CN110433530B - Super-hydrophilic/underwater super-oleophobic co-deposition coating and preparation method thereof - Google Patents

Super-hydrophilic/underwater super-oleophobic co-deposition coating and preparation method thereof Download PDF

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CN110433530B
CN110433530B CN201910791465.6A CN201910791465A CN110433530B CN 110433530 B CN110433530 B CN 110433530B CN 201910791465 A CN201910791465 A CN 201910791465A CN 110433530 B CN110433530 B CN 110433530B
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hydrophilic
mixed system
oleophobic
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CN110433530A (en
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郝红
李琳
杨萌晨
张静静
李星玥
赵夏
段延萍
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Northwestern University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • 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
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance

Abstract

The invention relates to a super-hydrophilic/underwater super-oleophobic codeposition coating and a preparation method thereof, wherein the method comprises the following steps of 1, adjusting the pH value of a sodium chloroacetate solution to 7-8, and reacting the solution and a monomer at 40-80 ℃ for 3-10 h to obtain a mixed system A; step 2, precipitating a product in the mixed system A and then drying to obtain a zwitterion monomer; step 3, adding the zwitterionic monomer and dopamine into a Tris buffer solution or a PBS buffer solution with the pH value of 7-10 to dissolve to obtain a mixed system B; and 4, immersing the substrate into the mixed system B, codepositing the polymerized dopamine and the polymerized monomer on the substrate to form a compound A, taking out the compound A for drying, and obtaining the polydopamine microsphere with the hydrophilic zwitterionic polymer on the surface of the codeposition coating through a polymerization codeposition technology, wherein the polydopamine microsphere has good super-hydrophilic/underwater super-oleophobic characteristics.

Description

Super-hydrophilic/underwater super-oleophobic co-deposition coating and preparation method thereof
Technical Field
The invention relates to the technical field of antifouling, in particular to a super-hydrophilic/underwater super-oleophobic co-deposition coating and a preparation method thereof.
Background
In recent years, mussel biomimetic chemistry has attracted much attention as a new surface modification technology, and is becoming a new favorite in the field of surface modification in a number of advanced disciplines such as chemistry, biology, energy and environment. Marine soft organisms such as mussels and oysters can be firmly adhered to the hard stone wall, the bottom of a navigation ship and even the surface of the culture net cage, and can withstand the impact of sea waves to a certain extent. It has been found that mussels have such strong adhesion under water because they secrete mucin, which has high strength, high toughness and water resistance, as well as special adhesive properties.
In 2007, Messermith et al found that dopamine can undergo oxidative self-polymerization in a weakly alkaline environment, and can form a polydopamine (abbreviated as PDA) coating on the surface of various substrates. The substance of the polymer also contains functional groups such as catechol and primary amine, and has strong adhesiveness similar to the structure of an adhesion site in mucus protein secreted by mussels. In addition, the strong adhesion property of polydopamine endows the surface modification technology with strong universality and universality, and the deposition can be completed on the surfaces of polymers, metals, metal oxides and even low-surface-energy polytetrafluoroethylene.
The super-hydrophilic/underwater super-oleophobic surface is a surface with a static contact angle to water in air below 10 degrees and an underwater oil contact angle above 150 degrees. The super-hydrophilic/underwater super-oleophobic surface has good application prospects in the fields of oil drop control, biological adhesion resistance, self-cleaning, ship pollution prevention, oil-water separation, petroleum transportation and the like. Scholars at home and abroad usually adopt a method of combining hydrophilic chemical composition with special micro-morphology to prepare the super-hydrophilic/underwater super-oleophobic material. Most of the existing preparation methods have the defects of complex process and high cost, and limit the practical application of the super-hydrophilic/underwater super-oleophobic coating.
Chinese patent publications CN105536296A and CN104888498A disclose oil-water separation nets with super-hydrophobic/super-oleophilic properties, which have good oil-water separation efficiency, but oleophilic materials have a tendency to be contaminated or clogged due to adsorbed oil, thereby reducing separation efficiency and repeatable separation performance. The chinese patent publication No. CN103893999A discloses an oil-water separation mesh membrane with super-hydrophilic and underwater super-oleophobic properties, which has the disadvantage of complex preparation process although the oil-water separation effect is achieved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the super-hydrophilic/underwater super-oleophobic co-deposition coating and the preparation method thereof, the preparation process is simple, the operation steps are few, the reaction condition is mild, the cost is low, the stability is good, the super-hydrophilic/underwater super-oleophobic co-deposition coating can be used for large-scale industrial preparation, and the super-hydrophilic/underwater super-oleophobic co-deposition coating has good super-oleophobic property.
The invention is realized by the following technical scheme:
a preparation method of a super-hydrophilic/underwater super-oleophobic co-deposition coating comprises the following steps,
step 1, adjusting the pH value of a sodium chloroacetate solution to 7-8 to obtain a solution A, and reacting the solution A with a monomer at 40-80 ℃ for 3-10 hours to obtain a mixed system A, wherein the monomer is amino-containing acrylic carboxylic acid esters or amino-containing acrylamides;
step 2, precipitating a product in the mixed system A and then drying to obtain a zwitterion monomer;
step 3, adding the zwitterionic monomer and dopamine into a Tris buffer solution or a PBS buffer solution with the pH value of 7-10 to dissolve to obtain a mixed system B;
and 4, immersing the substrate into the mixed system B, co-depositing the polymerized dopamine and the polymerized monomer on the substrate to form a compound A, taking out the compound A, and drying to obtain the super-hydrophilic/underwater super-oleophobic co-deposited coating.
Preferably, in the step 3, the copper sulfate, the hydrogen peroxide, the dopamine and the zwitterionic monomer are added into the Tris buffer solution or the PBS buffer solution together for dissolution to obtain a mixed system B, wherein the mass ratio of the copper sulfate, the hydrogen peroxide and the dopamine is (0-0.8): (0-0.4): 1, the ratio of the mass of the zwitterionic monomer to the mass of dopamine does not exceed 50.
