CN102433053B - 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
Functionally Graded Materials refers to the function of material, changes with space or Time Continuous as component, properity or a kind of high performance material of stepped change.Contact angle is the important physical amount of weighing the material surface wettability, and general contact angle is less, and surface can be larger.Gradient contact angle surface refers to that the material surface contact angle changes along certain direction gradient continuity of surface.Due to the peculiar property on gradient contact angle surface, it moves at drop, microfluidic flow, and the fields such as biological adsorption 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, X.Zhang etc. are " Surface Gradient Material:From Superhydrophobicity to Superhydrophilicity " (gradient surface material: from super-hydrophobic to super hydrophilic) article that " Langmuir " (the 22nd volume was the 4483rd～4486 page in 2006) delivered,, by the self-assembly effect, at coarse gold, realized the transformation of surface contact angle from super-hydrophobic (156.4 °) to super hydrophilic (＜10 °) at the end; At first obtain having by electrodip process the coarse gold end of micro-nano dual microtexture; Then,, by changing the solution rate of addition, formed contact angle continually varying gradient surface on ground, rate of addition is slower, and the gradient contact angle variation range that obtains is larger.in addition, Y.C.Han etc. are in " Low-Density Polyethylene (LDPE) Surface With a Wettability Gradient by Tuning its Microstructures " (regulation and control Low Density Polyethylene surface microscopic topographic builds the gradient wetted surface) article that " Macromolecular Rapid Communications " (the 26th volume was the 637th～642 page in 2005) delivered, (the contact angle: 165.8 ° of pointing out to have porous super hydrophobic, roll angle: 4 °) Low Density Polyethylene (LPDE) on surface is placed in the gradient temperature field, the temperature in hot junction is higher than the melting temperature T m of LPDE, place after 10 minutes in temperature field, because the surperficial crystalline structure in hot junction is destroyed, the surface high porosity reduces, hydrophobicity descends, so in the direction that raises along temperature, surface microstructure forms graded, formed the gradient wetted surface from super-hydrophobic to hydrophobic with this.In the above method for preparing gradient contact angle surface, ground is required high, the ground that requires that has has the self-assembly characteristic, and the ground that requires that has has certain susceptibility to temperature; These preparation 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 feature 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 realize the graded of contact angle on multiple unlike material ground.
Purpose of the present invention is achieved through the following technical solutions: 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, stir 5～20 part of first initiator 10～20 minutes with the rotating speeds of 30～80 rev/mins, obtains the first pre-polymerization monomer;
Second step,, in mass fraction,, with after 500～1000 part of second monomer mixes, stir 5～20 part of second initiator 10～30 minutes with the rotating speeds of 30～80 rev/mins, obtains the second pre-polymerization monomer;
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 the container of 250～400 rev/mins, dropwised in 0～60 minute, then the second pre-polymerization monomer that second step obtains progressively is added drop-wise in said vesse, dropwised in 20～60 minutes, finally, with the temperature heated and stirred of 90～140 ℃ 3～6 hours, obtain polymers soln;
In the 4th step, in mass fraction, the 3rd polymers soln that obtain of step, with after 1～5 part of solidifying agent mixes,, with the rotating speeds stirrings of 50～80 rev/mins 10～30 minutes, is obtained Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the clean ground in surface, 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 open container, and drips gradually the aqueous solution in container, guarantees when dropwising in 3～8 hours,, along just by complete wetting, obtains pre-functional coating on ground;
The 7th step, after the 6th pre-functional coating that obtain of step is placed in distilled water and cleans 2～3 times, dry under 40～60 ℃, after drying, obtain having gradient contact angle functional coating.
The first initiator described in step 1 is a kind of in Diisopropyl azodicarboxylate, benzoyl peroxide, acetyl peroxide, peroxidation 12 phosphinylidynes, dicumyl peroxide; Described the first monomer is a kind of in hydroxyethyl methylacrylate, Rocryl 410, vinylformic acid carboxylic ethyl ester, Propylene glycol monoacrylate.
