse 10min so that coupling agent is abundant Hydrolysis.
(4) modified synergic TiO2-SiO2The preparation of nano-particle：The coupling agent of prehydrolysis is added dropwise to pre-dispersed blending In micro-nano particle, agitating and heating promotes the two graft reaction, 80 DEG C, speed 700r/min, time 8h of heating-up temperature.Using dropwise addition Technique can make coupling agent fully dispersed, and coupling agent fully contacts with micro-nano particle, realize good modified effect.
(5) centrifugal treating, drying：The suspension that step (4) is obtained carries out centrifugal treating, and is repeatedly rushed with absolute ethyl alcohol Centrifugal treating again after washing, is finally placed in the dry 12h of 105 DEG C of drying box.
2. TiO is blended2-SiO2Nano-particle is added in dispersion solvent, and weight ratio is 1:3, and add dispersant B YK-163 Ultrasonic disperse 2h is carried out, it is rear to carry out mechanical agitation 2h.Dispersion solvent is butyl acetate, tert-butyl acetate, propylene glycol monomethyl ether acetic acid The mixed solution of ester and ethyl acetate, weight ratio are 1:1.5:2:1.5.Blend modified Nano particle is with dispersant B YK-163's Weight ratio is 18:1.
3. fluorine silicon resin is added into a certain amount of tert-butyl acetate, weight ratio is 10:1, carry out shearing and disperse, shear rate 5000r/min, time 0.7h, regulation viscosity are 20s, obtain base material emulsion.
4. by the blending and modifying TiO of step 22-SiO2Nano-particle suspension and the mixing of the base material emulsion of step 3, Wherein the weight of blend modified Nano particle and fluorine silicon resin ratio is 4:5.Coupling agent KH560 is added, heating-up temperature is 50 DEG C, is stirred Scattered 2h is mixed, is then disperseed using high speed shear dispersion machine, speed 8000rpm, shear time 1.5h, in shear history Add defoamer organosilicon 100, you can obtain super-amphiphobic coating.Weight ratio between KH560 and resin is 1:20.
5. prepared by super-amphiphobic coating：Super-amphiphobic coating is stirred, is sprayed at body surface, drying at room temperature 10 minutes is i.e. The wear-resisting fluorine silicon substrate-nano-TiO of wear-resisting bottom surface integration can successfully be prepared2-SiO2Super-amphiphobic coating.The spray pressure is 0.4MPa, spray gun and coating of objects distance 13cm.
The present embodiment is hydrolyzed using silane coupling agent vinyl triethoxysilane coupling agent and Nano-meter SiO_22With nano-TiO2 Between condensation reaction, form blend modified Nano TiO2-SiO2, by two kinds of TiO2-SiO2Nano-particle connects, and solves it Disperse the problem of uneven because density is different, and lipophilic group is grafted to inorganic particle surfaces, improve inorganic particle parent Water-based feature, and the compatibility of inorganic particle and organic environment is improved, the reunion between inorganic nanoparticles is effectively eliminated, Improve dispersiveness.Wherein blending and modifying particle such as following formula：
Wherein R is the lipophilic group of VTES coupling agent.
The wear-resisting fluorine silicon substrate-micro-nano TiO of bottom surface integration manufactured in the present embodiment2-SiO2Super-amphiphobic coating has excellent surpass Double thin characteristics, water contact angle can be to 151 °, 2 ° or so of roll angle, and for 20% alcohol, and contact angle is up to 100 °.With substrate it Between adhesion up to 2 grades, after finger or Sandpapering, ultra-amphosphobic can remain to continue to keep.
Embodiment 3：The wear-resisting fluorine silicon substrate-nanometer Al of bottom surface integration2O3-SiO2Super-amphiphobic coating preparation technology
1. nanometer Al2O3With Nano-meter SiO_22Modified synergic processing, obtain Modification on Al2O3-SiO2Nano-particle
(1) preparation of ball milling micro-nano powder is blended：Weigh two kinds of a certain amount of nanometer grade silica, nanoscale alchlor Particle, it is placed in batch mixer and is well mixed, is placed in batch mixer and is well mixed, be subsequently placed in planetary ball mill ball-milling treatment 2h, blending ball milling micro-nano powder is made.Nanoscale Al2O3With nanoscale SiO2Weight ratio between particle is 3:1.