Preferably, in step 3, the ratio of the mass of the zwitterionic monomer to the mass of dopamine does not exceed 50.
Preferably, in the step 4, the substrate is immersed into the mixed system B and then reacts for 10-480 min at a constant temperature of 20-60 ℃, and then the compound A is taken out.
Preferably, the substrate in step 4 is a polymer sheet, a glass sheet, a metal sheet, a screen, a silicon wafer or a fiber cloth.
Preferably, the substrate in step 4 is a substrate after surface cleaning, and the specific cleaning process is as follows,
firstly, soaking a substrate in anhydrous acetone, then ultrasonically cleaning the surface of the soaked substrate by sequentially adopting anhydrous ethanol, anhydrous acetone and distilled water, and finally naturally airing the cleaned substrate.
Preferably, the solvent of the sodium chloroacetate solution in step 1 is isopropanol, ethanol or distilled water.
Preferably, the mass ratio of the monomers to the sodium chloroacetate in the step 1 is 1: (0.5-5).
Preferably, the step 2 of precipitating the product in the mixed system A specifically comprises the following steps,
step 2a, cooling the mixed system A to room temperature, then performing reduced pressure rotary evaporation, and removing water in the mixed system A to obtain a mixed system a;
step 2b, dissolving the mixed system a by using methanol, filtering, and performing reduced pressure rotary evaporation on the obtained filtrate to obtain a mixture a;
step 2c, dissolving the mixture a with absolute ethyl alcohol at the temperature of 30-60 ℃, filtering at the temperature of 30-60 ℃, cooling the obtained filtrate, and performing rotary evaporation to remove the ethyl alcohol to obtain viscous liquid;
and 2d, adding the viscous liquid into anhydrous acetone to obtain a mixed system b, standing the mixed system b at 6-8 ℃ for 8-24 h, and separating out a product from the mixed system b, wherein the mass ratio of the anhydrous acetone to the viscous liquid is (5-10): 1.
the super-hydrophilic/underwater super-oleophobic co-deposition coating is obtained by the preparation method of the super-hydrophilic/underwater super-oleophobic co-deposition coating.
Compared with the prior art, the invention has the following beneficial technical effects:
firstly, reacting sodium chloroacetate with amino-containing acrylic carboxylate or amino-containing acrylamide in a weak alkali environment to obtain a zwitterionic monomer, then dissolving the zwitterionic monomer and dopamine in a Tris buffer solution or a PBS buffer solution with the pH value of 7-10, and immersing the dissolved zwitterionic monomer and dopamine in a substrate, so that the polymerization and codeposition processes of the dopamine, the polymerization and codeposition of the acrylic carboxylate or the amino-containing acrylamide monomer are integrated into a whole on the surface of the obtained super-hydrophilic/underwater super-oleophobic codeposition coating, and the polydopamine microsphere with the hydrophilic zwitterionic polymer is obtained on the surface of the codeposition coating by a polymerization codeposition technology, wherein the particle size of the polydopamine microsphere doped with the hydrophilic polymer is 150-200 nm; dopamine is used as an initiator of monomer polymerization, can initiate many common zwitterionic monomers to generate polymers, and in the codeposition process, the dopamine serves as an adhesion site to ensure that a polymerization product is stably fixed on the surface of a base material, so that the prepared codeposition coating has strong adhesion to almost all base materials, and is widely applied to various bases.
Further, adding copper sulfate, hydrogen peroxide, dopamine and zwitterionic monomer into Tris buffer solution or PBS buffer solution for dissolving, and dissolving dopamine and zwitterionic monomer in CuSO4And H2O2Under the synergistic effect of the components, the dopamine can be rapidly induced to be oxidized and polymerized, and a good deposition effect can be achieved in a very short time.
According to the super-hydrophilic/underwater super-oleophobic co-deposition coating, the polydopamine molecules have a cross-linking structure and can interact with polymer molecules through chemical and physical interaction, so that a stable co-deposition coating can be formed; the co-deposition coating is super-hydrophilic in air, and through an adhesive tape tearing experiment, a solution soaking experiment and a repeated use experiment, the contact angle of water in the air is smaller than 10 degrees, the underwater oil contact angle is larger than 150 degrees, which shows that the prepared super-hydrophilic/underwater super-oleophobic co-deposition coating has good mechanical stability, solution stability and repeated use stability.
Drawings
FIG. 1 shows sodium chloroacetate (ClCH) in example 1 of the present invention2COONa) and zwitterionic monomer (CBMAA-1).
FIG. 2 shows CuSO prepared according to example 1 of the present invention4/H2O2Color change profile over time for initiated dopamine oxidative polymerization.
FIG. 3 is a graph of color change over time for air-induced oxidative self-polymerization of dopamine in example 1 of the present invention.
FIG. 4 is an SEM image at 30000 magnification of a co-deposited coating obtained in example 1 of the present invention.
Fig. 5 is a plot of the water contact angle (55.0 °) in air for a clean blank PE web of example 1 of the present invention.
FIG. 6 is a plot of the water contact angle (0) in air for the P (CBMAA-1)/PDA co-deposited PE sheet of example 1 in accordance with the present invention.
Fig. 7 is a physical diagram of the underwater oil contact angle (140 °) of a clean blank PE sheet according to example 1 of the present invention.
