CN102433053A - Functional coating with gradient contact angle function and preparation method thereof - Google Patents
Functional coating with gradient contact angle function and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a functional coating with a gradient contact angle and a preparation method thereof. Firstly, monomers and initiators are mixed in a closed container to obtain first and second prepolymerized monomers, the first and second prepolymerized monomers are respectively added into a container containing solvents, and the mixtures are heated and agitated for 3-6 hours to obtain polymer solution; then the polymer solution is mixed with curing agent, the mixtures are coated on a substrate and the substrate is heated for 10-40 minutes for curing at 110-170 DEG C; and finally the cured coating layer is placed in an open container, water solution is slowly dripped into the container, the upper edge of the substrate is justly and fully infiltrated by the water solution after the water solution is dripped completely within 3-8 hours, and the obtained preformed functional coating is cleaned for 2-3 times and is dried at 40-60 DEG C to obtain the functional coating with the gradient contact angle. The contact angle can continuously change by gradients within temperature ranged from 95 DEG C plus or minus 5 DEG C to 15 DEG C plus or minus 5 DEG C, the change of the contact angle can be realized on different substrates, the preparation method is simple and feasible, the cost is low and the application scope of the functional coating with the gradient contact angle is expanded.
Description
Technical field
The present invention relates to field of functional materials, particularly a kind of functional coating and preparation technology thereof with contact angle continuity variation characteristic.
Background technology
FGM is meant the function of material, changes continuously with space or time or a kind of high performance material of stepped change like component, structure, performance.Contact angle is the important physical amount that is used for weighing the material surface wettability, and general contact angle is more little, and surface energy is big more.Gradient contact angle surface refers to that certain direction gradient continuity changes the material surface contact angle along the surface.Because the peculiar property on gradient contact angle surface, it moves at drop, microfluidic flow, and fields such as biological absorption and efficient heat transfer have shown broad prospect of application.
The existing preparation in the method for gradient contact angle material, ground there is high requirement.Such as; " the Surface Gradient Material:From Superhydrophobicity to Superhydrophilicity " that X.Zhang etc. deliver in " Langmuir " (2006 the 22nd volume the 4483rd～4486 page) (gradient surface material: from super-hydrophobic to the ultra hydrophilic) article; Through the self-assembly effect, realized the transformation of surface contact angle from super-hydrophobic (156.4 °) to ultra hydrophilic (＜10 °) at coarse gold at the end; At first obtain having the coarse gold end of micro-nano dual microtexture through electrodip process; Then, through changing the drips of solution acceleration stresses, on ground, formed contact angle continually varying gradient surface, rate of addition is slow more, and the gradient contact angle variation range that obtains is big more.In addition; Y.C.Han etc. are in " Low-Density Polyethylene (LDPE) Surface With a Wettability Gradient by Tuning its Microstructures " (regulation and control new LDPE (film grade) surface microscopic topographic makes up the gradient wetted surface) article that " Macromolecular Rapid Communications " (volume was the 637th～642 page in 2005 the 26th) delivered; (the contact angle: 165.8 ° of pointing out to have porous super hydrophobic; Roll angle: 4 °) new LDPE (film grade) (LPDE) on surface places in the gradient temperature field, and the temperature in hot junction is higher than the melting temperature T m of LPDE, in the temperature field, places after 10 minutes; Because the surperficial crystalline structure in hot junction is destroyed; The surface high porosity reduces, and hydrophobicity descends, so in the direction that raises along temperature; Surface microstructure forms graded, has formed the gradient wetted surface from super-hydrophobic to hydrophobic with this.More than prepare in the method on gradient contact angle surface, ground is required height, the ground that requires that has has the self-assembly characteristic, and the ground that requires that has has certain susceptibility to temperature; These preparing methods have limited the further application on gradient contact angle surface.
Summary of the invention
The object of the present invention is to provide a kind of simply, effectively, have coating of gradient contact angle characteristic and preparation method thereof.The preparation method of this functional coating can not only successfully prepare the functional coating of contact angle graded, can also on multiple unlike material ground, realize the graded of contact angle.