(2) the pre-dispersed of micro-nano particle is blended：Blending ball milling micro-nano powder is scattered in absolute ethyl alcohol, 8krpm speed The scattered 30min of rate shearing, it is 600rpm to switch to low-speed machinery stir speed (S.S.), adds a small amount of surfactant D NS-86, stirring 25min。
(3) prehydrolysis of coupling agent：By (methacryloxy) propyl trimethoxy silicane coupling agent be dissolved in ethanol with Deionized water is 9:In 1 mixed solution, using acetic acid by pH value be 4, ultrasonic disperse 7min so that coupling agent is fully hydrolyzed..
(4) modified synergic Al2O3-SiO2The preparation of nano-particle：The coupling agent of prehydrolysis is added dropwise to pre-dispersed blending In micro-nano particle, agitating and heating promotes the two graft reaction, 70 DEG C, speed 800r/min, time 9h of heating-up temperature.Using dropwise addition Technique can make coupling agent fully dispersed, and coupling agent fully contacts with micro-nano particle, realize good modified effect.
(5) centrifugal treating, drying：The suspension that step (4) is obtained carries out centrifugal treating, and is repeatedly rushed with absolute ethyl alcohol Centrifugal treating again after washing, is finally placed in the dry 20h of 100 DEG C of drying box.
2. Al is blended2O3-SiO2Nano-particle is added in dispersion solvent, and weight ratio is 1:4, and add dispersant B YK-163 Ultrasonic disperse 1h is carried out, it is rear to carry out mechanical agitation 2h.Dispersion solvent is butyl acetate, tert-butyl acetate, propylene glycol monomethyl ether acetic acid The mixed solution of ester and ethyl acetate, weight ratio are 1:1.5:1:1.5.Blend modified Nano particle is with dispersant B YK-163's Weight ratio is 16:1.
3. fluorine silicon resin is added into a certain amount of tert-butyl acetate, weight ratio is 10:1, carry out shearing and disperse, shear rate 6000r/min, time 0.7h, regulation viscosity are 20s, obtain base material emulsion.
4. by the blending and modifying Al of step (2)2O3-SiO2The base material emulsion of nano-particle suspension and step (3) Mixing, the wherein weight of blend modified Nano particle and fluorine silicon resin ratio are 4:5.Add coupling agent aluminate coupling agent, heating Temperature is 50 DEG C, is dispersed with stirring 3h, is then disperseed using high speed shear dispersion machine, speed 8000rpm, shear time 1h, Defoamer organosilicon 100 is added in shear history, you can obtain super-amphiphobic coating.Weight between aluminate coupling agent and resin Than for 1:20.
5. prepared by super-amphiphobic coating：Super-amphiphobic coating is stirred, is sprayed at body surface, drying at room temperature 25 minutes is i.e. The wear-resisting fluorine silicon substrate-nanometer Al of wear-resisting bottom surface integration can successfully be prepared2O3-SiO2Super-amphiphobic coating.The spray pressure is 0.4MPa, spray gun and coating of objects distance 15cm.
The present embodiment is hydrolyzed using silane coupler (methacryloxy) propyl trimethoxy and Nano-meter SiO_22With receiving Rice Al2O3Between condensation reaction, form blend modified Nano Al2O3-SiO2, by two kinds of Al2O3-SiO2Nano-particle connects, and Lipophilic group is grafted to inorganic particle surfaces, improves inorganic particle hydrophily feature, and improve inorganic particle with it is organic The compatibility of environment, the reunion between inorganic nanoparticles is effectively eliminated, improves dispersiveness.Wherein blending and modifying particle is such as Following formula：
Wherein R is the lipophilic group of (methacryloxy) propyl trimethoxy silicane coupling agent：γ-metering system Acyloxy.
