CN108192498A - Underwater superoleophobic automatically cleaning UV curing metals coating and its coating and preparation method and application - Google Patents
Underwater superoleophobic automatically cleaning UV curing metals coating and its coating and preparation method and application Download PDFInfo
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- CN108192498A CN108192498A CN201711307163.4A CN201711307163A CN108192498A CN 108192498 A CN108192498 A CN 108192498A CN 201711307163 A CN201711307163 A CN 201711307163A CN 108192498 A CN108192498 A CN 108192498A
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer
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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
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
Abstract
The invention belongs to UV curing materials technical fields, disclose a kind of underwater superoleophobic automatically cleaning UV curing metals coating and its coating and preparation method and the application in the fields such as smoke exhaust ventilator, non-stick pan, marine antifouling.Coating of the present invention is applied including primary coat knead dough, and primary coat is made of component A and component B.The present invention also provides a kind of coatings based on above-mentioned underwater superoleophobic automatically cleaning UV curing metal coating and preparation method thereof.Coating of the present invention can be in the application in the fields such as smoke exhaust ventilator, non-stick pan, marine antifouling.There is the composite construction of special nanometer and micron based on the metal coating obtained by coating of the present invention, there is hydrophilic polymer molecule brush configuration on the surface of composite construction, so that the coating has super hydrophilic super oleophylic in air, and superoleophobic property under water, it it is in air 0 ° to the contact angle of water and oil, 150 ° are more than to the contact angle of oil droplet under water, can be applied in the fields such as marine antifouling, smoke exhaust ventilator, non-stick pan.
Description
Technical field
The invention belongs to UV curing materials technical fields, more particularly to a kind of underwater superoleophobic automatically cleaning UV curing metals apply
Material and its coating and preparation method and the application in the fields such as smoke exhaust ventilator, non-stick pan, marine antifouling.
Background technology
At present, the research of special wettable surfaces mainly include super-hydrophobic, super hydrophilic, superoleophobic, super oleophylic, surpass parents,
It is super-amphiphobic, underwater superoleophobic etc., a series of progress is achieved, is obtained in daily life and industrial production
It is widely applied.Such as current self-cleaning material is mainly super hydrophilic or superhydrophobic surface material, has and is similar to lotus leaf surface
Self_cleaning effect；Superhydrophilic superoleophobic film or super oleophylic super-hydrophobic film obtain fabulous application in water-oil separating field.
Superhydrophilic superoleophobic, underwater superoleophobic surface in air, due to after being spontaneously wet out by water oil droplet cannot in its surface spreading,
The automatically cleaning effect of fabulous underwater greasy dirt can be obtained, so that underwater superoleophobic surface is not in smoke exhaust ventilator coating, glue
The fields such as pot coating, oceanographic equipment nonpolluting coating and water-oil separating are with a wide range of applications.
The surface tension of solid is bigger, easier to be soaked by liquid, and the wetability of liquid versus solid surfaces is mainly by surface
Chemical composition and surface geometry configuration determine.Therefore, to obtain ultraphobic surfaces must be provided simultaneously with two conditions：Low-surface-energy
Material and micro-nano binary coarse structure, so generally construction ultraphobic surfaces are there are mainly two types of method：It is constructed in low-energy surface
Coarse structure and the katakinetomere in rough surface grafting.Merely from the perspective of surface chemistry, super lyophilic surface is obtained
It is required that the surface tension of solid and liquid is relatively, and to obtain ultraphobic surfaces, it is desirable that solid surface tension is less than corresponding
The a quarter of surface tension of liquid.The surface tension of oil is all relatively low, and generally in 20~40mN/m, the surface tension of solid is general
Also than relatively low, so solid is all largely potential oleophilic drainage, solid surface tension it is minimum be fluoropolymer, at present
The minimum of report is 10.4mN/m, and fluorine-containing material can achieve the effect that hydrophobic oleophobic, and the surface tension of water is in all liquid
Highest (72.8mN/m) in body, if so preparing super oil-wetted surface, it is also very likely hydrophobic or super-hydrophobic simultaneously, so
Prepare super-hydrophobic super-oleophylic membrane material more relatively easily, and corresponding coarse structure only need to be constructed after the requirement for meeting surface tension
.
Existing superoleophobic material is both superoleophobic since the material preparation mainly using low-surface-energy forms
And it is super-hydrophobic, be a surface that cannot be soaked completely by most liquid, because having been used in preparation process big
The low-surface-energy fluorine material of amount, it is on the one hand expensive, cause such superoleophobic coating cost very high, on the other hand to environment
Toxic action with organism can not be assessed at present.
