CN113369109A - Preparation method of super-amphiphilic coating based on polydopamine codeposition - Google Patents
Preparation method of super-amphiphilic coating based on polydopamine codeposition Download PDFInfo
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a preparation method of a super-amphiphilic coating based on polydopamine codeposition, which comprises the following steps: dissolving dopamine hydrochloride and nano zero-valent iron in a tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution to obtain a mixed solution; at room temperature, soaking a material to be coated in the mixed solution to ensure that the material to be coated is fully contacted with the mixed solution; and (5) taking out the material obtained by dipping in the step S2, washing and drying, and then obtaining the super-amphiphilic coating based on polydopamine codeposition on the surface of the material to be coated. The coating prepared by the invention has super-hydrophilic and super-oleophilic super-amphiphilic performance, is flat and compact in surface, has a large number of chemical modification sites, can be further functionally modified, realizes more functional applications, and has wide application prospects in the fields of surface modification, composite material preparation and the like, particularly in the fields of self-cleaning and marine antifouling.
Description
Technical Field
The invention belongs to the technical field of polydopamine deposition, and particularly relates to a preparation method of a super-amphiphilic coating based on polydopamine codeposition.
Background
The super-amphiphilic material refers to a material with water drops and oil drops capable of being completely spread on the surface of the material, and is widely applied to the fields of self-cleaning, antifouling, catalysis and the like. At present, common construction methods comprise a sol-gel method, a plasma method, a hydrothermal method, an electrochemical deposition method, a self-assembly method and the like, but the common methods have the defects of complex process, special equipment, high energy consumption, selectivity on a substrate and the like.
Dopamine is used as a main component of mussel adhesive protein, and Lee and the like in 2007 find that the dopamine can be spontaneously polymerized in a weak alkaline solution and spontaneously deposited on the surface of any material, so that the mussel adhesive protein has good adhesive property, and the surface of polydopamine has a large number of chemical sites for secondary modification, so that the surface modification based on polydopamine deposition is a current research hotspot. A large number of hydrophilic hydroxyl groups and amino groups exist on the surface of the polydopamine coating, so that the wettability of the surface of the material can be greatly improved. The preparation process is simple, no organic solvent or special equipment is needed, and the polydopamine coating has the advantage of universality on a base material, so that the polydopamine coating has great potential in constructing the super-amphiphilic self-cleaning material.
However, the self-polymerization deposition of dopamine has the defects of slow reaction speed, uneven surface, poor solvent resistance and the like, so that various oxidants are used for the oxidation-induced polymerization of dopamine, including CuSO4、(NH4)2S2O8、NaIO4And the like (CN106000125A, CN 108785748A). But the oxidant improves the polymerization speed and the agglomeration phenomenon of the polydopamine is obvious; the use of large amounts of oxidizing agents also tends to cause environmental pollution, and these factors limit the application of dopamine. UV-induced polymerization has also been proposed for the polymeric deposition of dopamine, but it doesThe deposition speed is only 2 nm.h-1And the application prospect of dopamine is influenced. In addition, the hydrophilic effect of the polydopamine coating prepared by the method is poor (Xianhuashu et al, applied chemical engineering 2021, 50 (01): 250-.
Disclosure of Invention
The invention aims to overcome the defects that a large amount of oxidant harmful to the environment is used in the existing oxidant-induced poly-dopamine deposition method and the hydrophilization effect is poor, and provides a preparation method of a super-amphiphilic (having both super-hydrophilic and super-oleophilic properties) coating based on poly-dopamine codeposition. The method can quickly form the super-amphiphilic coating on the surface of any material, and is an environment-friendly, quick, simple and convenient preparation method of the super-amphiphilic coating.
The invention adopts the following specific technical scheme:
the invention provides a preparation method of a super-amphiphilic coating based on polydopamine codeposition, which comprises the following specific steps:
s1: dissolving dopamine hydrochloride and nano zero-valent iron in a tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution to obtain a mixed solution;
s2: at room temperature, soaking a material to be coated in the mixed solution to ensure that the material to be coated is fully contacted with the mixed solution;
s3: and (5) taking out the material obtained by dipping in the step S2, washing and drying, and then obtaining the super-amphiphilic coating based on polydopamine codeposition on the surface of the material to be coated.
Preferably, in the mixed solution of step S1, the molar concentrations of dopamine hydrochloride and nanoscale zero-valent iron are both 1 to 50 mM.
Preferably, the nano zero-valent iron is prepared by a liquid phase reduction method.
Preferably, in the step S2, the material to be coated is stirred in the mixed solution for 1-6 h at a stirring speed of 100-500 r.min-1And then allowed to settle by standing.
Preferably, the stirring method is magnetic stirring.