The wear-resisting fluorine silicon substrate-nanometer Al of bottom surface integration manufactured in the present embodiment2O3-SiO2Super-amphiphobic coating has excellent Super-amphiphobic characteristic, water contact angle can be to 150 °, 3 ° or so of roll angle, and for 20% alcohol, and contact angle is up to 100 °.With substrate Between adhesion up to 2 grades, after finger or Sandpapering, ultra-amphosphobic can remain to continue to keep.
Embodiment 4：The wear-resisting fluorine silicon substrate-nano-TiO of bottom surface integration2-Al2O3Super-amphiphobic coating preparation technology
1. nano-TiO2With nanometer Al2O3Modified synergic processing, obtain being modified TiO2-Al2O3Nano-particle
(1) preparation of ball milling micro-nano powder is blended：Weigh two kinds of a certain amount of Nano titanium dioxide, nanoscale alchlor Particle, it is placed in batch mixer and is well mixed, is placed in batch mixer and is well mixed, be subsequently placed in planetary ball mill ball-milling treatment 2h, blending ball milling micro-nano powder is made.Nanoscale Al2O3With nanoscale TiO2Weight ratio between particle is 1:2.
(2) the pre-dispersed of micro-nano particle is blended：Blending ball milling micro-nano powder is scattered in absolute ethyl alcohol, 8krpm speed The scattered 30min of rate shearing, it is 600rpm to switch to low-speed machinery stir speed (S.S.), adds a small amount of surfactant D NS-86, stirring 20min。
(3) prehydrolysis of coupling agent：By glycidoxypropyltrimethoxysilane alkane coupling agent be dissolved in ethanol and go from Sub- water is 9:In 1 mixed solution, using acetic acid by pH value be 4, ultrasonic disperse 7min so that coupling agent is fully hydrolyzed.
(4) modified synergic TiO2-Al2O3The preparation of nano-particle：The coupling agent of prehydrolysis is added dropwise to pre-dispersed blending In micro-nano particle, agitating and heating promotes the two graft reaction, 70 DEG C, speed 700r/min, time 10h of heating-up temperature.Using drop Processing skill can make coupling agent fully dispersed, and coupling agent fully contacts with micro-nano particle, realizes good modified effect.
(5) centrifugal treating, drying：The suspension that step (4) is obtained carries out centrifugal treating, and is repeatedly rushed with absolute ethyl alcohol Centrifugal treating again after washing, is finally placed in the dry 12-24h of 80 DEG C -105 DEG C of drying box.
2. TiO is blended2-Al2O3Nano-particle is added in dispersion solvent, and weight ratio is 1:4, and add dispersant B YK-163 Ultrasonic disperse 1.5h is carried out, it is rear to carry out mechanical agitation 2h.Dispersion solvent is butyl acetate, tert-butyl acetate, propylene glycol monomethyl ether vinegar The mixed solution of acid esters and ethyl acetate, weight ratio are 1:1.5:2:1.5.Blend modified Nano particle and dispersant B YK-163 Weight ratio be 17:1.
3. fluorine silicon resin is added into a certain amount of tert-butyl acetate, weight ratio is 10:1, carry out shearing and disperse, shear rate 5000r/min, time 0.7h, regulation viscosity are 20s, obtain base material emulsion.
4. by the blending and modifying TiO of step (2)2-Al2O3The base material emulsion of nano-particle suspension and step (3) Mixing, the wherein weight of blend modified Nano particle and fluorine silicon resin ratio are 4:5.Add coupling agent KH560, heating-up temperature 50 DEG C, 3h is dispersed with stirring, is then disperseed using high speed shear dispersion machine, speed 10000rpm, shear time 1.5h, is being sheared During add defoamer organosilicon 100, you can obtain super-amphiphobic coating.Weight ratio between KH560 and resin is 1:20.
5. prepared by super-amphiphobic coating：Super-amphiphobic coating is stirred, is sprayed at body surface, drying at room temperature 20 minutes is i.e. The wear-resisting fluorine silicon substrate-nano-TiO of wear-resisting bottom surface integration can successfully be prepared2-Al2O3Super-amphiphobic coating.The spray pressure is 0.4MPa, spray gun and coating of objects distance 10cm.