Described the second initiator of step 2 is a kind of in Diisopropyl azodicarboxylate, benzoyl peroxide, acetyl peroxide, peroxidation 12 phosphinylidynes, dicumyl peroxide; Described the second monomer is more than one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, methacrylic acid tetradecyl ester, methacrylic acid stearyl, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate and tert-butyl acrylate.
The described solvent of step 3 is more than one in toluene, dimethylbenzene, butylacetate and hexanaphthene.
The described solidifying agent of step 4 is aminoresin or isocyanic ester.
The described ground of step 5 is aluminium, copper, silver, gold, silicon or slide glass.
The described 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, more than one in sodium dodecyl sulfate solution.
Described gradient contact angle continuity monotone variation.
Described gradient contact angle variation range is 95 ° ± 5 °～15 ° ± 5 °.
A kind of have a gradient contact angle functional coating, by aforesaid method, prepared.
Gradient contact angle coating provided by the present invention belongs to field of functional materials.
The present invention is combined into basis with radical polymerization, prepare the methyl acrylic ester resin solution by solvent polymerization method, and with solidifying agent, carry out crosslinked, form the densified polymer film on ground, by changing the solution immersion time and infiltrate concentration, form the gradient contact angle surface with certain wetting scope.The present invention has not only successfully prepared the gradient wetted surface, and, due to 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 feature 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 the 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, is conducive to further popularization.
Embodiment
The present invention will be further described in detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
The first step, it is in the airtight magnetic stirring apparatus of 60 rev/mins that 15 gram Diisopropyl azodicarboxylates and 260 gram hydroxyethyl methylacrylates are joined rotating speed, stirs 15 minutes, obtains the first pre-polymerization monomer;
Second step, in mass fraction, it is in the airtight magnetic stirring apparatus of 60 rev/mins that 15 gram Diisopropyl azodicarboxylates and 800 gram methyl methacrylates are joined rotating speed, stirs 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, stir speed (S.S.) is in the four-hole boiling flask of 330 rev/mins, dropwised in 45 minutes, the the second pre-polymerization monomer dropping that again second step is obtained is in four-hole boiling flask, dropwised in 40 minutes, 110 ℃ of heated and stirred 5 hours, obtain polymers soln;
The 4th step, the 3rd polymers soln that obtain of step is mixed with 3 gram aminoresin, join rotating speed and be in the airtight magnetic stirring apparatus of 60 rev/mins, stirred 20 minutes, obtain Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the clean aluminium flake in surface, 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 open container, and drips gradually the sodium hydroxide solution that concentration is 0.02mol/L in container, at time for adding, after 3 hours,, along by complete wetting, obtains pre-functional coating on ground;
In the 7th step, be placed in distilled water with the 6th pre-functional coating that obtain of step and clean 3 times, after cleaning, dry under 40 ℃, after drying, complete the preparation with gradient contact angle functional coating, contact angle increases to short 100 ° of infiltrating time from long 20 ° of infiltrating time.
Embodiment 2
The first step, it is in the airtight magnetic stirring apparatus of 40 rev/mins that 10 gram dicumyl peroxides and 320 gram Propylene glycol monoacrylates are joined rotating speed, stirs 10 minutes, obtains the first pre-polymerization monomer;
Second step, it is in the airtight magnetic stirring apparatus of 45 rev/mins that 8 gram benzoyl peroxides and 900 gram Tert-butyl Methacrylates are joined rotating speed, stirs 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 the four-hole boiling flask of 330 rev/mins, the the second pre-polymerization monomer dropping that again second step is obtained is in four-hole boiling flask, dropwised in 30 minutes, 120 ℃ of heated and stirred 3 hours, obtain polymers soln;
The 4th step, the 3rd polymers soln that obtain of step is mixed with 1.5 gram aminoresin, join rotating speed and be in the airtight magnetic stirring apparatus of 80 rev/mins, stirred 18 minutes, obtain Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the clean silver strip in surface, 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 open container, and drips gradually the sodium carbonate solution that concentration is 0.07mol/L in container, at time for adding, after 7.5 hours,, along by complete wetting, obtains pre-functional coating on ground;
In the 7th step, be placed in distilled water with the 6th pre-functional coating that obtain of step and clean 2 times, after cleaning, dry under 55 ℃, after drying, complete the preparation with gradient contact angle functional coating, contact angle increases to short 92 ° of infiltrating time from long 17 ° of infiltrating time.