For the present invention from bionics, being prepared for surface has the underwater superoleophobic painting of hydrophilic polymer molecule brush configuration
Layer, when the ultra-hydrophilic surface with micro-nano compound structure contacts oil droplet, water can be first absorbed in micro-nano coarse structure, make its table
Unfold to form molecule brush configuration in water after the hydrophilic polymer molecule chain water absorption and swelling in face, lead to the shape of water/oil compound interface
Underwater superoleophobic property is shown into, this new compound interface, that is, the water being trapped in micro-nano coarse structure and hydrophilic poly-
Adduct molecule brush is the repulsion phase of oil droplet, plays the role of support oil droplet, prevents oil droplet from penetrating into surface of solids structure, so as to reach
Antifouling automatically cleaning effect.
Invention content
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide a kind of underwater super thin
Oily automatically cleaning UV curing metal coating.
Another object of the present invention is to provide a kind of painting based on above-mentioned underwater superoleophobic automatically cleaning UV curing metal coating
Layer.
Still a further object of the present invention is to provide the preparation method of above-mentioned coating.
Still a further object of the present invention be to provide above-mentioned underwater superoleophobic automatically cleaning UV curing metals coating in smoke exhaust ventilator, no
Application in the fields such as viscous pot, marine antifouling.
The purpose of the present invention is realized by following proposal：
A kind of underwater superoleophobic automatically cleaning UV curing metal coating, applies, primary coat is by component A and component B including primary coat knead dough
Composition, mass parts：
Component A includes：10~40 parts of 1,2- bis- (trimethoxy silicon substrate) ethane；500~700 parts of water；1~2 part of accelerating agent；
5~15 parts of stabilizers；50~80 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes；
Component B includes：15~25 parts of zirconium compounds；500~700 parts of water；Aluminium compound, the dosage of the aluminium compound is to adjust
The pH for saving component B is subject to 3~4；
Face, which applies, to be included：30~40 parts of propylene are acidified gallic acid；10~30 parts of propylene are acidified organic poly sesquisiloxane；10
~30 parts of simple function UV cure oligomer；10~20 portions of reactive diluents；1~10 part of photoinitiator.
The accelerating agent is accelerating agent commonly used in the art, can be acetic acid, nitric acid, hydrogen peroxide, molybdate
At least one of with cerium salt.
The stabilizer be stabilizer commonly used in the art, can be ethyl alcohol, methanol, glycerine, normal propyl alcohol,
At least one of isopropanol, methyl butynol and hexynol.
The zirconium compound is zirconium compounds commonly used in the art, preferably potassium fluorozirconate, sodium fluozirconate, fluorine
At least one of zirconic acid ammonium, fluorine zirconic acid and zirconium oxychloride.
Aluminium compound aluminium compound commonly used in the art, preferably aluminium chloride, aluminum nitrate and sulfuric acid
At least one of aluminium.
The reactive diluent be reactive diluent commonly used in the art, preferably hydroxy-ethyl acrylate,
The different ice of hydroxypropyl acrylate, lauryl acrylate, glycidyl methacrylate, isobornyl acrylate, methacrylic acid
At least one of piece ester and acrylic acid tetrahydrofuran methyl esters.
The photoinitiator is free radical photo-initiation, can be that free radical photo-initiation commonly used in the art is
Can, such as 1- hydroxycyclohexyl phenyl ketones (Irgacure-184), 2- hydroxy-2-methyl -1- phenylacetones (Irgacure-
1173), 2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- acetone (Irgacure-907), 2,4,6- front threes
In base benzoyl-diphenyl phosphine oxide (TPO), 2,4,6- trimethylbenzoyl phenyls phosphinic acid ethyl ester (TPO-L) at least
It is a kind of.
The simple function UV curing oligomer cures oligomer for simple function UV commonly used in the art, can be
At least one of methoxy polyethylene glycol acrylate and methoxy polyethylene glycol methacrylate-styrene polymer.
Further, the propylene acidification gallic acid described in coating of the present invention can be prepared by following methods：By two
First alcohol and gallic acid mixed catalytic esterification, obtain hydroxylating gallic acid；Again with (methyl) acrylic acid mixed catalytic ester
Change reaction, obtain the gallic acid of propylene acidification.
In the preparation method of the propylene acidification gallic acid：
The dihydric alcohol and the amount ratio that the amount ratio of gallic acid is that esterification reacts, such as can be molar ratio
0.5:1~1:0.5, preferably 0.9:1~1:1.