The object of the invention is realized through following technical scheme: a kind of preparation method with gradient contact angle functional coating is characterized in that comprising the steps:
The first step in mass fraction, with after 100～400 part of first monomer mixes, stirs 5～20 part of first initiator 10～20 minutes with 30～80 rev/mins rotating speeds, obtains the first pre-polymerization monomer;
In second step,, 5～20 part of second initiator with after 500～1000 part of second monomer mixes, with 30～80 rev/mins rotating speeds stirrings 10～30 minutes, obtained the second pre-polymerization monomer in mass fraction;
In the 3rd step, in mass fraction, the first pre-polymerization monomer dropping that the first step is obtained is to filling 900～3500 parts of solvents; Stir speed (S.S.) is in 250～400 rev/mins the container; In 0～60 minute, dropwise, the second pre-polymerization monomer that again second step was obtained progressively is added drop-wise in the said vesse, in 20～60 minutes, dropwises; At last, obtain polymers soln with 90～140 ℃ temperature heated and stirred 3～6 hours;
In the 4th step,, the 3rd polymers soln that obtain of step with after 1～5 part of solidifying agent mixes, with 50～80 rev/mins rotating speeds stirrings 10～30 minutes, is obtained Procuring solution in mass fraction;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the ground of surface cleaning, is warmed up to 110～170 ℃, and thermostatically heating was solidified 10～40 minutes, obtained solidified coating;
In the 6th step, the solidified coating that the 5th step was obtained is vertically placed in the open container, and in container, drips the aqueous solution gradually, guarantees when dropwising in 3～8 hours, and the ground upper edge is just soaked into fully, obtains preparatory functional coating;
The 7th step, after the 6th step, the preparatory functional coating that obtains placed zero(ppm) water to clean 2～3 times, 40～60 ℃ dry down, after the drying, obtain having gradient contact angle functional coating.
First initiator described in the step 1 is a kind of in Diisopropyl azodicarboxylate, Lucidol, acetylperoxide, peroxo-12 phosphinylidynes, the dicumyl peroxide; Said first monomer is a kind of in Rocryl 400, Rocryl 410, vinylformic acid carboxylic ethyl ester, the Propylene glycol monoacrylate.
Said second initiator of step 2 is a kind of in Diisopropyl azodicarboxylate, Lucidol, acetylperoxide, peroxo-12 phosphinylidynes, the dicumyl peroxide; Said second monomer is more than one in TEB 3K, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, methylacrylic acid tetradecyl ester, methylacrylic acid stearyl, methyl acrylate, ethyl propenoate, n-butyl acrylate, NSC 20949 and the tert-butyl acrylate.
The said solvent of step 3 is more than one in toluene, YLENE, butylacetate and the hexanaphthene.
The said solidifying agent of step 4 is aminoresin or isocyanic ester.
The said ground of step 5 is aluminium, copper, silver, gold, silicon or slide glass.
The said aqueous solution of step 6 is that concentration is sodium hydroxide solution, potassium hydroxide solution, hydrochloric acid soln, sulphuric acid soln, phosphoric acid solution, benzoic acid solution, sodium carbonate solution, phospho-wolframic acid and the salts solution thereof of 0.01mol/L～10mol/L, in the sodium dodecyl sulfate solution more than one.
Described gradient contact angle continuity monotone variation.
Said gradient contact angle variation range is 95 ° ± 5 °～15 ° ± 5 °.
A kind of have a gradient contact angle functional coating, by method for preparing.
Gradient contact angle coating provided by the present invention belongs to field of functional materials.
The present invention is combined into the basis with radical polymerization; Prepare the methyl acrylic ester resin solution through solvent polymerization method; And carry out crosslinked with solidifying agent; On ground, form the densified polymer film,, form gradient contact angle surface with certain wetting scope through changing the solution immersion time and soaking into concentration.The present invention has not only successfully prepared the gradient wetted surface, and because the coating characteristic of synthetic resins, has enlarged the range of choice of ground, for solid foundation has been laid in the further application of gradient wetted surface.
