CN118085722A - Antifouling coating based on natural wax molecule and siloxane polymer molecule composite, and preparation method and application thereof - Google Patents
Antifouling coating based on natural wax molecule and siloxane polymer molecule composite, and preparation method and application thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 96
- 239000011248 coating agent Substances 0.000 title claims abstract description 91
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 42
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title abstract description 17
- 229920000642 polymer Polymers 0.000 title abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 58
- 239000010410 layer Substances 0.000 claims abstract description 34
- 239000011247 coating layer Substances 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000155 melt Substances 0.000 claims abstract description 9
- 239000001993 wax Substances 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000004203 carnauba wax Substances 0.000 claims description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 239000002052 molecular layer Substances 0.000 claims description 13
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- 239000007787 solid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- -1 polysiloxane Polymers 0.000 claims description 4
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 4
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- 238000002156 mixing Methods 0.000 claims description 2
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- 102000004169 proteins and genes Human genes 0.000 description 10
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- 239000002390 adhesive tape Substances 0.000 description 4
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- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- 241000208720 Nepenthes Species 0.000 description 1
- 241000199919 Phaeophyceae Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
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- MHMNJMPURVTYEJ-UHFFFAOYSA-N fluorescein-5-isothiocyanate Chemical compound O1C(=O)C2=CC(N=C=S)=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 MHMNJMPURVTYEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
-
- 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
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
- C09D191/06—Waxes
-
- 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
-
- 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
- C09D5/1675—Polyorganosiloxane-containing compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention provides an antifouling coating based on the combination of natural wax molecules and siloxane polymer molecules, and a preparation method and application thereof. The preparation method realizes rapid polymerization by catalyzing siloxane molecules with trace acid on a smooth surface formed by natural wax, and comprises two steps: firstly, immersing a substrate into a melt of natural wax, and obtaining a coating layer with uniform thickness in a lifting and rotating mode, wherein a smooth and uniform wax layer is formed after the wax layer is completely solidified; secondly, the dimethyl dimethoxy silane molecules are catalyzed by a trace amount of sulfuric acid to be rapidly polycondensed in the solution to form a prepolymer solution, and the substrate coated with the wax layer is immersed in the prepolymer solution of the dimethyl dimethoxy silane, so that the siloxane molecules are compounded with the wax layer to prepare a composite coating, which has excellent anti-fouling capability and good application prospect in the field of underwater anti-fouling. The coating has low requirement on the substrate, good stability, and no toxicity and pollution to the environment.
Description
Technical Field
The invention belongs to the technical and application fields of biological materials, and particularly relates to an antifouling coating based on the combination of natural wax molecules and siloxane polymer molecules, and a preparation method and application thereof.
Background
Biofouling attached to the surfaces of underwater facilities such as ships, dykes and the like has a number of negative effects on the human environment, energy and economic development. Among the relevant biofouling control means, antifouling coating materials account for a large part.
At present, self-polishing type antifouling coating materials which do not contain organic tin still occupy the domestic and foreign coating markets. The paint is mainly characterized in that an antifouling agent filled in the paint is released through hydrolysis of base resin, toxic substances in the antifouling agent are utilized to kill fouling organisms, and fouling on the surface of equipment is removed through continuous removal of the base resin, so that a self-polishing effect is achieved. However, the release amount of toxic substances in the anti-fouling agent is not easy to control, and the long-term release of the toxic substances can inevitably pollute the water environment, and the ecological balance is destroyed in serious cases.
The low surface energy materials exhibit excellent properties in the areas of surface anti-fouling, self-cleaning and drag reduction. The fouling release type antifouling coating material with low surface energy makes it difficult for fouling organisms to form a firm adhesion layer on the surface of the material, thereby achieving the antifouling effect. The traditional organosilicon and organic fluorine materials for preparing the low-surface-energy fouling desorption type antifouling coating material are generally poor in combination performance with a substrate, and have high requirements on the substrate, so that the stability of the coating is not strong, and the static antifouling capability is not ideal.
The lubricated surface exhibits excellent slidability and anti-adhesion effects for a variety of substances, playing an important role in achieving fluid transport, self-cleaning and anti-fouling areas. The creation of a lubricated surface is related to the natural inspired nepenthes predation principle, and in 2011, aizenberg developed a technology (Slippery Porous Lubricant-infused Surfaces, SLIPS) for injecting a lubricated liquid into a porous surface, i.e. injecting a low surface energy liquid (such as silicone oil) into a material surface with interconnected pores, so as to prepare a liquid surface with super-slippery effect, which makes it difficult for fouling organisms to adhere to the surface. However, in an underwater environment, the liquid lubricant tends to bleed out from the porous surface, resulting in a weaker stability of the coating, i.e. the long-term stability of the SLIPS system under water still faces a great challenge.