FIG. 8 is a pictorial view of a P (CBMAA-1)/PDA co-deposited PE sheet in underwater oil contact (155 deg.) according to example 1 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention relates to a preparation method of a super-hydrophilic/underwater super-oleophobic co-deposition coating, which comprises the following steps,
step 1, cleaning the surface of a substrate,
taking a block of 20X 20mm2Soaking the substrate sheet in anhydrous acetone for 8-24 h, then respectively ultrasonically cleaning the surface for 10-30 min by sequentially adopting anhydrous ethanol, anhydrous acetone and distilled water, and finally naturally drying;
the substrate can be a polymer sheet, a glass sheet, a metal sheet, a screen, a silicon wafer and a fiber cloth;
step 2, preparing Tris buffer solution or PBS buffer solution according to the prior method,
the preparation of the Tris buffer solution comprises the following steps: weighing Tris (hydroxymethyl) aminomethane (namely Tris), adding distilled water, stirring and dissolving to be complete, and adjusting the pH to 7-10 by using an acid substance to obtain a Tris buffer solution, wherein the concentration of the Tris buffer solution is 10-100 mmol/L; the acid substance is one or more of inorganic acid and organic acid;
the preparation of the PBS buffer solution specifically comprises the following steps: respectively weighing disodium hydrogen phosphate and sodium dihydrogen phosphate, adding distilled water, stirring and dissolving until the disodium hydrogen phosphate and the sodium dihydrogen phosphate are completely dissolved, and adjusting the pH to 7-10 by changing the adding amount of the disodium hydrogen phosphate and the sodium dihydrogen phosphate to obtain a PBS (phosphate buffer solution), wherein the sum of the concentrations of the disodium hydrogen phosphate and the sodium dihydrogen phosphate in the PBS buffer solution is 10-100 mmol/L;
step 3, preparation of the zwitterionic monomer,
taking amino-containing acrylic carboxylic acid ester or amino-containing acrylamide reaction monomer and sodium chloroacetate as raw materials, taking isopropanol, ethanol or distilled water as a solvent, heating to 40-80 ℃ for reaction for 3-10 h, then cooling to room temperature, performing rotary evaporation at 0.8MPa and 60 ℃ to remove water in a reaction system, fully dissolving a crude product with methanol, filtering, performing rotary evaporation at 0.8MPa and 30 ℃ to remove methanol, dissolving the rest mixture with 30-60 ℃ absolute ethanol, and filtering at 30-60 ℃ to obtain a filtrate; after the filtrate is cooled, the filtrate is rotated and evaporated under 0.8MPa and at 50 ℃ to remove the ethanol, and viscous liquid is obtained; and adding anhydrous acetone into the viscous liquid, wherein the mass ratio of the anhydrous acetone to the viscous liquid is (5-10): 1, placing the mixture at 6-8 ℃ for 8-24 h to separate out a white product, and drying the white product in a vacuum oven at 30-60 ℃ for 8-24 h to obtain a zwitterion monomer comprising ethylenic bond-containing zwitterion carboxylic acid esters, ethylenic bond-containing zwitterion sulfonic acid esters or ethylenic bond-containing phosphorylcholine;
the mass ratio of the reaction monomer to the sodium chloroacetate is 1: (0.5-5), considering that the reaction system contains sodium chloroacetate, the solvent can be isopropanol, ethanol or distilled water; the drying time can be shortened by adopting a drying mode, and the experimental efficiency is improved;
step 4, preparing a fast co-deposition coating of the zwitterionic monomer and the dopamine,
adding dopamine, the monomer obtained in the step 3 and the substrate cleaned in the step 1 into the Tris buffer solution or the PBS buffer solution obtained in the step 2, adding a certain amount of copper sulfate and hydrogen peroxide, reacting in a constant temperature shaking table at the constant temperature of 20-60 ℃ for 10-480 min, taking out a sample, washing with distilled water for three times to remove non-adhered polydopamine particles on the surface, and then drying in vacuum at the temperature of 20-60 ℃ for 12-24 h to obtain the super-hydrophilic/underwater super-oleophobic co-deposition coating;
wherein the mass ratio of the copper sulfate, the hydrogen peroxide and the dopamine is (0-0.8): (0-0.4): 1, the ratio of the mass of the zwitterionic monomer to the mass of the dopamine is not more than 50, and the concentration of the dopamine is 0.5-5 mg/mL after the zwitterionic monomer is added into a Tris buffer solution or a PBS buffer solution;
the super-hydrophilic/underwater super-oleophobic codeposition coating integrates dopamine polymerization, monomer polymerization and codeposition process into a whole in CuSO4/H2O2The fast oxidation polymerization can reach excellent deposition effect in short time.
The surface of the deposition coating is provided with hydrophilic polydopamine microspheres of zwitterionic polymers, and the particle size of the polydopamine microspheres doped with hydrophilic polymers is 150-200 nm; the coating is super-hydrophilic in air, the contact angle is less than 10 degrees, and the underwater contact angle to oil is more than 150 degrees; the oil can be edible oil such as oleum Rapae, oleum Lini, oleum ricini, soybean oil, peanut oil, oleum Maydis, oleum gossypii semen, oleum Olivarum, etc.; crude oil, gasoline, kerosene, diesel oil, lubricating oil; n-hexane, n-heptane, and liquid paraffin.