The present invention compared with prior art has following advantage and beneficial effect:
(1) prepared functional coating has the characteristic of the continuous monotone variation of gradient contact angle.
(2) prepared functional coating can be realized contact angle variation within the specific limits.
(3) prepared functional coating can be realized on grounds such as aluminium, copper, silver, gold, silicon or slide glass, has enlarged the range of choice of ground, for solid foundation has been laid in the further application of gradient wetted surface.
(4) prepared functional coating has good film performance.
(5) raw material of the present invention obtains easily, and the preparation method is simple, and is with low cost, helps further popularization.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed explanation, but embodiment of the present invention is not limited thereto.
Embodiment 1
The first step, 15 gram Diisopropyl azodicarboxylates and 260 are restrained Rocryl 400s, and to join rotating speed be in 60 rev/mins the airtight magnetic stirring apparatus, stirred 15 minutes, obtains the first pre-polymerization monomer;
In second step, in mass fraction, 15 gram Diisopropyl azodicarboxylates and 800 are restrained TEB 3Ks, and to join rotating speed be in 60 rev/mins the airtight magnetic stirring apparatus, stirred 20 minutes, obtains the second pre-polymerization monomer;
The 3rd step; The first pre-polymerization monomer that the first step is obtained progressively is added drop-wise to and fills 2300 gram toluene, and stir speed (S.S.) is in 330 rev/mins the four-hole boiling flask, in 45 minutes, to dropwise; Again with the second second pre-polymerization monomer dropping that obtain of step in four-hole boiling flask; In 40 minutes, dropwise, 110 ℃ of heated and stirred 5 hours obtain polymers soln;
The 4th step restrained aminoresin with the 3rd polymers soln that obtains of step and 3 and mixes, and joined rotating speed and was in 60 rev/mins the airtight magnetic stirring apparatus, stirred 20 minutes, obtained Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the aluminium flake of surface cleaning, and the baking oven of putting into 120 ℃ was heating and curing 30 minutes, obtained solidified coating;
In the 6th step, the solidified coating that the 5th step was obtained is vertically placed in the open container, and in container, drips the sodium hydroxide solution that concentration is 0.02mol/L gradually, and after 3 hours dropping time, the ground upper edge is soaked into fully, obtains preparatory functional coating;
The 7th step placed zero(ppm) water to clean 3 times the 6th preparatory functional coating that obtain of step, and after the cleaning, 40 ℃ dry down, after the drying, accomplishes the preparation with gradient contact angle functional coating, and contact angle increases to short 100 ° of infiltrating time from long 20 ° of infiltrating time.
Embodiment 2
The first step, 10 gram dicumyl peroxides and 320 are restrained Propylene glycol monoacrylates, and to join rotating speed be in 40 rev/mins the airtight magnetic stirring apparatus, stirred 10 minutes, obtains the first pre-polymerization monomer;
In second step, 8 gram Lucidols and 900 are restrained the methacrylic tert-butyl acrylates, and to join rotating speed be in 45 rev/mins the airtight magnetic stirring apparatus, stirred 28 minutes, obtains the second pre-polymerization monomer;
The 3rd step; The first pre-polymerization monomer that the first step is obtained is added to and fills 3200 gram butylacetates; Stir speed (S.S.) is in 330 rev/mins the four-hole boiling flask, and the second pre-polymerization monomer dropping that again second step was obtained dropwised in 30 minutes in four-hole boiling flask; 120 ℃ of heated and stirred 3 hours obtain polymers soln;
The 4th step restrained aminoresin with the 3rd polymers soln that obtains of step and 1.5 and mixes, and joined rotating speed and was in 80 rev/mins the airtight magnetic stirring apparatus, stirred 18 minutes, obtained Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the silver strip of surface cleaning, and the baking oven of putting into 115 ℃ was heating and curing 38 minutes, obtained solidified coating;
In the 6th step, the solidified coating that the 5th step was obtained is vertically placed in the open container, and in container, drips the sodium carbonate solution that concentration is 0.07mol/L gradually, and after 7.5 hours dropping time, the ground upper edge is soaked into fully, obtains preparatory functional coating;
The 7th step placed zero(ppm) water to clean 2 times the 6th preparatory functional coating that obtain of step, and after the cleaning, 55 ℃ dry down, after the drying, accomplishes the preparation with gradient contact angle functional coating, and contact angle increases to short 92 ° of infiltrating time from long 17 ° of infiltrating time.