The hydroxylating gallic acid and the amount ratio that the amount ratio of (methyl) acrylic acid is that esterification reacts, it is excellent
It is selected as molar ratio 1:4~1:5.
The dihydric alcohol can be at least one of ethylene glycol, propylene glycol and butanediol.
The esterification preferably carries out under catalyst, and used catalyst is for esterification catalysts
Can, such as can be one kind in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid.
The reaction process preferably carries out under solvent environment, and more preferably gallic acid is first dissolved in solvent and is carried out again
Reaction, is preferably dissolved in acetone, preferably 1 mass parts gallic acid is dissolved in 5 parts by volume solvents, g/mL.
After the completion of the reaction, solvent can be removed by conventional methods such as vacuum distillations, obtain not having for product propylene acidification
Gallate-based.
Further, the acidification of propylene described in coating of the present invention organic poly sesquisiloxane (propylene is acidified POSS), specifically
For to cage modle organic poly sesquisiloxane (POSS) carry out propylene be acidified to obtain, can by by hydroxyl POSS or amino POSS with
(methyl) acrylic acid carries out esterification or neutralization reaction obtains.
The molar ratio of hydroxyl POSS or amino POSS used and (methyl) acrylic acid can be 1:8~1:9.
The present invention also provides a kind of coatings based on above-mentioned underwater superoleophobic automatically cleaning UV curing metal coating.
The present invention also provides a kind of preparation method of above-mentioned coating, by the way that primary coat is sprayed at substrate surface, after dry, then
Face is applied into dip-coating or is sprayed in primary coat, UV curings obtain underwater superoleophobic automatically cleaning UV curing metal coatings.
The UV cured times are preferably 3~5min.The cured UV optical wavelength of UV is preferably 245~405nm.
The drying can be to spontaneously dry.
It is described that primary coat is sprayed at substrate surface, concretely component A and B component are uniformly mixed, and profit is adjusted with acid
PH is 4~6, then is sprayed at substrate surface.
The acid can be acetic acid or nitric acid.
The component A can by by 10~40 parts of 1,2- bis- (trimethoxy silicon substrate) ethane, 500~700 parts of water, 1~2 part
Accelerating agent, 5~15 parts of stabilizers sequentially add mixing, and stirring 12~for 24 hours, add 50~80 parts of γ-glycidyl ether oxygens third
Base trimethoxy silane stirs 6~12h and obtains.
The B component is by the way that each component to be mixed to obtain.
The face is applied by the way that each component to be mixed to obtain.It is described to be mixed preferably in 1000~2000r/min
10~20min of lower dispersion.
The base material can be metal base.The base material is preferably polished, is cleaned using preceding.
There is the composite construction of special nanometer and micron based on the metal coating obtained by coating of the present invention, in composite construction
Surface on there is hydrophilic polymer molecule brush configuration so that the coating has super hydrophilic super oleophylic in air, and in water
Under superoleophobic property.The underwater superoleophobic metal coating of the present invention is in air 0 ° to the contact angle of water and oil, under water
150 ° are more than to the contact angle of oil droplet.
The underwater superoleophobic automatically cleaning UV curing metal coating of the present invention can be applied to marine antifouling, smoke exhaust ventilator, not glue
In the fields such as pot, so as to obtain underwater superoleophobic automatically cleaning UV curing metal coatings, the washing automated cleaning of greasy dirt is realized.
The present invention is had the following advantages and advantageous effect relative to the prior art：
(1) base material of the invention is metal base, and the finishing coat prepared is super-hydrophilic coating, therefore coating is easily to inhale
Water, the corrosion of base material in order to prevent has carried out base material the processing of organosilicon corrosion-inhibiting coating.Processing has with two big advantages,
One can have fabulous Corrosion Protection for the organic silicon coating with the phosphorating treatment on substituted metal surface；Second, due to protection
Primary coat is organosilicon material, and the POSS material in being applied with face has fabulous compatibility, has so that face is coated on base material
Fabulous adhesive force.
(2) natural reproducible resource gallic acid is introduced the preparation of coating by the present invention, has been synthesized a kind of biology base UV and has been consolidated
Change polyfunctional monomer, open new application field for natural material, improve its use value, alleviate the pressure of petrochemical industry
Power.
(3) film of the invention has high hardness, and up to 6H mainly has both sides reason.One is introduces
Inorganic component POSS can largely improve hardness of organic coating；Secondly it is by gallic acid and POSS in the present invention
Conversion is 4 energy degree and 8 degrees of functionality respectively, therefore POSS is after UV curings with organic component for UV curing monomers
Chemical crosslinking, and due to high degree of functionality, there is the high degree of cross linking after UV film-formings, so as to which film be made to have up to
The hardness of 6H.