Example 1
The invention relates to a preparation method of a super-hydrophilic/underwater super-oleophobic co-deposition coating, which specifically comprises the following steps,
step 1, cleaning the surface of a PE sheet,
taking a block of 20X 20mm2Soaking the PE sheet in anhydrous acetone for 12h, sequentially performing ultrasonic treatment on the PE sheet by using anhydrous ethanol, anhydrous acetone and distilled water for 10min, and naturally drying the PE sheet;
step 2, preparing a Tris buffer solution,
accurately weighing 0.97g of Tris (hydroxymethyl) aminomethane (Tris), adding distilled water, stirring and dissolving until the solution is completely dissolved, adjusting the pH to 8 by using hydrochloric acid, and adjusting the concentration of the solution to 80 mmol/L;
step 3, preparing the zwitterionic monomer 1-carboxyl-N, N-dimethyl-N-methacrylamide propyl inner salt (CBMAA-1),
weighing 2.5g of N- (3-dimethylaminopropyl) methacrylamide (DMAPMA) according to a certain raw material mass ratio, fully dissolving the DMAPMA with 2ml of distilled water, transferring the DMAPMA into a 100ml four-neck flask, installing a condensing tube and a thermometer, heating, refluxing and magnetically stirring;
1.6g of sodium chloroacetate (ClCH) are weighed2COONa), dissolved in 5ml of distilled water, and then dissolved in sodium hydroxide solutionAdjusting the pH value of the sodium chloroacetate solution to be alkalescent, wherein the pH value is 7;
slowly adding a sodium chloroacetate solution when the temperature of the DMAPMA solution in the four-neck flask reaches 70 ℃, heating to 80 ℃, stopping the reaction after reacting for 7 hours, cooling, and rotationally evaporating at 60 ℃ under 0.8MPa to remove water in a reaction system;
dissolving the crude product with methanol, filtering, rotary evaporating at 30 deg.C under 0.8MPa to remove methanol, and dissolving the rest mixture with 40 deg.C anhydrous ethanol; filtering at 40 deg.C, cooling the filtrate, and rotary evaporating at 50 deg.C under 0.8MPa to remove ethanol to obtain viscous liquid; adding 5 times of anhydrous acetone into the viscous liquid, standing at 6 deg.C for 24 hr to separate out white product, and drying in a vacuum oven at 60 deg.C for 12 hr to obtain zwitterionic monomer CBMAA-1;
from the reactant ClCH of FIG. 12As can be seen by comparing infrared spectrograms of COONa and the product CBMAA-1, 769cm-1The absorption peak attributed to C-Cl stretching vibration appears only in the reactant ClCH2COONa, but not in the IR spectrum of the product CBMAA-1, indicating the disappearance of C-Cl, i.e. ClCH, in the product CBMAA-12COONa undergoes a quaternization reaction with DMAPMA. In the infrared spectrum of the product CBMAA-1, at 1390cm-1And 1535cm-1Two strong absorption peaks appear at the position, and the two peaks respectively belong to carboxylate radical (COO)-1) Symmetric stretching vibration peaks and asymmetric stretching vibration peaks of the groups; 1654cm-1And 1618cm-1The strong absorption peaks of (a) are respectively attributed to the carbonyl group (C ═ O) and the carbon-carbon double bond (C ═ C) in the amide of CBMAA-1; 1329cm-1The absorption peak belongs to the C-N stretching vibration peak in the CBMAA-1 structure. The above analysis shows that the product contains carboxylate radicals (COO)-1) Group, which proves that the prepared product is the target product obtained by quaternization, namely the zwitterionic monomer CBMAA-1;
step 4, preparing a co-deposition coating of the zwitterionic monomer and dopamine P (CBMAA-1)/PDA,
1000mg of CBMAA-1, 20mg of DA were added to 20mL of Tris buffer solution, followed by 10mg of CuSO4And 5mg of H2O2Fully stirring the mixture,And (2) after dissolving, quickly immersing the PE sheet cleaned in the step (1) into the deposition solution, reacting for 30min at 25 ℃ in a temperature-controlled shaking table, co-depositing the polymerized dopamine and the polymerized monomer on the substrate to form a composite membrane, taking out the substrate after the reaction is finished, cleaning the sample for three times by using ultrapure water, and finally placing the substrate in a vacuum drying oven at 60 ℃ until the weight is constant to obtain the super-hydrophilic/underwater super-oleophobic co-deposition coating P (CBMAA-1)/PDA.
FIG. 2 shows that CuSO is added simultaneously4/H2O2The latter solution turned reddish brown at 10min and dark black after 15min, indicating that dopamine was rapidly oxidized and polymerized to produce PDA. FIG. 3 shows no CuSO added4/H2And the dopamine deposition of O, namely the color changes from colorless transparency to grey brown after 40min, and the oxidative polymerization speed is very slow, which indicates that the dopamine deposition efficiency caused by air is not high.
The surface morphology of the P (CBMAA-1)/PDA co-deposited coating was observed by a German ZEISS SIGMA type scanning electron microscope. As shown in FIG. 4, polydopamine microspheres with a particle size of about 150nm were formed on the surface of the P (CBMAA-1)/PDA co-deposition coating. The blank PE sheet obtained in the step 1 and the P (CBMAA-1)/PDA co-deposition PE sheet obtained in the step 4 are tested to have a contact angle of 2 microliters of distilled water in the air and a contact angle of 8 microliters of underwater oil by using an SL200KB type contact angle tester, the water contact angles in the air are respectively 55.0 degrees and 0 degrees, as shown in figures 5 and 6, and the underwater oil contact angles are respectively 140 degrees and 155 degrees, as shown in figures 7 and 8, so that the P (CBMAA-1)/PDA co-deposition coating has good super-hydrophilic and underwater super-oleophobic properties.
Wetting the blank PE sheet obtained in the step 1 and the P (CBMAA-1)/PDA codeposition PE sheet obtained in the step 4 with water respectively, then sucking a certain amount of crude oil by using a disposable dropper to drip to two surfaces of the blank PE sheet and the P (CBMAA-1)/PDA codeposition PE sheet, and then respectively putting the two PE sheets into a beaker filled with distilled water, wherein only part of the crude oil on the blank PE sheet in the step 1 falls off and cannot be washed cleanly with water; and the crude oil on the P (CBMAA-1)/PDA co-deposition PE sheet obtained in the step 4 quickly falls off and becomes clean. After crude oil is added into a beaker for deposition, the crude oil can be quickly cleaned by clear water and can be reused for many times, which shows that the P (CBMAA-1)/PDA codeposition coating has good oil adhesion resistance and is stable and not easy to damage.