Embodiment 3
The first step, it is in the airtight magnetic stirring apparatus of 55 rev/mins that 8 gram benzoyl peroxides and 175 gram Rocryl 410s are joined rotating speed, stirs 13 minutes, obtains the first pre-polymerization monomer;
Second step, it is in the airtight magnetic stirring apparatus of 55 rev/mins that 14.5 gram benzoyl peroxides and 920 gram methyl acrylates are joined rotating speed, stirs 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, stir speed (S.S.) is in the four-hole boiling flask of 270 rev/mins, dropwised in 38 minutes, the the second pre-polymerization monomer dropping that again second step is obtained is in four-hole boiling flask, dropwised in 27 minutes, 125 ℃ of heated and stirred 4.8 hours, obtain polymers soln;
The 4th step, the 3rd polymers soln that obtain of step is mixed with 3.7 gram isocyanic ester, join rotating speed and be in the airtight magnetic stirring apparatus of 65 rev/mins, stirred 18 minutes, obtain Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the clean copper sheet in surface, 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 open container, and to dripping gradually concentration in container, is the hydrochloric acid soln of 5mol/L and the Salkowski's solution of 0.0001mol/L, at time for adding after 3.2 hours,, along by complete wetting, obtain pre-functional coating on ground;
In the 7th step, be placed in distilled water with the 6th pre-functional coating that obtain of step and clean 3 times, after cleaning, dry under 47 ℃, after drying, complete the preparation with gradient contact angle functional coating, contact angle increases to short 100 ° of infiltrating time from long 12 ° of infiltrating time.
Embodiment 4
The first step, it is in the airtight magnetic stirring apparatus of 80 rev/mins that 20 gram benzoyl peroxides and 380 gram Rocryl 410s are joined rotating speed, stirs 20 minutes, obtains the first pre-polymerization monomer;
Second step, it is in the airtight magnetic stirring apparatus of 80 rev/mins that 20 gram Diisopropyl azodicarboxylates and 300 gram methyl methacrylates and 700 gram isobutyl acrylate are joined rotating speed, stirs 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 dimethylbenzene, stir speed (S.S.) is in the four-hole boiling flask of 400 rev/mins, dropwised in 58 minutes, the the second pre-polymerization monomer dropping that again second step is obtained is in four-hole boiling flask, dropwised in 60 minutes, 130 ℃ of heated and stirred 6 hours, obtain polymers soln;
The 4th step, the 3rd polymers soln that obtain of step is mixed with 5 gram isocyanic ester, join rotating speed and be in the airtight magnetic stirring apparatus of 75 rev/mins, stirred 30 minutes, obtain Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the clean copper sheet in surface, 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 open container, and drips gradually the sulphuric acid soln that concentration is 1mol/L in container, at time for adding, after 6 hours,, along by complete wetting, obtains pre-functional coating on ground;
In the 7th step, be placed in distilled water with the 6th pre-functional coating that obtain of step and clean 3 times, after cleaning, dry under 50 ℃, after drying, complete the preparation with gradient contact angle functional coating, contact angle increases to short 90 ° of infiltrating time from long 10 ° of infiltrating time.