Embodiment 3
The first step, 8 gram Lucidols and 175 are restrained Rocryl 410s, and to join rotating speed be in 55 rev/mins the airtight magnetic stirring apparatus, stirred 13 minutes, obtains the first pre-polymerization monomer;
In second step, 14.5 gram Lucidols and 920 are restrained methyl acrylates, and to join rotating speed be in 55 rev/mins the airtight magnetic stirring apparatus, stirred 17 minutes, obtains the second pre-polymerization monomer;
The 3rd step; The first pre-polymerization monomer that the first step is obtained progressively is added drop-wise to and fills 2250 gram hexanaphthenes, and stir speed (S.S.) is in 270 rev/mins the four-hole boiling flask, in 38 minutes, to dropwise; Again with the second second pre-polymerization monomer dropping that obtain of step in four-hole boiling flask; In 27 minutes, dropwise, 125 ℃ of heated and stirred 4.8 hours obtain polymers soln;
The 4th step restrained isocyanic ester with the 3rd polymers soln that obtains of step and 3.7 and mixes, and joined rotating speed and was in 65 rev/mins the airtight magnetic stirring apparatus, stirred 18 minutes, obtained Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the copper sheet of surface cleaning, and the baking oven of putting into 120 ℃ was heating and curing 12 minutes, obtained solidified coating;
The 6th step; The 5th solidified coating that obtain of step is vertically placed in the open container, and in container, to drip concentration gradually be the hydrochloric acid soln of 5mol/L and the Salkowski's solution of 0.0001mol/L, after 3.2 hours dropping time; The ground upper edge is soaked into fully, obtains preparatory functional coating;
The 7th step placed zero(ppm) water to clean 3 times the 6th preparatory functional coating that obtain of step, and after the cleaning, 47 ℃ dry down, after the drying, accomplishes the preparation with gradient contact angle functional coating, and contact angle increases to short 100 ° of infiltrating time from long 12 ° of infiltrating time.
Embodiment 4
The first step, 20 gram Lucidols and 380 are restrained Rocryl 410s, and to join rotating speed be in 80 rev/mins the airtight magnetic stirring apparatus, stirred 20 minutes, obtains the first pre-polymerization monomer;
In second step, 20 gram Diisopropyl azodicarboxylates and 300 gram TEB 3Ks and 700 are restrained NSC 20949s, and to join rotating speed be in 80 rev/mins the airtight magnetic stirring apparatus, stirred 30 minutes, obtains the second pre-polymerization monomer;
The 3rd step; The first pre-polymerization monomer that the first step is obtained progressively is added drop-wise to and fills 3500 gram YLENE, and stir speed (S.S.) is in 400 rev/mins the four-hole boiling flask, in 58 minutes, to dropwise; Again with the second second pre-polymerization monomer dropping that obtain of step in four-hole boiling flask; In 60 minutes, dropwise, 130 ℃ of heated and stirred 6 hours obtain polymers soln;
The 4th step restrained isocyanic ester with the 3rd polymers soln that obtains of step and 5 and mixes, and joined rotating speed and was in 75 rev/mins the airtight magnetic stirring apparatus, stirred 30 minutes, obtained Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the copper sheet of surface cleaning, and the baking oven of putting into 110 ℃ was heating and curing 40 minutes, obtained solidified coating;
In the 6th step, the solidified coating that the 5th step was obtained is vertically placed in the open container, and in container, drips the sulphuric acid soln that concentration is 1mol/L gradually, and after 6 hours dropping time, the ground upper edge is soaked into fully, obtains preparatory functional coating;
The 7th step placed zero(ppm) water to clean 3 times the 6th preparatory functional coating that obtain of step, and after the cleaning, 50 ℃ dry down, after the drying, accomplishes the preparation with gradient contact angle functional coating, and contact angle increases to short 90 ° of infiltrating time from long 10 ° of infiltrating time.