Example 2
The invention relates to a preparation method of a super-hydrophilic/underwater super-oleophobic co-deposition coating, which specifically comprises the following steps,
step 1, cleaning the surface of a glass sheet,
taking a block of 20X 20mm2Soaking the glass sheet in anhydrous acetone for 18h, sequentially performing ultrasonic treatment on the glass sheet by using anhydrous ethanol, anhydrous acetone and distilled water for 10min, and naturally drying the glass sheet;
step 2, preparing a Tris buffer solution,
accurately weighing 0.48g of Tris (hydroxymethyl) aminomethane (Tris), adding distilled water, stirring and dissolving until the solution is completely dissolved, adjusting the pH value to 8.5 by using sulfuric acid, and adjusting the concentration of the solution to 40 mmol/L;
step 3, preparing a zwitterion monomer of dimethyl ethyl carboxyl amino ethyl methacrylate (CBMA),
weighing 3.5g of dimethylaminoethyl methacrylate (DMAEMA) according to a certain raw material mass ratio, fully dissolving the DMAEMA with 5ml of distilled water, transferring the DMAEMA into a 100ml four-mouth flask, installing a condenser tube and a thermometer, heating, refluxing and magnetically stirring;
5g of sodium chloroacetate (ClCH) are weighed2COONa) is fully dissolved by 5ml of distilled water, and then the pH value of the sodium chloroacetate solution is adjusted to be alkalescent by using a sodium hydroxide solution, wherein the pH value is 8;
slowly adding a sodium chloroacetate solution when the temperature of the DMAEMA solution reaches 60 ℃, heating to 70 ℃, stopping the reaction after reacting for 8 hours, cooling, and rotationally evaporating at 60 ℃ under 0.8MPa to remove water in a reaction system;
dissolving the crude product with methanol, filtering, rotary evaporating at 30 deg.C under 0.8MPa to remove methanol, and dissolving the rest mixture with 50 deg.C anhydrous ethanol; filtering at 50 deg.C, cooling, and rotary evaporating at 50 deg.C under 0.8MPa to remove ethanol to obtain viscous liquid; adding 8 times of anhydrous acetone into the viscous liquid, standing at 7 deg.C for 20h to separate out white product, and drying in a vacuum oven at 60 deg.C for 18h to obtain zwitterionic monomer CBMA;
step 4, preparing a co-deposition coating of the zwitterionic monomer and dopamine P (CBMA)/PDA,
500mg of P (CBMA), 20mg of DA were added to 20mL of Tris buffer solution, followed by 10mg of CuSO4And 5mg of H2O2After fully stirring and dissolving, quickly immersing the glass sheet cleaned according to the step 1 into the deposition solution, reacting for 40min at 30 ℃ in a temperature-controlled shaking table, and cleaning a sample with ultrapure water for three times; and finally, placing the sample in a vacuum drying oven at 60 ℃ to constant weight to obtain the super-hydrophilic/underwater super-oleophobic co-deposition coating P (CBMA)/PDA.
The codeposition coating prepared by the embodiment has a water contact angle of 5 degrees in air and an underwater oil contact angle of 152 degrees, and achieves a good oil adhesion resistant effect.
Example 3
The invention relates to a preparation method of a super-hydrophilic/underwater super-oleophobic co-deposition coating, which specifically comprises the following steps,
step 1, cleaning the surface of a copper sheet,
taking a block of 20X 20mm2Soaking the copper sheet in anhydrous acetone for 8h, sequentially performing ultrasonic treatment on the copper sheet by using anhydrous ethanol, anhydrous acetone and distilled water for 10min, and naturally drying the copper sheet;
step 2, preparing a Tris buffer solution,
accurately weighing 0.73g of Tris (hydroxymethyl) aminomethane (Tris), adding distilled water, stirring and dissolving until the solution is complete, adjusting the pH to 9 by using nitric acid, and adjusting the concentration of the solution to 60 mmol/L;
step 3, preparing the zwitterionic monomer 1-carboxyl-N, N-dimethyl-N-acrylamide propyl inner salt (CBMAA-2),
weighing 6g of N- (3-dimethylaminopropyl) acrylamide (DMAPAA) according to a certain raw material mass ratio, fully dissolving the DMAPAA with 10ml of distilled water, transferring the DMAPAA into a 100ml four-neck flask, installing a condenser tube and a thermometer, heating, refluxing and magnetically stirring;
8g of sodium chloroacetate (ClCH) are weighed2COONa) is fully dissolved by 9ml of distilled water, and then the pH value of the sodium chloroacetate solution is adjusted to be alkalescent by using a sodium hydroxide solution, wherein the pH value is 7.5;
slowly adding a sodium chloroacetate solution when the temperature of the DMAPAA solution in the four-neck flask reaches 50 ℃, starting timing after the reaction temperature reaches 60 ℃, stopping the reaction after reacting for 6 hours, cooling, pouring out the reaction solution, and rotationally evaporating at 0.8MPa and 60 ℃ to remove water in the reaction system;
dissolving the crude product with methanol, filtering, and rotary evaporating at 30 deg.C under 0.8MPa to remove methanol; dissolving the rest mixture with 60 deg.C anhydrous ethanol; filtering at 60 deg.C, cooling, and rotary evaporating at 50 deg.C under 0.8MPa to remove ethanol to obtain viscous liquid; then 10 times of anhydrous acetone is added into the viscous liquid, the viscous liquid is placed at the temperature of 8 ℃ for 16 hours, a white product is separated out, and the viscous liquid is dried in a vacuum oven at the temperature of 60 ℃ for 18 hours to obtain a zwitterionic monomer CBMAA-2;
step 4, preparing a co-deposition coating of the zwitterionic monomer and dopamine P (CBMAA-2)/PDA,
20mg of CBMAA-2 and 20mg of DA were added to 20mL of Tris buffer solution, followed by 10mg of CuSO4And 5mg of H2O2After fully stirring and dissolving, quickly immersing the glass sheet cleaned in the step 1 of the processed substrate into the deposition solution, reacting for 50min at 40 ℃ in a temperature-controlled shaking table, and cleaning the sample with ultrapure water for three times after the reaction is finished; and finally, placing the sample in a vacuum drying oven at 50 ℃ to constant weight to obtain the super-hydrophilic/underwater super-oleophobic co-deposition coating P (CBMAA-2)/PDA.