Embodiment 5
The first step, it is in the airtight magnetic stirring apparatus of 77 rev/mins that 19 gram peroxidation 12 phosphinylidynes and 395 gram vinylformic acid carboxylic ethyl esters are joined rotating speed, stirs 12 minutes, obtains the first pre-polymerization monomer;
Second step, it is in the airtight magnetic stirring apparatus of 77 rev/mins that 17 gram acetyl peroxides and 100 gram n-BMAs and 570 gram n-butyl acrylates are joined rotating speed, stirs 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 dimethylbenzene, stir speed (S.S.) is in the four-hole boiling flask of 370 rev/mins, dropwised in 25 minutes, the the second pre-polymerization monomer dropping that again second step is obtained is in four-hole boiling flask, dropwised in 58 minutes, 135 ℃ of heated and stirred 3.4 hours, obtain polymers soln;
The 4th step, the 3rd polymers soln that obtain of step is mixed with 3.6 gram aminoresin, join rotating speed and be in the airtight magnetic stirring apparatus of 78 rev/mins, stirred 29 minutes, obtain Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the clean aluminium flake in surface, 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 open container, and drips gradually the sodium carbonate solution that concentration is 7mol/L in container, at time for adding, after 5.5 hours,, along by complete wetting, obtains pre-functional coating on ground;
In the 7th step, be placed in distilled water with the 6th pre-functional coating that obtain of step and clean 3 times, after cleaning, dry under 50 ℃, after drying, complete the preparation with gradient contact angle functional coating, contact angle increases to short 90 ° of infiltrating time from long 20 ° of infiltrating time.
Embodiment 6
The first step, it is in the airtight magnetic stirring apparatus of 50 rev/mins that 12 gram acetyl peroxides and 350 gram vinylformic acid carboxylic ethyl esters are joined rotating speed, stirs 18 minutes, obtains the first pre-polymerization monomer;
Second step, it is in the airtight magnetic stirring apparatus of 70 rev/mins that 10 gram dicumyl peroxides and 750 gram Propenoic acid, 2-methyl, isobutyl esters are joined rotating speed, stirs 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, stir speed (S.S.) is in the four-hole boiling flask of 380 rev/mins, dropwised in 40 minutes, the the second pre-polymerization monomer dropping that again second step is obtained is in four-hole boiling flask, dropwised in 50 minutes, 115 ℃ of heated and stirred 4.5 hours, obtain polymers soln;
The 4th step, the 3rd polymers soln that obtain of step is mixed with 4.5 gram isocyanic ester, join rotating speed and be in the airtight magnetic stirring apparatus of 68 rev/mins, stirred 28 minutes, obtain Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the clean silicon chip in surface, 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 open container, and drips gradually the phosphoric acid solution that concentration is 5mol/L in container, at time for adding, after 4.8 hours,, along by complete wetting, obtains pre-functional coating on ground;
In the 7th step, be placed in distilled water with the 6th pre-functional coating that obtain of step and clean 2 times, after cleaning, dry under 45 ℃, after drying, complete the preparation with gradient contact angle functional coating, contact angle increases to short 98 ° of infiltrating time from long 13 ° of infiltrating time.
Embodiment 7
The first step, it is in the airtight magnetic stirring apparatus of 69 rev/mins that 9 gram Diisopropyl azodicarboxylates and 240 gram hydroxyethyl methylacrylates are joined rotating speed, stirs 14 minutes, obtains the first pre-polymerization monomer;
Second step, it is in the airtight magnetic stirring apparatus of 78 rev/mins that 6 gram dicumyl peroxides and 540 gram Tert-butyl Methacrylates are joined rotating speed, stirs 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 dimethylbenzene, stir speed (S.S.) is in the four-hole boiling flask of 380 rev/mins, dropwised in 55 minutes, the the second pre-polymerization monomer dropping that again second step is obtained is in four-hole boiling flask, dropwised in 32 minutes, 135 ℃ of heated and stirred 5.5 hours, obtain polymers soln;
The 4th step, the 3rd polymers soln that obtain of step is mixed with 2.2 gram aminoresin, join rotating speed and be in the airtight magnetic stirring apparatus of 75 rev/mins, stirred 18 minutes, obtain Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the clean slide glass in surface, 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 open container, and to dripping gradually potassium hydroxide solution that concentration is 9mol/L and the phospho-wolframic acid one substituted ammonium salt solution of 0.0005mol/L in container, at time for adding after 7.7 hours,, along by complete wetting, obtain pre-functional coating on ground;
In the 7th step, be placed in distilled water with the 6th pre-functional coating that obtain of step and clean 2 times, after cleaning, dry under 58 ℃, after drying, complete the preparation with gradient contact angle functional coating, contact angle increases to short 99 ° of infiltrating time from long 13 ° of infiltrating time.