Embodiment 5
The first step, 19 gram peroxo-12 phosphinylidynes and 395 are restrained vinylformic acid carboxylic ethyl esters, and to join rotating speed be in 77 rev/mins the airtight magnetic stirring apparatus, stirred 12 minutes, obtains the first pre-polymerization monomer;
In second step, 17 gram acetylperoxides and 100 gram n-BMAs and 570 are restrained n-butyl acrylates, and to join rotating speed be in 77 rev/mins the airtight magnetic stirring apparatus, stirred 26 minutes, obtains the second pre-polymerization monomer;
The 3rd step; The first pre-polymerization monomer that the first step is obtained progressively is added drop-wise to and fills 3450 gram YLENE, and stir speed (S.S.) is in 370 rev/mins the four-hole boiling flask, in 25 minutes, to dropwise; Again with the second second pre-polymerization monomer dropping that obtain of step in four-hole boiling flask; In 58 minutes, dropwise, 135 ℃ of heated and stirred 3.4 hours obtain polymers soln;
The 4th step restrained aminoresin with the 3rd polymers soln that obtains of step and 3.6 and mixes, and joined rotating speed and was in 78 rev/mins the airtight magnetic stirring apparatus, stirred 29 minutes, obtained Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the aluminium flake of surface cleaning, and the baking oven of putting into 113 ℃ was heating and curing 18 minutes, obtained solidified coating;
In the 6th step, the solidified coating that the 5th step was obtained is vertically placed in the open container, and in container, drips the sodium carbonate solution that concentration is 7mol/L gradually, and after 5.5 hours dropping time, the ground upper edge is soaked into fully, obtains preparatory functional coating;
The 7th step placed zero(ppm) water to clean 3 times the 6th preparatory functional coating that obtain of step, and after the cleaning, 50 ℃ dry down, after the drying, accomplishes the preparation with gradient contact angle functional coating, and contact angle increases to short 90 ° of infiltrating time from long 20 ° of infiltrating time.
Embodiment 6
The first step, 12 gram acetylperoxides and 350 are restrained vinylformic acid carboxylic ethyl esters, and to join rotating speed be in 50 rev/mins the airtight magnetic stirring apparatus, stirred 18 minutes, obtains the first pre-polymerization monomer;
In second step, 10 gram dicumyl peroxides and 750 are restrained Propenoic acid, 2-methyl, isobutyl esters, and to join rotating speed be in 70 rev/mins the airtight magnetic stirring apparatus, stirred 25 minutes, obtains the second pre-polymerization monomer;
The 3rd step; The first pre-polymerization monomer that the first step is obtained progressively is added drop-wise to and fills 500 gram toluene and 2200 gram butylacetates, and stir speed (S.S.) is in 380 rev/mins the four-hole boiling flask, in 40 minutes, to dropwise; Again with the second second pre-polymerization monomer dropping that obtain of step in four-hole boiling flask; In 50 minutes, dropwise, 115 ℃ of heated and stirred 4.5 hours obtain polymers soln;
The 4th step restrained isocyanic ester with the 3rd polymers soln that obtains of step and 4.5 and mixes, and joined rotating speed and was in 68 rev/mins the airtight magnetic stirring apparatus, stirred 28 minutes, obtained Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the silicon chip of surface cleaning, and the baking oven of putting into 140 ℃ was heating and curing 28 minutes, obtained solidified coating;
In the 6th step, the solidified coating that the 5th step was obtained is vertically placed in the open container, and in container, drips the phosphoric acid solution that concentration is 5mol/L gradually, and after 4.8 hours dropping time, the ground upper edge is soaked into fully, obtains preparatory functional coating;
The 7th step placed zero(ppm) water to clean 2 times the 6th preparatory functional coating that obtain of step, and after the cleaning, 45 ℃ dry down, after the drying, accomplishes the preparation with gradient contact angle functional coating, and contact angle increases to short 98 ° of infiltrating time from long 13 ° of infiltrating time.