Description of the drawings
Fig. 1 be embodiment 1 prepared by automatically cleaning metal coating in air in contact angle (a) air of water to oil
Contact angle (b) and under water to oil contact angle (c).
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Material involved in the following example can be obtained from commercial channel.
Embodiment 1
(1) the propylene acidification of gallic acid：The ratio for being dissolved in 5mL acetone according to every 1g gallic acids dissolves gallic acid
In acetone, after according to molar ratio 0.9:Ethylene glycol and gallic acid are carried out esterification by 1 ratio under sulfuric acid catalysis, are obtained
To hydroxylating gallic acid；By obtained hydroxylating gallic acid and acrylic acid according to molar ratio 1:5 ratio is urged in sulfuric acid
Agent effect is lower to carry out esterification, and vacuum distillation removes solvent acetone, obtains the gallic acid of propylene acidification；
(2) the propylene acidification of cage modle organic poly sesquisiloxane (POSS)：By hydroxyl POSS and acrylic acid in molar ratio 1:8
Ratio be esterified, obtain propylene acidification POSS；
(3) preparation of the metal base with organosilicon protective coating：It counts in parts by weight, takes 10 parts of 1,2-, bis- (front threes
Oxygroup silicon substrate) ethane add in 500 parts of deionized waters in mix, sequentially add 1 part of accelerating agent acetic acid and 5 parts of stabilizer alcohols,
After stirring 12h, 50 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes are added, continues to stir 6h, mixture is prepared
A；15 parts of zirconium compound potassium fluorozirconates are added in 500 parts of deionized waters and are mixed, is stirred, is added aluminium compound aluminium chloride and adjust
PH value is 3, you can mixture B is made；Mixture B obtained above under stirring is added in into mixture A, then passes through vinegar
It is 4 that acid, which controls mixed pH value, you can metallic substrate surface inorganic agent is made；Metal base is polished, it, will after cleaning up
Above-mentioned metallic substrate surface inorganic agent is sprayed at its surface, spontaneously dries to get to the Metal Substrate with organosilicon protective coating
Material.
(4) preparation of underwater superoleophobic UV curing metals coating：By step (1) obtained propylene acidification gallic acid,
Step (2) obtained propylene acidification organic poly sesquisiloxane, is lived at simple function UV curing oligomer (Taiwan Changxing EM3101)
It is coating material solidified that property diluent glycidyl methacrylate and photoinitiator TPO are uniformly mixed to obtain UV, mass ratio 40:
20:20:10:10；The coating material solidified use dip-coatings of above-mentioned UV or spray coating method are coated on to the metal base table prepared by step (3)
Face, UV curings are to get to underwater superoleophobic UV curing metals coating.
Using Dataphysics OCA40Micro type surface contact angles tester test in air water in coating surface
Contact angle, see Fig. 1 (a), oil is shown in Fig. 1 (b) in the contact angle of coating surface in air, underwater oil film surface contact angle,
See that Fig. 1 (c), Fig. 1 prove that the coating has super hydrophilic super oleophylic in air, underwater superoleophobic property.
Embodiment 2
(1) the propylene acidification of gallic acid：The ratio for being dissolved in 5mL acetone according to every 1g gallic acids dissolves gallic acid
In acetone, after according to molar ratio 1:Propylene glycol and gallic acid are carried out esterification by 1 ratio under hydrochloric acid catalysis, are obtained
Hydroxylating gallic acid；By obtained hydroxylating gallic acid and methacrylic acid according to molar ratio 1:5 ratio is in hydrochloric acid
Catalysis is lower to carry out esterification, and vacuum distillation removes solvent acetone, obtains the gallic acid of propylene acidification；
(2) the propylene acidification of cage modle organic poly sesquisiloxane (POSS)：By amino POSS and methacrylic acid by mole
Than 1:9 ratio carries out neutralization reaction, obtains propylene acidification POSS；
(3) preparation of the metal base with organosilicon protective coating：It counts in parts by weight, takes 40 parts of 1,2-, bis- (front threes
Oxygroup silicon substrate) ethane add in 700 parts of deionized waters in mix, sequentially add 2 parts of accelerating agent nitric acid and 15 parts of stabilizer methanol,
After stirring for 24 hours, 80 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes are added, continues to stir 12h, mixing is prepared
Object A；25 parts of zirconium compound sodium fluozirconates are added in 700 parts of deionized waters and are mixed, is stirred, is added aluminium compound aluminum nitrate and adjust
It is 4 to save pH value, you can mixture B is made；Mixture B obtained above under stirring is added in into mixture A, is then passed through
It is 6 that nitric acid, which controls mixed pH value, you can metallic substrate surface inorganic agent is made；Metal base is polished, after cleaning up,
Above-mentioned metallic substrate surface inorganic agent is sprayed at its surface, is spontaneously dried to get to the metal with organosilicon protective coating
Base material.