Studies have shown that grafting flexible molecules onto smooth surfaces is an effective strategy for preparing lubricated surfaces ("Liquid-like" strategy), in which the flexible molecules that provide lubrication are bound to relatively smooth surfaces by chemical bonding that renders the coating more stable than SLIPS surfaces. Currently, methods including vapor deposition, heat treatment, ultraviolet irradiation, and end-group functionalized complementary bonding are used to prepare Liquid-like surfaces. In these methods, flexible molecular polymers have a relatively stringent requirement on the substrate, and the substrate needs to be subjected to hydroxylation treatment or functionalization treatment of special reactive groups to form chemical bonds with the polymer, which not only increases the complexity and cost of coating preparation, but also makes such coatings difficult to mass-produce.
The currently reported methods have more problems, firstly, the flexible molecular layer playing a key lubrication function is extremely easy to be corroded by external environment and loses the lubrication effect in practical underwater application. Moreover, the thickness of the flexible molecular layer prepared by the current technology is in the nanometer level and is generally lower than 100 nanometers, and in practical applications, such as ship surfaces, the roughness of the flexible molecular layer is generally in the micrometer level, so that the flexible molecular layer prepared by the current method cannot fully cover the surface of a real object, the sliding property of the flexible molecular layer is greatly reduced, and in addition, the possibility that the flexible molecular layer is damaged is further increased due to the excessively high surface roughness. In summary, the overall resistance of the coatings obtained by the current reporting process is low. Second, the flexible molecular layer is capable of bonding to the surface of the object if the surface of the object is required to contain a necessary functional group, such as a hydroxyl group. While surfaces of things, such as marine surfaces, typically contain corrosion protection layers, such as paints, the corrosion protection layer surface is an inert layer and contains little reactive functionality. Therefore, how to effectively graft flexible molecules on the surface of an object and to prepare an antifouling coating with high underwater tolerance is a challenging task. More importantly, according to our observations, the lubricity of the coating is not the only determinant of its underwater antifouling properties, and the underwater anti-bioadhesion properties of the coating are related to the chemical properties of the coating, such as the type and number of chemical functional groups, etc. Therefore, on the basis of the flexible molecular layer, we should also explore a new antifouling strategy to synergistically increase the underwater antifouling performance of the coating.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an antifouling coating based on the combination of natural wax molecules and siloxane polymer molecules, a preparation method and application thereof, and a substance which is easy to form a film and can fully cover the surface of a substrate is introduced, so that a flat surface layer is formed on the surface of an object, the roughness of the object is reduced, and the substance contains rich chemical functional groups.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The first object of the present invention is to provide a method for preparing an antifouling coating based on the complexing of natural wax molecules with silicone polymer molecules, comprising the following specific steps:
S1, immersing a substrate into a melt of natural wax, and obtaining a coating layer with uniform thickness in a lifting and rotating mode, wherein a smooth and uniform wax layer is formed after the wax layer is completely solidified;
S2, mixing siloxane monomer molecules with isopropanol, adding concentrated sulfuric acid, and rapidly polycondensing to form a prepolymer solution;
s3, immersing the substrate coated with the wax layer into a prepolymer solution of siloxane monomer molecules to enable the siloxane molecules to be compounded with the wax layer, and forming a stable polysiloxane oligomer molecular layer.
Further, the natural wax at least completely covers the substrate after being melted, and the thickness of the natural wax layer covered on the surface of the substrate is 0.1-100 mu m.
Further, the volume ratio of the siloxane monomer molecules to the isopropyl alcohol is 1: (4-5), the volume ratio of the siloxane monomer molecules to the concentrated sulfuric acid is 2mL: (100-120) mu L.
Further, the natural wax includes palm wax or beeswax.
Further, the siloxane monomer molecule comprises dimethyldimethoxy silane.
Further, in step S1, the preparation process of the melt of the natural wax includes weighing the natural wax in a beaker, heating the beaker in a water bath at 80-85 ℃, continuously heating and homogenizing the solid natural wax for 20-60 min after the solid natural wax is completely converted into liquid, and keeping Wen Daiyong in the water bath after bubbles in the melt are completely discharged.
In step S1, the curing time is 2-6 hours.
The second object of the invention is an antifouling coating prepared by the preparation method.
Further, the drop sliding angle of the composite coating is: at 10 μl droplet, slip angle <40 0.
The second purpose of the invention is to apply the antifouling coating prepared by the preparation method to the preparation of underwater antifouling products.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a preparation method of an antifouling coating based on the combination of natural wax molecules and siloxane polymer molecules, which realizes rapid polymerization by catalyzing siloxane molecules with trace acid on a smooth surface formed by natural wax, and comprises the following two steps: firstly, immersing a substrate into a melt of natural wax, and obtaining a coating layer with uniform thickness in a lifting and rotating mode, wherein a smooth and uniform wax layer is formed after the wax layer is completely solidified; and secondly, rapidly polycondensing dimethyl dimethoxy silane molecules in a solution to form a prepolymer solution by using a trace amount of sulfuric acid, immersing the substrate coated with the wax layer into the dimethyl dimethoxy silane prepolymer solution to enable siloxane molecules to be compounded with the wax layer, and forming a stable polysiloxane oligomer molecular layer (DMS). The two substances are compounded, so that the composite coating has an excellent anti-fouling capability due to the fact that the natural wax substances have rich chemical functional groups and the chemical functional groups are synergistic.