The codeposition coating prepared by the embodiment has a water contact angle of 3 degrees in air and an oil contact angle of 153 degrees under water, and achieves a good oil adhesion resistant effect.
Example 4
The invention relates to a preparation method of a super-hydrophilic/underwater super-oleophobic co-deposition coating, which specifically comprises the following steps,
step 1, cleaning the surface of a stainless steel screen,
taking a block of 20X 20mm2Soaking a stainless steel screen of 200 meshes in anhydrous acetone for 10h, sequentially performing ultrasonic treatment for 10min by using anhydrous ethanol, anhydrous acetone and distilled water, and naturally drying;
step 2, preparing a Tris buffer solution,
accurately weighing 0.61g of Tris (hydroxymethyl) aminomethane (Tris), adding distilled water, stirring and dissolving until the solution is complete, adjusting the pH to 8 by using phosphoric acid, and adjusting the solution concentration to 50 mmol/L;
step 3, preparation of zwitterionic monomer 1-carboxyl-N, N-dimethyl-N-methacrylamide propyl inner salt (CBMAA-1):
weighing 5g of N- (3-dimethylaminopropyl) methacrylamide (DMAPMA) according to a certain raw material mass ratio, fully dissolving the DMAPMA with 5ml of distilled water, transferring the DMAPMA into a 100ml four-neck flask, installing a condensing tube and a thermometer, heating, refluxing and magnetically stirring;
7.5g of sodium chloroacetate (ClCH) are weighed2COONa), fully dissolving the mixture by using 6ml of distilled water, adjusting the pH value of a sodium chloroacetate solution to be alkalescent by using a sodium hydroxide solution, wherein the pH value is 7.3, slowly adding the sodium chloroacetate solution when the temperature of a DMAPMA solution in a four-neck flask reaches 45 ℃, heating to 55 ℃, stopping reaction after reacting for 6 hours, and cooling;
rotary evaporation is carried out under 0.8MPa and 60 ℃ to remove the water in the reaction system; dissolving the crude product with methanol, filtering, and rotary evaporating to remove methanol; dissolving the rest mixture with 55 deg.C anhydrous ethanol; filtering at 55 deg.C, cooling, and rotary evaporating at 50 deg.C under 0.8MPa to remove ethanol to obtain viscous liquid; adding 6 times of anhydrous acetone into the viscous liquid, standing at 8 deg.C for 18h to separate out white product, and drying in a vacuum oven at 60 deg.C for 15h to obtain zwitterionic monomer CBMAA-1;
step 4, preparing a co-deposition coating of the zwitterionic monomer and dopamine P (CBMAA-1)/PDA,
500mg of CBMAA-1, 20mg of DA were added to 20mL of Tris buffer solution, followed by 12mg of CuSO4And 6mg of H2O2After fully stirring and dissolving, quickly immersing the stainless steel screen mesh cleaned in the step 1 on the treated substrate into the deposition solution, reacting for 40min at 35 ℃ in a temperature-controlled shaking table, and cleaning the sample with ultrapure water for three times after the reaction is finished; and finally, placing the sample in a vacuum drying oven at 60 ℃ to constant weight to obtain the super-hydrophilic/underwater super-oleophobic co-deposition coating P (CBMAA-1)/PDA.
The codeposition coating prepared by the embodiment has a water contact angle of 5 degrees in air and an underwater oil contact angle of 151 degrees, and achieves a good oil adhesion resistant effect.
Example 5
The invention relates to a preparation method of a super-hydrophilic/underwater super-oleophobic co-deposition coating, which specifically comprises the following steps,
step 1, cleaning the surface of non-woven fabric,
taking a block of 20X 20mm2Soaking the non-woven fabric in anhydrous acetone for 8h, sequentially performing ultrasonic treatment on the non-woven fabric for 10min by using anhydrous ethanol, the anhydrous acetone and distilled water, and naturally drying the non-woven fabric;
step 2, preparing a Tris buffer solution,
accurately weighing 0.24g of Tris (hydroxymethyl) aminomethane (Tris), adding distilled water, stirring and dissolving until the solution is complete, adjusting the pH value to 7.5 by using boric acid, and adjusting the concentration of the solution to 20 mmol/L;
step 3, preparation of a zwitterionic monomer, namely dimethyl ethyl carboxyl amino ethyl methacrylate (CBMA):
weighing 7g of dimethylaminoethyl methacrylate (DMAEMA) according to a certain raw material ratio, fully dissolving the DMAEMA with 7ml of distilled water, transferring the DMAEMA into a 100ml four-neck flask, installing a condenser tube and a thermometer, heating, refluxing and magnetically stirring;
8g of sodium chloroacetate (ClCH) are weighed2COONa), fully dissolving with 10ml of distilled water, adjusting the pH value of the sodium chloroacetate solution to alkalescence by using a sodium hydroxide solution, wherein the pH value is 7.8, slowly adding the sodium chloroacetate solution when the temperature of the DMAEMA solution reaches 65 ℃, heating to 85 ℃, stopping the reaction after reacting for 4 hours, and cooling;
rotary evaporation is carried out under 0.8MPa and 60 ℃ to remove the water in the reaction system; dissolving the crude product with methanol, filtering, and rotary evaporating to remove methanol; dissolving the rest mixture with 40 deg.C anhydrous ethanol; filtering at 40 deg.C, cooling the filtrate, and rotary evaporating at 50 deg.C under 0.8MPa to remove ethanol to obtain viscous liquid; adding 5 times of anhydrous acetone into the viscous liquid, standing at 7 deg.C for 22h to separate out white product, and drying in a vacuum oven at 60 deg.C for 24h to obtain zwitterionic monomer CBMA;
step 4, preparing a co-deposition coating of the zwitterionic monomer and dopamine P (CBMA)/PDA,
600mg of P (CBMA), 20mg of DA were added to the buffer solution of 20mL Tris, followed by 14mg of CuSO4And 7mg of H2O2After fully stirring and dissolving, rapidly immersing the non-woven fabric cleaned according to the step 1 into the deposition solution, reacting for 10min at 50 ℃ in a temperature-controlled shaking table, cleaning the sample with ultrapure water for three times, and finally placing the sample in a vacuum drying oven at 60 ℃ until the weight is constant to obtain the super-hydrophilic/underwater super-oleophobic codeposition coating P (CBMA)/PDA.