Preferably, in the step S3, the drying temperature is 50 to 120 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention can quickly construct the super-amphiphilic coating on the surface of any material, and the highest deposition rate per unit area can reach 0.367 mg.h-1·cm-2The obtained coating has super-hydrophilic and super-oleophilic super-amphiphilic performance, the surface of the coating is flat and compact, and the coating has a large number of chemical modification sites, so that functional modification can be further performed, and more functional applications can be realized. The reaction system of the invention is a water solvent system, and the nano zero-valent iron is also environment-friendly. The coating prepared by the method has high surface reactivity, and the secondary modification effect is better than that of the traditional method. The preparation method provided by the invention has wide application prospects in the fields of surface modification, composite material preparation, self-cleaning, marine corrosion prevention, antifouling and the like.
Drawings
FIG. 1 is an optical photograph of the water contact angle of the super-amphiphilic coating obtained in example 1;
FIG. 2 is a chart of the oil (CHCl) for the super-amphiphilic coating obtained in example 13) Contact angle optical pictures.
Detailed Description
The invention will be further elucidated and described with reference to the drawings and the detailed description. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
Example 1
The preparation method of the super-amphiphilic coating in the embodiment specifically comprises the following steps:
(1) and ultrasonically degreasing the glass slide in ethanol for 30min, washing the glass slide for 3 times by using deionized water, and then drying the glass slide in a blast oven at the temperature of 80 ℃ for 2h for later use.
(2) 6.057g of tris (hydroxymethyl) aminomethane is weighed in a beaker, dissolved by adding a proper amount of ultrapure water, transferred to a 1L volumetric flask, subjected to constant volume, and adjusted to pH 8.5 by using hydrochloric acid, thus obtaining tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution.
(3) 0.1g of dopamine hydrochloride and 0.014g of nano zero-valent iron were weighed in a 100mL beaker, 50mL of the tris-hydroxymethyl aminomethane-hydrochloric acid buffer solution prepared in step (2) was added, and magnetic stirring was performed to obtain a mixed solution.
(4) Immersing the glass slide in the mixed solution obtained in the step (3) for deposition for 1h while stirring with magnetic force, wherein the stirring speed is 280 r-min-1And taking out the glass slide, cleaning the glass slide for 5 times by using deionized water, and drying the glass slide in a blast oven at the temperature of 80 ℃ for 2 hours to prepare the super-amphiphilic coating on the surface of the glass slide.
In this example, the weight of the slide glass was increased by 0.0018g, and the deposition rate per unit area was 0.225 mg.h-1·cm-2. As shown in FIG. 1, which is an optical picture of the water contact angle of the super-amphiphilic coating obtained in this example, it can be seen that the water drop spreads completely on the coating surface. As shown in fig. 2, which is an optical image of the oil contact angle of the super-amphiphilic coating obtained in this example, it can be seen that oil droplets (chloroform) are completely spread on the surface of the coating.
Example 2
The preparation method of the super-amphiphilic coating in the embodiment specifically comprises the following steps:
(1) and ultrasonically degreasing the glass slide in ethanol for 30min, washing the glass slide for 3 times by using deionized water, and then drying the glass slide in a blast oven at the temperature of 80 ℃ for 2h for later use.
(2) 6.057g of tris (hydroxymethyl) aminomethane is weighed in a beaker, dissolved by adding a proper amount of ultrapure water, transferred to a 1L volumetric flask, subjected to constant volume, and adjusted to pH 8.5 by using hydrochloric acid, thus obtaining tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution.
(3) 0.1g of dopamine hydrochloride and 0.014g of nano zero-valent iron were weighed in a 100mL beaker, 50mL of the tris-hydroxymethyl aminomethane-hydrochloric acid buffer solution prepared in step (2) was added, and magnetic stirring was performed to obtain a mixed solution.
(4) Immersing the glass slide in the solution obtained in the step (3) for deposition for 4h while stirring with magnetic force at a stirring speed of 500 r.min-1And taking out the glass slide, cleaning the glass slide for 5 times by using deionized water, and drying the glass slide in a blast oven at the temperature of 80 ℃ for 2 hours to prepare the super-amphiphilic coating on the surface of the glass slide.
In this example, the weight of the slide glass was increased by 0.0050g, and the deposition rate per unit area was 0.156 mg.h-1·cm-2。
Example 3
The preparation method of the super-amphiphilic coating in the embodiment specifically comprises the following steps:
(1) ultrasonically degreasing glass microfiber filter paper in ethanol for 30min, washing for 3 times by using deionized water, and drying in a 50 ℃ blast oven for 4h for later use.
(2) 6.057g of tris (hydroxymethyl) aminomethane is weighed in a beaker, dissolved by adding a proper amount of ultrapure water, transferred to a 1L volumetric flask, subjected to constant volume, and adjusted to pH 8.5 by using hydrochloric acid, thus obtaining tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution.
(3) 0.1g of dopamine hydrochloride and 0.028g of nano zero-valent iron are weighed in a 100mL beaker, 50mL of the tris-hydroxymethyl aminomethane-hydrochloric acid buffer solution prepared in the step (2) is added, and magnetic stirring is carried out to obtain a mixed solution.