(4) preparation of underwater superoleophobic UV curing metals coating：By step (1) obtained propylene acidification gallic acid,
Step (2) obtained propylene acidification organic poly sesquisiloxane, is lived at simple function UV curing oligomer (Taiwan Changxing EM3102)
Property diluent hydroxy-ethyl acrylate and photoinitiator Irgacure-184 are uniformly mixed to obtain that UV is coating material solidified, and mass ratio is
40:19:30:10:1；The coating material solidified use dip-coatings of above-mentioned UV or spray coating method are coated on to the metal base table prepared by step (3)
Face, UV curings are to get to underwater superoleophobic UV curing metals coating.
Using Dataphysics OCA40Micro type surface contact angles tester test in air water in coating surface
Contact angle, oil is in the contact angle of coating surface in air, and underwater oil is in the contact angle of film surface, acquired results and embodiment 1
It is similar, it was demonstrated that the coating has super hydrophilic super oleophylic in air, underwater superoleophobic property.
Embodiment 3
(1) the propylene acidification of gallic acid：The ratio for being dissolved in 5mL acetone according to every 1g gallic acids dissolves gallic acid
In acetone, after according to molar ratio 1:1,4-butanediol and gallic acid are carried out esterification by 1 ratio under nitric acid catalysis,
Obtain hydroxylating gallic acid；By obtained hydroxylating gallic acid and acrylic acid according to molar ratio 1:4 ratio is in nitric acid
Catalysis is lower to carry out esterification, and vacuum distillation removes solvent acetone, obtains the gallic acid of propylene acidification；
(2) the propylene acidification of cage modle organic poly sesquisiloxane (POSS)：By hydroxyl POSS and acrylic acid in molar ratio 1:8
Ratio carry out esterification, obtain propylene acidification POSS；
(3) preparation of the metal base with organosilicon protective coating：It counts in parts by weight, takes 25 parts of 1,2-, bis- (front threes
Oxygroup silicon substrate) ethane adds in 600 parts of deionized waters and mixes, sequentially add 1.5 parts and promote agent hydrogen peroxides and 10 parts of stabilizers
Glycerine after stirring 18h, adds 65 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes, continues to stir 8h, be prepared into
To mixture A；20 parts of zirconium compound ammonium fluozirconates are added in 600 parts of deionized waters and are mixed, stirs, adds aluminium compound sulfuric acid
Aluminium simultaneously adjusts pH value as 3.5, you can mixture B is made；Mixture B obtained above is added in into mixture A under stirring,
Then it is 5 to control mixed pH value by acetic acid, you can metallic substrate surface inorganic agent is made；Metal base is polished, clearly
After wash clean, above-mentioned metallic substrate surface inorganic agent is sprayed at its surface, spontaneously dries and protects painting to get to organosilicon
The metal base of layer.
(4) preparation of underwater superoleophobic UV curing metals coating：By step (1) obtained propylene acidification gallic acid,
Step (2) obtained propylene acidification organic poly sesquisiloxane, is lived at simple function UV curing oligomer (Taiwan Changxing EM3101)
Property diluent hydroxypropyl acrylate and photoinitiator Irgacure-1173 are uniformly mixed to obtain that UV is coating material solidified, and mass ratio is
40:10:25:20:5；The coating material solidified use dip-coatings of above-mentioned UV or spray coating method are coated on to the metal base table prepared by step (3)
Face, UV curings are to get to underwater superoleophobic UV curing metals coating.
Using Dataphysics OCA40Micro type surface contact angles tester test in air water in coating surface
Contact angle, oil is in the contact angle of coating surface in air, and underwater oil is in the contact angle of film surface, acquired results and embodiment 1
It is similar, it was demonstrated that the coating has super hydrophilic super oleophylic in air, underwater superoleophobic property.