The co-deposition coating prepared by the embodiment has a water contact angle of 6 degrees in air and an oil contact angle of 152 degrees under water, and achieves a good oil adhesion resistant effect.
Example 6
The invention relates to a preparation method of a super-hydrophilic/underwater super-oleophobic co-deposition coating, which specifically comprises the following steps,
step 1, cleaning the surface of a silicon wafer,
taking a block of 20X 20mm2Soaking the silicon wafer in anhydrous acetone for 8h, sequentially performing ultrasonic treatment on the silicon wafer for 10min by using anhydrous ethanol, anhydrous acetone and distilled water, and naturally drying the silicon wafer;
step 2, preparing a Tris buffer solution,
accurately weighing 1.21g of Tris (hydroxymethyl) aminomethane (Tris), adding distilled water, stirring and dissolving until the solution is complete, adjusting the pH to 9.5 by using glacial acetic acid, and adjusting the solution concentration to 100 mmol/L;
step 3, preparation of zwitterionic monomer 1-carboxyl-N, N-dimethyl-N-acrylamide propyl inner salt (CBMAA-2):
weighing 10g of N- (3-dimethylaminopropyl) acrylamide (DMAPAA) according to a certain raw material mass ratio, fully dissolving the DMAPAA with 15ml of distilled water, transferring the DMAPAA into a 100ml four-neck flask, installing a condenser tube and a thermometer, heating, refluxing and magnetically stirring;
12g of sodium chloroacetate (ClCH) are weighed2COONa) is fully dissolved by 18ml of distilled water, the pH value of the sodium chloroacetate solution is adjusted to be alkalescent by using a sodium hydroxide solution, the pH value is 7, when the temperature of the DMAPAA solution in the four-neck flask reaches 45 ℃, the sodium chloroacetate solution is slowly added, the reaction temperature reaches 65 ℃, the timing is started, and the reaction is carried out for 8 hoursStopping the reaction, cooling and pouring out the reaction liquid;
rotary evaporation is carried out under 0.8MPa and 60 ℃ to remove the water in the reaction system; dissolving the crude product with methanol, filtering, and rotary evaporating to remove methanol; dissolving the mixture obtained by rotary evaporation in 50 ℃ absolute ethyl alcohol; filtering at 50 deg.C, cooling, and rotary evaporating at 50 deg.C under 0.8MPa to remove ethanol to obtain viscous liquid; adding 6 times of anhydrous acetone into the viscous liquid, standing at 6 deg.C for 18h to separate out white product, and drying in a vacuum oven at 60 deg.C for 12h to obtain zwitterionic monomer CBMAA-2;
step 4, preparing a co-deposition coating of the zwitterionic monomer and dopamine P (CBMAA-2)/PDA,
150mg of CBMAA-2, 20mg of DA were added to 20mL of Tris buffer solution, followed by 5mg of CuSO4And 2.5mg of H2O2After fully stirring and dissolving, quickly immersing the silicon wafer cleaned in the step 1 on the processed substrate into the deposition solution, reacting for 20min at 60 ℃ in a temperature-controlled shaking table, and cleaning the sample with ultrapure water for three times after the reaction is finished; and finally, placing the sample in a vacuum drying oven at 60 ℃ to constant weight to obtain the super-hydrophilic/underwater super-oleophobic co-deposition coating P (CBMAA-2)/PDA.
The codeposition coating prepared by the embodiment has a water contact angle in air of 6 degrees and an underwater oil contact angle of 151 degrees, and achieves a good oil adhesion resistant effect.