Embodiment 7
The first step, 9 gram Diisopropyl azodicarboxylates and 240 are restrained Rocryl 400s, and to join rotating speed be in 69 rev/mins the airtight magnetic stirring apparatus, stirred 14 minutes, obtains the first pre-polymerization monomer;
In second step, 6 gram dicumyl peroxides and 540 are restrained the methacrylic tert-butyl acrylates, and to join rotating speed be in 78 rev/mins the airtight magnetic stirring apparatus, stirred 24 minutes, obtains the second pre-polymerization monomer;
The 3rd step; The first pre-polymerization monomer that the first step is obtained progressively is added drop-wise to and fills 1000 gram toluene and 1000 gram YLENE, and stir speed (S.S.) is in 380 rev/mins the four-hole boiling flask, in 55 minutes, to dropwise; Again with the second second pre-polymerization monomer dropping that obtain of step in four-hole boiling flask; In 32 minutes, dropwise, 135 ℃ of heated and stirred 5.5 hours obtain polymers soln;
The 4th step restrained aminoresin with the 3rd polymers soln that obtains of step and 2.2 and mixes, and joined rotating speed and was in 75 rev/mins the airtight magnetic stirring apparatus, stirred 18 minutes, obtained Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the slide glass of surface cleaning, and the baking oven of putting into 165 ℃ was heating and curing 35 minutes, obtained solidified coating;
The 6th step; The solidified coating that the 5th step was obtained is vertically placed in the open container; And in container, drip potassium hydroxide solution that concentration is 9mol/L and the phospho-wolframic acid one substituted ammonium salt solution of 0.0005mol/L gradually; After 7.7 hours dropping time, the ground upper edge is soaked into fully, obtains preparatory functional coating;
The 7th step placed zero(ppm) water to clean 2 times the 6th preparatory functional coating that obtain of step, and after the cleaning, 58 ℃ dry down, after the drying, accomplishes the preparation with gradient contact angle functional coating, and contact angle increases to short 99 ° of infiltrating time from long 13 ° of infiltrating time.
Embodiment 8
The first step, 7 gram peroxo-12 phosphinylidynes and 180 are restrained Propylene glycol monoacrylates, and to join rotating speed be in 67 rev/mins the airtight magnetic stirring apparatus, stirred 13 minutes, obtains the first pre-polymerization monomer;
In second step, 14 gram dicumyl peroxides and 200 gram ethyl propenoates and 550 are restrained the methylacrylic acid stearyl, and to join rotating speed be in 67 rev/mins the airtight magnetic stirring apparatus, stirred 18 minutes, obtains the second pre-polymerization monomer;
The 3rd step; The first pre-polymerization monomer that the first step is obtained progressively is added drop-wise to and fills 450 gram YLENE and 2100 gram toluene, and stir speed (S.S.) is in 320 rev/mins the four-hole boiling flask, in 48 minutes, to dropwise; Again with the second second pre-polymerization monomer dropping that obtain of step in four-hole boiling flask; In 55 minutes, dropwise, 135 ℃ of heated and stirred 4.8 hours obtain polymers soln;
The 4th step restrained aminoresin with the 3rd polymers soln that obtains of step and 3.6 and mixes, and joined rotating speed and was in 78 rev/mins the airtight magnetic stirring apparatus, stirred 24 minutes, obtained Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the slide glass of surface cleaning, and the baking oven of putting into 160 ℃ was heating and curing 35 minutes, obtained solidified coating;
In the 6th step, the solidified coating that the 5th step was obtained is vertically placed in the open container, and in container, drips the benzoic acid solution that concentration is 0.75mol/L gradually, and after 8 hours dropping time, the ground upper edge is soaked into fully, obtains preparatory functional coating;
The 7th step placed zero(ppm) water to clean 2 times the 6th preparatory functional coating that obtain of step, and after the cleaning, 55 ℃ dry down, after the drying, accomplishes the preparation with gradient contact angle functional coating, and contact angle increases to short 100 ° of infiltrating time from long 20 ° of infiltrating time.