Embodiment 4
(1) the propylene acidification of gallic acid：The ratio for being dissolved in 5mL acetone according to every 1g gallic acids dissolves gallic acid
In acetone, after according to molar ratio 1:1,3-BDO and gallic acid are carried out esterification by 1 ratio under phosphoric acid catalyzed,
Obtain hydroxylating gallic acid；By obtained hydroxylating gallic acid and acrylic acid according to molar ratio 1:5 ratio is in phosphoric acid
Catalysis is lower to carry out esterification, and vacuum distillation removes solvent acetone, obtains the gallic acid of propylene acidification；
(2) the propylene acidification of cage modle organic poly sesquisiloxane (POSS)：By amino POSS and acrylic acid in molar ratio 1:9
Ratio carry out neutralization reaction, obtain propylene acidification POSS；
(3) preparation of the metal base with organosilicon protective coating：It counts in parts by weight, takes 40 parts of 1,2-, bis- (front threes
Oxygroup silicon substrate) ethane add in 500 parts of deionized waters in mix, sequentially adding 2 parts of accelerating agent molybdates and 15 parts of stabilizers just
Propyl alcohol after stirring for 24 hours, adds 80 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes, continues to stir 12h, be prepared
Mixture A；25 parts of zirconium compound fluorine zirconic acids are added in 700 parts of deionized waters and are mixed, stirs, adds aluminium compound aluminium chloride simultaneously
It is 4 to adjust pH value, you can mixture B is made；Mixture B obtained above is added in into mixture A, Ran Houtong under stirring
It is 6 that peracetic acid, which controls mixed pH value, you can metallic substrate surface inorganic agent is made；Metal base is polished, is cleaned up
Afterwards, above-mentioned metallic substrate surface inorganic agent is sprayed at its surface, spontaneously dried to get to the gold with organosilicon protective coating
Belong to base material.
(4) preparation of underwater superoleophobic UV curing metals coating：By step (1) obtained propylene acidification gallic acid,
Step (2) obtained propylene acidification organic poly sesquisiloxane, is lived at simple function UV curing oligomer (Taiwan Changxing EM3102)
Property diluent lauryl acrylate and photoinitiator Irgacure-907 are uniformly mixed to obtain that UV is coating material solidified, and mass ratio is
35:20:20:15:10；The coating material solidified use dip-coatings of above-mentioned UV or spray coating method are coated on to the metal base prepared by step (3)
Surface, UV curings are to get to underwater superoleophobic UV curing metals coating.
Using Dataphysics OCA40Micro type surface contact angles tester test in air water in coating surface
Contact angle, oil is in the contact angle of coating surface in air, and underwater oil is in the contact angle of film surface, acquired results and embodiment 1
It is similar, it was demonstrated that the coating has super hydrophilic super oleophylic in air, underwater superoleophobic property.
Embodiment 5
(1) the propylene acidification of gallic acid：The ratio for being dissolved in 5mL acetone according to every 1g gallic acids dissolves gallic acid
In acetone, after according to molar ratio 1:Ethylene glycol and gallic acid are carried out esterification by 1 ratio under catalyst action, are obtained
To hydroxylating gallic acid；By obtained hydroxylating gallic acid and acrylic acid according to molar ratio 1:4 ratio is in catalyst
Effect is lower to carry out esterification, and vacuum distillation removes solvent acetone, obtains the gallic acid of propylene acidification；
(2) the propylene acidification of cage modle organic poly sesquisiloxane (POSS)：By hydroxyl POSS and methacrylic acid by mole
Than 1:8 ratio carries out esterification, obtains propylene acidification POSS；
(3) preparation of the metal base with organosilicon protective coating：It counts in parts by weight, takes 40 parts of 1,2-, bis- (front threes
Oxygroup silicon substrate) ethane add in 700 parts of deionized waters in mix, sequentially add 2 portions of accelerating agent cerium salt and 15 parts of stabilizer isopropyls
Alcohol after stirring 12h, adds 80 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes, continues to stir 12h, be prepared mixed
Close object A；15 parts of zirconium compound zirconium oxychlorides are added in 600 parts of deionized waters and are mixed, stirs, adds aluminium compound aluminum sulfate simultaneously
It is 3 to adjust pH value, you can mixture B is made；Mixture B obtained above is added in into mixture A, Ran Houtong under stirring
It is 6 that pernitric acid, which controls mixed pH value, you can metallic substrate surface inorganic agent is made；Metal base is polished, is cleaned up
Afterwards, above-mentioned metallic substrate surface inorganic agent is sprayed at its surface, spontaneously dried to get to the gold with organosilicon protective coating
Belong to base material.