The present embodiment is hydrolyzed using silane coupler glycidyl ether propyl trimethoxy and nano-TiO2With nanometer Al2O3Between condensation reaction, form blend modified Nano TiO2-Al2O3, by two kinds of TiO2-Al2O3Nano-particle connects, and will Lipophilic group is grafted to inorganic particle surfaces, improves inorganic particle hydrophily feature, and improve inorganic particle and organic ring The compatibility in border, the reunion between inorganic nanoparticles is effectively eliminated, improves dispersiveness.Wherein blending and modifying particle is as follows Formula：
Wherein, R is the lipophilic group of glycidoxypropyltrimethoxysilane alkane coupling agent.
The wear-resisting fluorine silicon substrate-micro-nano TiO of bottom surface integration manufactured in the present embodiment2-Al2O3Super-amphiphobic coating has excellent Super-amphiphobic characteristic, water contact angle can be to 151 °, 4 ° or so of roll angle, and for 20% alcohol, and contact angle is up to 96 °.With substrate Between adhesion up to 2 grades, after finger or Sandpapering, ultra-amphosphobic can remain to continue to keep.
Embodiment 5：The wear-resisting fluorine silicon substrate-nano-TiO of bottom surface integration2-SiO2-Al2O3Super-amphiphobic coating preparation technology
1. nano-TiO2, Nano-meter SiO_22With nanometer Al2O3With modified synergic handle, obtain being modified TiO2-SiO2-Al2O3Receive Rice corpuscles
(1) preparation of ball milling micro-nano powder is blended：Weigh two kinds of a certain amount of Nano titanium dioxide, nanoscale alchlor Particle, it is placed in batch mixer and is well mixed, is placed in batch mixer and is well mixed, be subsequently placed in planetary ball mill ball-milling treatment 2h, blending ball milling micro-nano powder is made.Nanoscale TiO2, nanoscale SiO2With nanoscale Al2O3Weight ratio between particle is 1: 1.5:1。
(2) the pre-dispersed of micro-nano particle is blended：Blending ball milling micro-nano powder is scattered in absolute ethyl alcohol, 8krpm speed The scattered 30min of rate shearing, it is 600rpm to switch to low-speed machinery stir speed (S.S.), adds a small amount of surfactant D NS-86, stirring 20min。
(3) prehydrolysis of coupling agent：It is 9 that mercaptopropyltriethoxysilane coupling agent is dissolved in into ethanol with deionized water:1 In mixed solution, using acetic acid by pH value be 4, ultrasonic disperse 10min so that coupling agent is fully hydrolyzed.
(4) modified synergic TiO2-SiO2-Al2O3The preparation of nano-particle：The coupling agent of prehydrolysis is added dropwise to pre-dispersed Blending micro-nano particle in, agitating and heating promotes the two graft reaction, 70 DEG C, speed 800r/min, time 8h of heating-up temperature.Adopt With technique is added dropwise coupling agent can be made fully dispersed, coupling agent fully contacts with micro-nano particle, realizes good modified effect.
(5) centrifugal treating, drying：The suspension that step (4) is obtained carries out centrifugal treating, and is repeatedly rushed with absolute ethyl alcohol Centrifugal treating again after washing, is finally placed in the dry 12h of 105 DEG C of drying box.
2. TiO is blended2-SiO2-Al2O3Nano-particle is added in dispersion solvent, and weight ratio is 1:4, and add dispersant BYK-163 carries out ultrasonic disperse 1h, rear to carry out mechanical agitation 3h.Dispersion solvent is butyl acetate, tert-butyl acetate, propane diols first The mixed solution of ether acetate and ethyl acetate, weight ratio are 1:1:1.5:1.Blend modified Nano particle and dispersant B YK- 163 weight ratio is 18:1.
3. fluorine silicon resin is added into a certain amount of tert-butyl acetate, weight ratio is 10:1, carry out shearing and disperse, shear rate 5000r/min, time 0.7h, regulation viscosity are 25s, obtain base material emulsion.