Embodiment 8
The first step, it is in the airtight magnetic stirring apparatus of 67 rev/mins that 7 gram peroxidation 12 phosphinylidynes and 180 gram Propylene glycol monoacrylates are joined rotating speed, stirs 13 minutes, obtains the first pre-polymerization monomer;
Second step, it is in the airtight magnetic stirring apparatus of 67 rev/mins that 14 gram dicumyl peroxides and 200 gram ethyl propenoates and 550 gram methacrylic acid stearyl are joined rotating speed, stirs 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 dimethylbenzene and 2100 gram toluene, stir speed (S.S.) is in the four-hole boiling flask of 320 rev/mins, dropwised in 48 minutes, the the second pre-polymerization monomer dropping that again second step is obtained is in four-hole boiling flask, dropwised in 55 minutes, 135 ℃ of heated and stirred 4.8 hours, obtain polymers soln;
The 4th step, the 3rd polymers soln that obtain of step is mixed with 3.6 gram aminoresin, join rotating speed and be in the airtight magnetic stirring apparatus of 78 rev/mins, stirred 24 minutes, obtain Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the clean slide glass in surface, 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 open container, and drips gradually the benzoic acid solution that concentration is 0.75mol/L in container, at time for adding, after 8 hours,, along by complete wetting, obtains pre-functional coating on ground;
In the 7th step, be placed in distilled water with the 6th pre-functional coating that obtain of step and clean 2 times, after cleaning, dry under 55 ℃, after drying, complete the preparation with gradient contact angle functional coating, contact angle increases to short 100 ° of infiltrating time from long 20 ° of infiltrating time.
Embodiment 9
The first step, it is in the airtight magnetic stirring apparatus of 75 rev/mins that 17 gram benzoyl peroxides and 190 gram hydroxyethyl methylacrylates are joined rotating speed, stirs 18 minutes, obtains the first pre-polymerization monomer;
Second step, in mass fraction, it is in the airtight magnetic stirring apparatus of 78 rev/mins that 19 gram Diisopropyl azodicarboxylates and 200 gram methyl methacrylates and 700 gram n-butyl acrylates are joined rotating speed, stirs 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 dimethylbenzene and 1700 gram hexanaphthenes, stir speed (S.S.) is in the four-hole boiling flask of 385 rev/mins, dropwised in 58 minutes, the the second pre-polymerization monomer dropping that again second step is obtained is in four-hole boiling flask, dropwised in 55 minutes, 138 ℃ of heated and stirred 3.5 hours, obtain polymers soln;
The 4th step, in mass fraction, the 3rd polymers soln that obtain of step is mixed with 1.3 gram isocyanic ester, join rotating speed and be in the airtight magnetic stirring apparatus of 78 rev/mins, stirred 26 minutes, obtain Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the clean copper sheet in surface, 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 open container, and to dripping gradually concentration in container, be the sodium hydroxide solution of 1mol/L and the sodium dodecyl sulfate solution of 0.0002mol/L, at time for adding after 7.8 hours,, along by complete wetting, obtain pre-functional coating on ground;
In the 7th step, be placed in distilled water with the 6th pre-functional coating that obtain of step and clean 3 times, after cleaning, dry under 46 ℃, after drying, complete the preparation with gradient contact angle functional coating, contact angle increases to short 96 ° of infiltrating time from long 11 ° of infiltrating time.