(4) preparation of underwater superoleophobic UV curing metals coating：By step (1) obtained propylene acidification gallic acid,
Step (2) obtained propylene acidification organic poly sesquisiloxane, is lived at simple function UV curing oligomer (Taiwan Changxing EM3101)
It is coating material solidified that property diluent isobornyl acrylate and photoinitiator TPO-L are uniformly mixed to obtain UV, mass ratio 30:20:
30:15:5；The coating material solidified use dip-coatings of above-mentioned UV or spray coating method are coated on the metallic substrate surface prepared by step (3), UV
Curing is to get to underwater superoleophobic UV curing metals coating.
Using Dataphysics OCA40Micro type surface contact angles tester test in air water in coating surface
Contact angle, oil is in the contact angle of coating surface in air, and underwater oil is in the contact angle of film surface, acquired results and embodiment 1
It is similar, it was demonstrated that the coating has super hydrophilic super oleophylic in air, underwater superoleophobic property.
Embodiment 6
(1) the propylene acidification of gallic acid：The ratio for being dissolved in 5mL acetone according to every 1g gallic acids dissolves gallic acid
In acetone, after according to molar ratio 0.9:Dihydric alcohol and gallic acid are carried out esterification by 1 ratio under catalyst action,
Obtain hydroxylating gallic acid；Then by obtained hydroxylating gallic acid and (methyl) acrylic acid according to molar ratio 1:5
Ratio carries out esterification under catalyst action, and vacuum distillation removes solvent acetone, obtains the gallic acid of propylene acidification；
(2) the propylene acidification of cage modle organic poly sesquisiloxane (POSS)：By amino POSS and acrylic acid in molar ratio 1:9
Ratio carry out neutralization reaction, obtain propylene acidification POSS；
(3) preparation of the metal base with organosilicon protective coating：It counts in parts by weight, takes 30 parts of 1,2-, bis- (front threes
Oxygroup silicon substrate) ethane add in 600 parts of deionized waters in mix, sequentially add 1.5 parts of accelerating agent nitric acid and 10 parts of stabilizer first
Base butynol after stirring 20h, adds 60 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes, continues to stir 8h, prepare
Obtain mixture A；20 parts of zirconium compound potassium fluorozirconates are added in 600 parts of deionized waters and are mixed, stirs, adds aluminium compound nitre
Sour aluminium simultaneously adjusts pH value as 4, you can mixture B is made；Mixture B obtained above is added in into mixture A under stirring,
Then it is 5 to control mixed pH value by nitric acid, you can metallic substrate surface inorganic agent is made；Metal base is polished, clearly
After wash clean, above-mentioned metallic substrate surface inorganic agent is sprayed at its surface, spontaneously dries and protects painting to get to organosilicon
The metal base of layer.
(4) preparation of underwater superoleophobic UV curing metals coating：By step (1) obtained propylene acidification gallic acid,
Step (2) obtained propylene acidification organic poly sesquisiloxane, is lived at simple function UV curing oligomer (Taiwan Changxing EM3102)
It is coating material solidified that property diluent acrylic acid tetrahydrofuran methyl esters and photoinitiator TPO are uniformly mixed to obtain UV, mass ratio 40:
10:30:15:5；The coating material solidified use dip-coatings of above-mentioned UV or spray coating method are coated on the metallic substrate surface prepared by step (3),
UV curings are to get to underwater superoleophobic UV curing metals coating.
Using Dataphysics OCA40Micro type surface contact angles tester test in air water in coating surface
Contact angle, oil is in the contact angle of coating surface in air, and underwater oil is in the contact angle of film surface, acquired results and embodiment 1
It is similar, it was demonstrated that the coating has super hydrophilic super oleophylic in air, underwater superoleophobic property.
Performance test embodiment
Hardness analysis measures the hardness of paint film according to GB/T 6739-1996；The measure of adhesive force is according to GB/T9286-
1998 method test.
Contact angle is tested, and contact angle test is using the test of Germany Dataphysics OCA40Micro types surface contact angle
Instrument, 3 μ L of water droplet or so, each sample test 10 times, removes a maximum value, is averaged after a minimum value.Each embodiment
Test result be shown in Table 1.