4. by the blending and modifying TiO of step 22-SiO2-Al2O3The base material milkiness of nano-particle suspension and step 3 Liquid mixes, and wherein the weight of blend modified Nano particle and fluorine silicon resin ratio is 3:5.Coupling agent aluminate coupling agent is added, is added Hot temperature is 50 DEG C, is dispersed with stirring 2h, is then disperseed using high speed shear dispersion machine, speed 9000rpm, shear time 1.5h, defoamer organosilicon 100 is added in shear history, you can obtain super-amphiphobic coating.Between aluminate coupling agent and resin Weight ratio be 1:20.
5. prepared by super-amphiphobic coating：Super-amphiphobic coating is stirred, is sprayed at body surface, drying at room temperature 10 minutes is i.e. The wear-resisting fluorine silicon substrate-nano-TiO of wear-resisting bottom surface integration can successfully be prepared2-SiO2-Al2O3Super-amphiphobic coating.The spray pressure For 0.5MPa, spray gun and coating of objects distance 15cm.
The present embodiment is hydrolyzed using silane coupler mercaptopropyltriethoxysilane and nano-TiO2, Nano-meter SiO_22, nanometer Al2O3Between condensation reaction, form blend modified Nano TiO2-SiO2-Al2O3, by three kinds of TiO2-SiO2-Al2O3Nanoparticle Son connection, and lipophilic group is grafted to inorganic particle surfaces, inorganic particle hydrophily feature is improved, and improve inorganic particulate Grain and the compatibility of organic environment, effectively eliminate the reunion between inorganic nanoparticles, improve dispersiveness.Wherein blending changes Property particle such as following formula：
Wherein, R is the lipophilic group of mercaptopropyltriethoxysilane.
The wear-resisting fluorine silicon substrate-nano-TiO of bottom surface integration manufactured in the present embodiment2-SiO2-Al2O3Super-amphiphobic coating has excellent Different super-amphiphobic characteristic, water contact angle can be to 153 °, 1 ° or so of roll angle, and for 20% alcohol, and contact angle is up to 100 °.With Adhesion is up to 1 grade between substrate, and after finger or Sandpapering, ultra-amphosphobic can remain to continue to keep.
The preferred embodiment of the application is the foregoing is only, is not limited to the application, for the skill of this area For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.

Claims (10)

1. the preparation method of particle is blended in a kind of modified synergic for fluorine silicon substrate super-amphiphobic coating, it is characterised in that：Including such as Lower step：
1) weigh selected from micron silica, nanometer grade silica, Nano titanium dioxide, nanoscale alchlor two Kind or a variety of particles, after being well mixed, ball-milling treatment, blending ball-milled powder is made；
2) blending ball-milled powder is added in organic solvent, shearing mixes, and adds surfactant thereto, is well mixed；
3) coupling agent of prehydrolysis is added in the pre-dispersed blending ball-milled powder solution prepared in step 2), heated, occurred Graft reaction, obtain modified synergic blending particle.
2. preparation method according to claim 1, it is characterised in that：In step 2), the rotating speed for shearing mixing is 6krpm- 10krpm, the time of shearing is 10-30min；
Preferably, in step 2), the mixing speed added after surfactant is 500-800rpm；
It is further preferred that in step 2), the surfactant is anion surfactant-allyloxy polyoxyethylene nonyl phenyl Vinethene ichthyodin.
3. preparation method according to claim 1, it is characterised in that：In step 3), the prehydrolysis of the coupling agent of prehydrolysis Method is to be dissolved in coupling agent in the ethanol water that pH value is 3-4, ultrasonic disperse 5-10min, be fully hydrolyzed coupling agent；
Preferably, in step 3), in the ethanol water, the volume ratio of ethanol and deionized water is 9:1-19:1；
Preferably, in step 3), the coupling agent is silane coupler or silicon fluoride coupling agent, and the silane coupler is ethene Ethyl triethoxy silicane alkane, glycidoxypropyltrimethoxysilane alkane, (methacryloxy) propyl trimethoxy silicane Or mercaptopropyltriethoxysilane；The silicon fluoride coupling agent is ten difluoro heptyl propyl trimethoxy silicanes, ten trifluoro octyl groups Triethoxysilane or perfluoro decyl triethoxysilane；
It is further preferred that the concentration of the coupling agent of the prehydrolysis is 3%-6%.Concentration herein is mass fraction；
Preferably, in step 3), the temperature of graft reaction is 70 DEG C -100 DEG C, reaction time 6-12h, stir speed (S.S.) 600- 1000r/min；
Preferably, in step 3), the feed postition of the coupling agent of the prehydrolysis is dropwise addition.