Claims (7)
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, stir 5～20 part of first initiator 10～20 minutes with the rotating speeds of 30～80 rev/mins, obtains the first pre-polymerization monomer;
Second step,, in mass fraction,, with after 500～1000 part of second monomer mixes, stir 5～20 part of second initiator 10～30 minutes with the rotating speeds of 30～80 rev/mins, obtains the second pre-polymerization monomer;
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 the container of 250～400 rev/mins, dropwised in 0～60 minute, then the second pre-polymerization monomer that second step obtains progressively is added drop-wise in said vesse, dropwised in 20～60 minutes, finally, with the temperature heated and stirred of 90～140 ℃ 3～6 hours, obtain polymers soln;
In the 4th step, in mass fraction, the 3rd polymers soln that obtain of step, with after 1～5 part of solidifying agent mixes,, with the rotating speeds stirrings of 50～80 rev/mins 10～30 minutes, is obtained Procuring solution;
In the 5th step, the Procuring solution that the 4th step was obtained evenly is coated on the clean ground in surface, 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 open container, and drips gradually the aqueous solution in container, guarantees when dropwising in 3～8 hours,, along just by complete wetting, obtains pre-functional coating on ground;
The 7th step, after the 6th pre-functional coating that obtain of step is placed in distilled water and cleans 2～3 times, dry under 40～60 ℃, after drying, obtain having gradient contact angle functional coating;
The first initiator described in step 1 is a kind of in Diisopropyl azodicarboxylate, benzoyl peroxide, acetyl peroxide, peroxidation 12 phosphinylidynes, dicumyl peroxide; Described the first monomer is a kind of in hydroxyethyl methylacrylate, Rocryl 410, vinylformic acid carboxylic ethyl ester, Propylene glycol monoacrylate;
Described the second initiator of step 2 is a kind of in Diisopropyl azodicarboxylate, benzoyl peroxide, acetyl peroxide, peroxidation 12 phosphinylidynes, dicumyl peroxide; Described the second monomer is more than one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, methacrylic acid tetradecyl ester, methacrylic acid stearyl, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate and tert-butyl acrylate;
The described solidifying agent of step 4 is aminoresin or isocyanic ester.
2. a kind of preparation method with gradient contact angle functional coating according to claim 1, it is characterized in that: the described solvent of step 3 is more than one in toluene, dimethylbenzene, butylacetate and hexanaphthene.
3. a kind of preparation method with gradient contact angle functional coating according to claim 1, it is characterized in that: the described ground of step 5 is aluminium, copper, silver, gold, silicon or slide glass.
4. a kind of preparation method with gradient contact angle functional coating according to claim 1 is characterized in that: the described 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, more than one in sodium dodecyl sulfate solution.
5. one of according to claim 1-4 described a kind of preparation methods with gradient contact angle functional coating, is characterized in that: described gradient contact angle continuity monotone variation.
6. a kind of preparation method with gradient contact angle functional coating according to claim 5, it is characterized in that: described gradient contact angle variation range is 95 ° ± 5 °～15 ° ± 5 °.
7. one kind has a gradient contact angle functional coating by the described preparation method of one of claim 1-5 preparation.
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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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| 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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Address after: 510640 room 1509-1510, Jinying building, No.1 Jinying Road, Tianhe District, Guangzhou City, Guangdong Province Patentee after: GUANGZHOU KUIKE ELECTROMECHANICAL TECHNOLOGY Co.,Ltd. Address before: Room 04, upper floor, 513 Qingnian Road, Guangzhou Development Zone, Guangdong 510660 Patentee before: GUANGZHOU KUIKE ELECTROMECHANICAL TECHNOLOGY Co.,Ltd. |