1 each embodiment the performance test results of table
| Embodiment | Hardness | Adhesive force | Water contact angle/° | Oily contact angle in air/° | Underwater oil contact angle/° |
| Embodiment 1 | 6H | 0 grade | 0 | 0 | 165 |
| Embodiment 2 | 6H | 0 grade | 0 | 1 | 170 |
| Embodiment 3 | 6H | 0 grade | 0 | 1 | 171 |
| Embodiment 4 | 6H | 0 grade | 1 | 0 | 168 |
| Embodiment 5 | 6H | 0 grade | 2 | 0 | 167 |
| Embodiment 6 | 6H | 0 grade | 0 | 2 | 159 |
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of underwater superoleophobic automatically cleaning UV curing metal coating, it is characterised in that applied including primary coat knead dough, primary coat is by component A
It is formed with component B, mass parts：
Component A includes：10~40 parts of 1,2- bis- (trimethoxy silicon substrate) ethane；500~700 parts of water；1~2 part of accelerating agent；5~
15 parts of stabilizers；50~80 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes；
Component B includes：15~25 parts of zirconium compounds；500~700 parts of water；Aluminium compound, the dosage of the aluminium compound is to adjust group
The pH for dividing B is subject to 3~4；
Face, which applies, to be included：30~40 parts of propylene are acidified gallic acid；10~30 parts of propylene are acidified organic poly sesquisiloxane；10~30
Part simple function UV curing oligomer；10~20 portions of reactive diluents；1~10 part of photoinitiator.
2. underwater superoleophobic automatically cleaning UV curing metal coating according to claim 1, it is characterised in that：The propylene
Acidification gallic acid is prepared by following methods：By dihydric alcohol and gallic acid mixed catalytic esterification, hydroxylating is obtained
Gallic acid；Again with (methyl) acrylic acid mixed catalytic esterification, the gallic acid of propylene acidification is obtained.
3. underwater superoleophobic automatically cleaning UV curing metal coating according to claim 2, it is characterised in that：The dihydric alcohol
With the molar ratio 0.5 of gallic acid:1~1:0.5；The molar ratio 1 of the hydroxylating gallic acid and (methyl) acrylic acid:4~
1:5；The dihydric alcohol is at least one of ethylene glycol, propylene glycol and butanediol.
4. underwater superoleophobic automatically cleaning UV curing metal coating according to claim 1, it is characterised in that：The acrylic acid
Change organic poly sesquisiloxane by the way that hydroxyl POSS or amino POSS and (methyl) acrylic acid are carried out esterification or neutralized anti-
It should obtain.
5. underwater superoleophobic automatically cleaning UV curing metal coating according to claim 4, it is characterised in that：Hydroxyl used
The molar ratio of POSS or amino POSS and (methyl) acrylic acid is 1:8~1:9.
6. underwater superoleophobic automatically cleaning UV curing metal coating according to claim 1, it is characterised in that：The promotion
Agent is at least one of acetic acid, nitric acid, hydrogen peroxide, molybdate and cerium salt；
The stabilizer is at least one in ethyl alcohol, methanol, glycerine, normal propyl alcohol, isopropanol, methyl butynol and hexynol
Kind；
The zirconium compound is at least one of potassium fluorozirconate, sodium fluozirconate, ammonium fluozirconate, fluorine zirconic acid and zirconium oxychloride；
The aluminium compound is at least one of aluminium chloride, aluminum nitrate and aluminum sulfate；
The reactive diluent is hydroxy-ethyl acrylate, hydroxypropyl acrylate, lauryl acrylate, Glycidyl methacrylate are sweet
At least one of grease, isobornyl acrylate, isobornyl methacrylate and acrylic acid tetrahydrofuran methyl esters；
The photoinitiator is 1- hydroxycyclohexyl phenyl ketones, 2- hydroxy-2-methyl -1- phenylacetones, 2- methyl -2-
(4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- acetone, 2,4,6- trimethylbenzoy-diphenies phosphine oxide, 2,4,6-
At least one of trimethylbenzoyl phenyl phosphinic acid ethyl ester；
The simple function UV curing oligomer is methoxy polyethylene glycol acrylate and methoxy poly (ethylene glycol) metering system
At least one of acid esters.
7. a kind of coating based on claim 1~6 any one of them superoleophobic automatically cleaning UV curing metal coating under water.
8. the preparation method of the coating described in a kind of claim 7, it is characterised in that by the way that primary coat is sprayed at substrate surface, do
After dry, then face is applied into dip-coating or is sprayed in primary coat, UV curings obtain underwater superoleophobic automatically cleaning UV curing metal coatings.
9. preparation method according to claim 8, it is characterised in that the UV cured times are 3~5min；The UV
The cured a length of 245~405nm of UV light waves.
10. superoleophobic automatically cleaning UV curing metals coating glues claim 1~6 any one of them in smoke exhaust ventilator, not under water
Application in pot, marine antifouling field.
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