Example 7
The invention relates to a preparation method of a super-hydrophilic/underwater super-oleophobic co-deposition coating, which specifically comprises the following steps,
step 1, cleaning the PPMM surface of a polypropylene microporous membrane,
taking a block of 20X 20mm2Soaking the PPMM in anhydrous acetone for 10h, sequentially performing ultrasonic treatment on the PPMM for 10min by using anhydrous ethanol, anhydrous acetone and distilled water, and naturally drying the PPMM;
step 2, preparing a Tris buffer solution,
accurately weighing 0.48g of Tris (hydroxymethyl) aminomethane (Tris), adding distilled water, stirring and dissolving until the solution is completely dissolved, adjusting the pH value to 9 by using oxalic acid, and adjusting the concentration of the solution to 10 mmol/L;
step 3, preparation of zwitterionic monomer 1-carboxyl-N, N-dimethyl-N-acrylamide propyl inner salt (CBMAA-2):
weighing 10g of N- (3-dimethylaminopropyl) acrylamide (DMAPAA) according to a certain raw material mass ratio, fully dissolving the DMAPAA with 15ml of distilled water, transferring the DMAPAA into a 100ml four-neck flask, installing a condenser tube and a thermometer, heating, refluxing and magnetically stirring;
12g of sodium chloroacetate (ClCH) are weighed2COONa), fully dissolving the mixture by using 18ml of distilled water, adjusting the pH value of a sodium chloroacetate solution to be alkalescent by using a sodium hydroxide solution, wherein the pH value is 8, slowly adding the sodium chloroacetate solution when the temperature of a DMAPAA solution in a four-neck flask reaches 45 ℃, starting timing after the reaction temperature reaches 65 ℃, stopping the reaction after reacting for 8 hours, cooling, and pouring out a reaction solution;
rotary evaporation is carried out under 0.8MPa and 60 ℃ to remove the water in the reaction system; dissolving the crude product with methanol, filtering, and rotary evaporating to remove methanol; dissolving the mixture obtained by rotary evaporation in 50 ℃ absolute ethyl alcohol; filtering at 50 deg.C, cooling, and rotary evaporating at 50 deg.C under 0.8MPa to remove ethanol to obtain viscous liquid; adding 6 times of anhydrous acetone into the viscous liquid, standing at 8 deg.C for 8 hr to separate out white product, and drying in a vacuum oven at 60 deg.C for 15 hr to obtain zwitterionic monomer CBMAA-2;
step 4, preparing a co-deposition coating of the zwitterionic monomer and dopamine P (SBMA)/PDA,
250mg of CBMAA-2, 20mg of DA were added to 20mL of Tris buffer solution, followed by 2.5mg of CuSO4And 2mg of H2O2After fully stirring and dissolving, quickly immersing the PPMM cleaned in the step 1 on the treated substrate into the deposition solution, reacting for 55min at 45 ℃ in a temperature-controlled shaking table, and cleaning the sample with ultrapure water for three times after the reaction is finished; and finally, placing the sample in a vacuum drying oven at 60 ℃ until the weight is constant, and obtaining the super-hydrophilic/underwater super-oleophobic co-deposition coating P (SBMA-2)/PDA.
The contact angle of water in the air of the prepared codeposition coating is 3 degrees, the contact angle of oil under water is 152 degrees, and a good oil adhesion resistant effect is achieved.
Examples 8 to 16
The specific procedure of examples 8-16 of the present invention was different only from the materials and parameters of examples 1-7, and therefore, the materials and parameters changed in examples 8-16 are listed below as shown in tables 1 and 2. Through the preparation and testing of the co-deposition coatings, the corresponding water contact angles in air are all less than 10 degrees, and the underwater oil contact angles are all more than 150 degrees.
TABLE 1 specific substances and parameters referred to in examples 8 to 11 of the present invention
Figure BDA0002179668680000181
TABLE 2 specific substances and parameters referred to in examples 12 to 16 of the present invention
Figure BDA0002179668680000191

Claims (5)

1. A preparation method of a super-hydrophilic/underwater super-oleophobic co-deposition coating is characterized by comprising the following steps,
step 1, adjusting the pH value of a sodium chloroacetate solution to 7-8, wherein the solvent of the sodium chloroacetate solution is isopropanol, ethanol or distilled water to obtain a solution A, and reacting the solution A and a monomer at 40-80 ℃ for 3-10 hours to obtain a mixed system A, wherein the monomer is amino-containing acrylic carboxylate or amino-containing acrylamide, and the mass ratio of the monomer to the sodium chloroacetate is 1: (0.5 to 5);
step 2, precipitating a product in the mixed system A and then drying to obtain a zwitterion monomer;
and 3, adding copper sulfate, hydrogen peroxide, a zwitterionic monomer and dopamine into a Tris buffer solution or a PBS buffer solution with the pH value of 7-10 together for dissolution to obtain a mixed system B, wherein the mass ratio of the copper sulfate to the hydrogen peroxide to the dopamine is (0.1-0.8): (0.05-0.4): 1, the ratio of the mass of the zwitterionic monomer to the mass of dopamine does not exceed 50;
and 4, immersing the substrate into the mixed system B, reacting at a constant temperature of 20-60 ℃ for 10-480 min, co-depositing polymerized dopamine and polymerized monomers on the substrate to form a compound A, taking out the compound A, and drying to obtain the super-hydrophilic/underwater super-oleophobic co-deposited coating.
2. The method for preparing the super-hydrophilic/underwater super-oleophobic co-deposition coating according to claim 1, wherein the substrate in step 4 is a polymer sheet, a glass sheet, a metal sheet, a screen, a silicon wafer or a fiber cloth.
3. The preparation method of the super-hydrophilic/underwater super-oleophobic co-deposition coating according to claim 1, characterized in that the substrate in step 4 is a surface-cleaned substrate, and the specific cleaning process is as follows,
firstly, soaking a substrate in anhydrous acetone, then ultrasonically cleaning the surface of the soaked substrate by sequentially adopting anhydrous ethanol, anhydrous acetone and distilled water, and finally naturally airing the cleaned substrate.
4. The preparation method of the super-hydrophilic/underwater super-oleophobic co-deposition coating according to claim 1, characterized in that the product in the mixed system A is precipitated in step 2, and the method specifically comprises the following steps,
step 2a, cooling the mixed system A to room temperature, then performing reduced pressure rotary evaporation, and removing water in the mixed system A to obtain a mixed system a;
step 2b, dissolving the mixed system a by using methanol, filtering, and performing reduced pressure rotary evaporation on the obtained filtrate to obtain a mixture a;
step 2c, dissolving the mixture a with absolute ethyl alcohol at the temperature of 30-60 ℃, filtering at the temperature of 30-60 ℃, cooling the obtained filtrate, and performing rotary evaporation to remove the ethyl alcohol to obtain viscous liquid;
and 2d, adding the viscous liquid into anhydrous acetone to obtain a mixed system b, standing the mixed system b at 6-8 ℃ for 8-24 h, and separating out a product from the mixed system b, wherein the mass ratio of the anhydrous acetone to the viscous liquid is (5-10): 1.
5. the super-hydrophilic/underwater super-oleophobic co-deposition coating obtained by the preparation method of the super-hydrophilic/underwater super-oleophobic co-deposition coating according to any one of claims 1-4.
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