(4) Dipping glass microfiber filter paper in the mixed solution obtained in the step (3) for deposition for 4h while stirring with magnetic force at the stirring speed of 100 r-min-1And taking out the glass microfiber filter paper, washing the glass microfiber filter paper for 5 times by using deionized water, and drying the glass microfiber filter paper in a 50 ℃ blast oven for 4 hours to prepare the super-amphiphilic coating on the surface of the glass microfiber filter paper.
In the embodiment, the weight of the glass microfiber filter paper is increased by 0.0117g, and the deposition speed per unit area is 0.169 mg.h-1·cm-2。
Example 4
The preparation method of the super-amphiphilic coating in the embodiment specifically comprises the following steps:
(1) ultrasonically degreasing 304 stainless steel in ethanol for 30min, washing for 3 times by using deionized water, and then drying in a blast oven at 120 ℃ for 1h for later use.
(2) 6.057g of tris (hydroxymethyl) aminomethane is weighed in a beaker, dissolved by adding a proper amount of ultrapure water, transferred to a 1L volumetric flask, subjected to constant volume, and adjusted to pH 8.5 by using hydrochloric acid, thus obtaining tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution.
(3) 0.1g of dopamine hydrochloride and 0.014g of nano zero-valent iron were weighed in a 100mL beaker, 50mL of the tris-hydroxymethyl aminomethane-hydrochloric acid buffer solution prepared in step (2) was added, and magnetic stirring was performed to obtain a mixed solution.
(4) Dipping 304 stainless steel into the mixed solution obtained in the step (3) for deposition for 3 hours while stirring with magnetic force, wherein the stirring speed is 150 r.min-1And taking out the 304 stainless steel, washing the stainless steel for 5 times by using deionized water, and drying the stainless steel in a blast oven at 120 ℃ for 1 hour to prepare the super-amphiphilic coating on the surface of the 304 stainless steel.
In the example, the weight of 304 stainless steel is increased by 0.0055g, and the deposition rate per unit area is 0.367 mg.h-1·cm-2。
Example 5
The preparation method of the super-amphiphilic coating in the embodiment specifically comprises the following steps:
(1) and ultrasonically degreasing the glass slide in ethanol for 30min, washing the glass slide for 3 times by using deionized water, and then drying the glass slide in a blast oven at the temperature of 80 ℃ for 2h for later use.
(2) 6.057g of tris (hydroxymethyl) aminomethane is weighed in a beaker, dissolved by adding a proper amount of ultrapure water, transferred to a 1L volumetric flask, subjected to constant volume, and adjusted to pH 8.5 by using hydrochloric acid, thus obtaining tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution.
(3) 0.1g of dopamine hydrochloride and 0.014g of nano zero-valent iron were weighed in a 100mL beaker, and 50mL of the tris-hydroxymethyl aminomethane-hydrochloric acid buffer solution prepared in step (2) was added to obtain a mixed solution.
(4) Immersing the glass slide in the solution obtained in the step (3) for deposition for 6h while stirring with magnetic force, wherein the stirring speed is 340 r.min-1And taking out the glass slide, cleaning the glass slide for 5 times by using deionized water, and drying the glass slide in a blast oven at the temperature of 80 ℃ for 2 hours to prepare the super-amphiphilic coating on the surface of the glass slide.
In this example, the weight of the slide glass was increased by 0.0064g, and the deposition rate per unit area was 0.133 mg. h-1·cm-2。
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
Claims (6)
1. A preparation method of a super-amphiphilic coating based on polydopamine codeposition is characterized by comprising the following specific steps:
s1: dissolving dopamine hydrochloride and nano zero-valent iron in a tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution to obtain a mixed solution;
s2: at room temperature, soaking a material to be coated in the mixed solution to ensure that the material to be coated is fully contacted with the mixed solution;
s3: and (5) taking out the material obtained by dipping in the step S2, washing and drying, and then obtaining the super-amphiphilic coating based on polydopamine codeposition on the surface of the material to be coated.
2. The method for preparing the poly-dopamine co-deposition-based super-amphiphilic coating according to claim 1, wherein the molar concentrations of dopamine hydrochloride and nano zero-valent iron in the mixed solution of step S1 are both 1-50 mM.
3. The method for preparing the poly-dopamine co-deposition-based super-amphiphilic coating according to claim 1, wherein the nano zero-valent iron is prepared by a liquid-phase reduction method.
4. The method for preparing the poly-dopamine co-deposition-based super-amphiphilic coating according to claim 1, wherein in step S2, the material to be coated is deposited in the mixed solution for 1-6 h, and the stirring speed is 100-500 r-min-1And then allowed to settle by standing.
5. The method for preparing the poly-dopamine co-deposition based super-amphiphilic coating according to claim 1, wherein the stirring manner is magnetic stirring.
6. The method for preparing the poly-dopamine co-deposition-based super-amphiphilic coating according to claim 1, wherein the drying temperature in step S3 is 50-120 ℃.
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