4. preparation method according to claim 1, it is characterised in that：Also include grain is blended to the modified synergic being prepared Son carries out the step of separation of solid and liquid, cleaning and drying；
Preferably, the cleaning step is that centrifugation is cleaned into 10-30min using supersonic wave cleaning machine, is repeated three times；
Preferably, the temperature of drying is 80-105 DEG C, and the time of drying is 12-24h.
5. prepared by the preparation method of any modified synergic blending particles for fluorine silicon substrate super-amphiphobic coating of claim 1-4 Obtained modified synergic blending particle.
A kind of 6. fluorine silicon substrate super-amphiphobic coating, it is characterised in that：Modified synergic blending particle, fluorine silicon tree as described in claim 5 Fat is prepared with coupling agent reaction；
Preferably, the coupling agent is KH550, KH792, KH560 or KH570.
It is further preferred that the mass ratio of the coupling agent and fluorine silicon resin is 1:20-1:15.
Preferably, the mass ratio of the modified synergic blending particle and fluorine silicon resin is 1:1-1:3.
7. the preparation method of fluorine silicon substrate super-amphiphobic coating described in claim 6, it is characterised in that：Comprise the following steps：
1) modified synergic blending particle is added in dispersion solvent, and adds dispersant thereto, shearing is scattered, is hanged Turbid；
2) tert-butyl acetate is added into fluorine silicon resin, shearing is scattered, obtains base material emulsion；
3) suspension and base material emulsion are mixed, coupling agent is added into mixed liquor, and in shearing dispersion process Middle addition defoamer, produce fluorine silicon substrate super-amphiphobic coating.
8. preparation method according to claim 7, it is characterised in that：In step 1), modified synergic blending particle with The weight ratio of dispersion solvent is 1:5-1:3.
It is further preferred that the dispersion solvent is butyl acetate, tert-butyl acetate, propylene glycol methyl ether acetate and ethyl acetate Mixed solution, the weight ratio of each component is followed successively by 1:1-1.5:1.5-2:1.5-2.
Preferably, in step 1), the weight ratio of the modified synergic blending particle and dispersant is 15:1-20:1.
It is further preferred that the dispersant is BYK-163.
Preferably, in step 2), the weight ratio of fluorine silicon resin and tert-butyl acetate is 10:1-4:1.
Preferably, in step 2), it is 4000-7000r/min to shear scattered speed, and time 0.5-1h, regulation viscosity is 15- 30s。
Preferably, in step 3), the weight ratio of modified synergic blending particle and fluorine silicon resin is 1:3-1:1.
Preferably, in step 3), the coupling agent is KH550, KH792, KH560 or KH570.
Preferably, in step 3), the defoamer is the defoamer of organosilicon 100.
Preferably, in step 3), after adding coupling agent into mixed liquor, 1-3h, Ran Hou are dispersed with stirring at 40 DEG C -60 DEG C Disperse 0.5h-1.5h under 7000-10000rpm shear rates.
A kind of 9. preparation method of the wear-resisting fluorine silicon substrate super-amphiphobic coating of bottom surface integration, it is characterised in that：Comprise the following steps：Will After super-amphiphobic coating stirs described in claim 6, body surface is sprayed at, is produced after drying.
Preferably, the pressure of the spraying is 0.3MPa-0.6MPa, spray gun and coating of objects distance 10-30cm.
10. the wear-resisting fluorine silicon substrate super-amphiphobic coating of bottom surface integration that preparation method described in claim 9 is prepared；
Or, super-amphiphobic coating described in claim 6 and the super-amphiphobic coating anticorrosion, waterproof, automatically cleaning or it is ice-covering-proof in Application.
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