Embodiment 9
The first step, 17 gram Lucidols and 190 are restrained Rocryl 400s, and to join rotating speed be in 75 rev/mins the airtight magnetic stirring apparatus, stirred 18 minutes, obtains the first pre-polymerization monomer;
In second step, in mass fraction, 19 gram Diisopropyl azodicarboxylates and 200 gram TEB 3Ks and 700 are restrained n-butyl acrylates, and to join rotating speed be in 78 rev/mins the airtight magnetic stirring apparatus, stirred 27 minutes, obtains the second pre-polymerization monomer;
The 3rd step; The first pre-polymerization monomer that the first step is obtained progressively is added drop-wise to and fills 1500 gram YLENE and 1700 gram hexanaphthenes, and stir speed (S.S.) is in 385 rev/mins the four-hole boiling flask, in 58 minutes, to dropwise; Again with the second second pre-polymerization monomer dropping that obtain of step in four-hole boiling flask; In 55 minutes, dropwise, 138 ℃ of heated and stirred 3.5 hours obtain polymers soln;
The 4th step in mass fraction, restrained isocyanic ester with the 3rd polymers soln that obtains of step and 1.3 and mixes, and joined rotating speed and was in 78 rev/mins the airtight magnetic stirring apparatus, stirred 26 minutes, obtained Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the copper sheet of surface cleaning, and the baking oven of putting into 116 ℃ was heating and curing 14 minutes, obtained solidified coating;
The 6th step; The solidified coating that the 5th step was obtained is vertically placed in the open container; And in container, to drip concentration gradually be the sodium hydroxide solution of 1mol/L and the sodium dodecyl sulfate solution of 0.0002mol/L; After 7.8 hours dropping time, the ground upper edge is soaked into fully, obtains preparatory functional coating;
The 7th step placed zero(ppm) water to clean 3 times the 6th preparatory functional coating that obtain of step, and after the cleaning, 46 ℃ dry down, after the drying, accomplishes the preparation with gradient contact angle functional coating, and contact angle increases to short 96 ° of infiltrating time from long 11 ° of infiltrating time.
Claims (10)
1. the preparation method with gradient contact angle functional coating is characterized in that comprising the steps:
The first step in mass fraction, with after 100～400 part of first monomer mixes, stirs 5～20 part of first initiator 10～20 minutes with 30～80 rev/mins rotating speeds, obtains the first pre-polymerization monomer;
In second step,, 5～20 part of second initiator with after 500～1000 part of second monomer mixes, with 30～80 rev/mins rotating speeds stirrings 10～30 minutes, obtained the second pre-polymerization monomer in mass fraction;
In the 3rd step, in mass fraction, the first pre-polymerization monomer dropping that the first step is obtained is to filling 900～3500 parts of solvents; Stir speed (S.S.) is in 250～400 rev/mins the container; In 0～60 minute, dropwise, the second pre-polymerization monomer that again second step was obtained progressively is added drop-wise in the said vesse, in 20～60 minutes, dropwises; At last, obtain polymers soln with 90～140 ℃ temperature heated and stirred 3～6 hours;
In the 4th step,, the 3rd polymers soln that obtain of step with after 1～5 part of solidifying agent mixes, with 50～80 rev/mins rotating speeds stirrings 10～30 minutes, is obtained Procuring solution in mass fraction;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the ground of surface cleaning, is warmed up to 110～170 ℃, and thermostatically heating was solidified 10～40 minutes, obtained solidified coating;
In the 6th step, the solidified coating that the 5th step was obtained is vertically placed in the open container, and in container, drips the aqueous solution gradually, guarantees when dropwising in 3～8 hours, and the ground upper edge is just soaked into fully, obtains preparatory functional coating;
The 7th step, after the 6th step, the preparatory functional coating that obtains placed zero(ppm) water to clean 2～3 times, 40～60 ℃ dry down, after the drying, obtain having gradient contact angle functional coating.
2. a kind of preparation method with gradient contact angle functional coating according to claim 1 is characterized in that: first initiator described in the step 1 is a kind of in Diisopropyl azodicarboxylate, Lucidol, acetylperoxide, peroxo-12 phosphinylidynes, the dicumyl peroxide; Said first monomer is a kind of in Rocryl 400, Rocryl 410, vinylformic acid carboxylic ethyl ester, the Propylene glycol monoacrylate.
3. a kind of preparation method with gradient contact angle functional coating according to claim 1 is characterized in that: said second initiator of step 2 is a kind of in Diisopropyl azodicarboxylate, Lucidol, acetylperoxide, peroxo-12 phosphinylidynes, the dicumyl peroxide; Said second monomer is more than one in TEB 3K, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, methylacrylic acid tetradecyl ester, methylacrylic acid stearyl, methyl acrylate, ethyl propenoate, n-butyl acrylate, NSC 20949 and the tert-butyl acrylate.
4. a kind of preparation method with gradient contact angle functional coating according to claim 1 is characterized in that: the said solvent of step 3 is more than one in toluene, YLENE, butylacetate and the hexanaphthene.
5. a kind of preparation method with gradient contact angle functional coating according to claim 1 is characterized in that: the said solidifying agent of step 4 is aminoresin or isocyanic ester.
6. a kind of preparation method with gradient contact angle functional coating according to claim 1 is characterized in that: the said ground of step 5 is aluminium, copper, silver, gold, silicon or slide glass.
7. a kind of preparation method with gradient contact angle functional coating according to claim 1 is characterized in that: the said aqueous solution of step 6 is that concentration is sodium hydroxide solution, potassium hydroxide solution, hydrochloric acid soln, sulphuric acid soln, phosphoric acid solution, benzoic acid solution, sodium carbonate solution, phospho-wolframic acid and the salts solution thereof of 0.01mol/L～10mol/L, in the sodium dodecyl sulfate solution more than one.
8. according to the described a kind of preparation method of one of claim 1-7, it is characterized in that: described gradient contact angle continuity monotone variation with gradient contact angle functional coating.
9. a kind of preparation method with gradient contact angle functional coating according to claim 8 is characterized in that: said gradient contact angle variation range is 95 ° ± 5 °～15 ° ± 5 °.
10. one kind has a gradient contact angle functional coating by one of claim 1-8 preparation.
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| CN110434337A (en) * | 2019-08-23 | 2019-11-12 | 广州番禺职业技术学院 | A kind of 3D printing prepares the preparation method of bionic intelligence metal material surface |
| CN115156004A (en) * | 2022-08-08 | 2022-10-11 | 广州番禺职业技术学院 | Preparation method of patterned gradient wetting functional surface with biocompatibility |
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| US5098972A (en) * | 1989-04-28 | 1992-03-24 | Atochem | Hardenable, fluorinated copolymer, process for its manufacture and its application in varnishes and paints |
| CN101914185A (en) * | 2010-09-08 | 2010-12-15 | 廊坊金汇利工业涂料有限公司 | Hydroxy acrylic resin aqueous dispersion and water-based coating prepared therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5098972A (en) * | 1989-04-28 | 1992-03-24 | Atochem | Hardenable, fluorinated copolymer, process for its manufacture and its application in varnishes and paints |
| CN101914185A (en) * | 2010-09-08 | 2010-12-15 | 廊坊金汇利工业涂料有限公司 | Hydroxy acrylic resin aqueous dispersion and water-based coating prepared therefrom |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110434337A (en) * | 2019-08-23 | 2019-11-12 | 广州番禺职业技术学院 | A kind of 3D printing prepares the preparation method of bionic intelligence metal material surface |
| CN115156004A (en) * | 2022-08-08 | 2022-10-11 | 广州番禺职业技术学院 | Preparation method of patterned gradient wetting functional surface with biocompatibility |
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