(2) The present invention utilizes the complexing ability of natural waxes with silicone polymers to produce a composite coating on a relatively rough and inert substrate surface. The coating has obvious influence on the physical and chemical properties and wettability of the surface of the material, and the antifouling capacity of the surface of the substrate is greatly improved. The micro-nano structure of the coating endows the surface of the material with good hydrophobic property; the coating has good antifouling capacity due to the synergistic effect of the rich functional groups of the natural wax substances and the flexible molecular layer, wherein the low surface energy and the lubricating effect are achieved; has excellent anti-adhesion effect on inorganic nano particles, proteins, marine microalgae and other pollutants. Experiments on underwater hanging plates show that the coating can reduce the adhesion of sludge, algae and other pollutants in water to a certain extent in a static water area environment. And the raw material natural wax has the characteristics of easy availability, green and non-toxicity, low price, reproducibility, good film forming capability and the like, so that the preparation method of the coating is simple, the requirement on a substrate is low, the stability is good, the environment is non-toxic and pollution-free, and the coating is a coating material with development prospect in the field of underwater pollution prevention.
(3) Because of the relatively low surface energy and stable composite effect of the two raw material molecules, the coating has low surface energy and excellent lubricity, and pollutant molecules are not easy to adhere to the surface of the coating, so that the coating has good anti-adhesion effect on the surfaces of various pollutants. The main materials of the composite coating are natural waxes (such as carnauba wax CW and beeswax BW and waxes with active hydroxyl or hydroxy fatty acid esters in other components) and siloxane monomer molecules. The natural wax has excellent film forming property, and the melted natural wax has good flowing effect, can rapidly form a film on the surface of a substrate, and more importantly, the natural wax contains rich chemical functional groups, can generate synergistic effect with a flexible molecular layer, and can increase the anti-bioadhesion performance of the coating under water; siloxane monomer molecules (such as dimethyl dimethoxy silane) are polymerized into siloxane oligomer under the catalysis of trace sulfuric acid, and silane chains have good flexibility and are easy to form a lubricating surface. The natural wax cooperates with the siloxane low polymer molecules with lubricating effect through active groups to form a stable composite coating.
Drawings
FIGS. 1a and 1b are graphs comparing the wiener structure and roughness of a DMS@CW coating layer and a DMS@BW coating layer;
FIG. 2 is a graph showing the surface energy, wettability and sliding properties of the surfaces of the substrates before and after the modification of the ship plate substrate by the DMS@CW coating and the DMS@BW coating, respectively;
FIG. 3 is a graph of the stability of the bonding of the DMS@CW coating to the substrate;
FIG. 4 is a graph of the anti-fouling effect of a DMS@CW coating on proteins;
FIG. 5 is a graph of the antifouling effect of a DMS@CW coating on marine microalgae;
FIG. 6 is a graph of the anti-fouling effect of a DMS@CW coating on nanoparticles;
FIG. 7 is a graph of the underwater antifouling effect of DMS@CW coating.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description of the specific embodiments of the present invention will be given with reference to the accompanying drawings. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In practice, the natural wax is melted to cover the substrate at least completely, and the natural wax layer on the surface of the substrate may have a thickness of 0.1 μm to 100 μm.
Contact angle and sliding angle measurements in this example: testing wettability of the surface of the coating by adopting a contact angle/interfacial tension measuring instrument; the test liquid is water and n-hexadecane; for contact angle testing, the liquid volumes were all 10.0 μl, and the contact angles were measured 5 times at different locations for each sample, and averaged; for the slip angle test, the liquid volumes were all 10.0 μl, and the slip angles were measured 5 times at different locations for each sample, and averaged.
Example 1
(1) Pretreatment of a material substrate:
Placing the substrate in an ultrasonic cleaning instrument, cleaning for 10min by deionized water, drying by nitrogen, cleaning for 10min by absolute ethyl alcohol, and drying by nitrogen for later use.
(2) Preparation of palm wax melt:
30.0g of flaky carnauba wax is weighed into a 100ml beaker, placed into a water bath kettle at 85 ℃ for heating, and heated and homogenized for 30min after all the solid carnauba wax is converted into liquid, so that bubbles in the liquid are completely discharged and then kept in the water bath kettle Wen Daiyong.
(3) Preparing a DMS prepolymer solution:
2.0mL of a dimethyldimethoxysilane solution was taken and mixed with 10.0mL of isopropanol, 100. Mu.L of concentrated sulfuric acid was added, and the mixture was stirred at room temperature on a magnetic stirrer at 4500rpm for 10 minutes. The prepolymer solution is ready-to-use.
(4) Preparation of DMS@CW composite coating
The surface of the ship plate substrate (2 cm multiplied by 2 cm) is coated and modified by a dip coating method, the pretreated ship plate is immersed into palm wax melt, and the ship plate is vertically lifted and rotated after being preheated until a uniform palm wax coating layer is formed. Taking out and naturally solidifying for 3 hours at room temperature. Immersing the solidified palm wax coated substrate into DMS prepolymer solution, directly taking out after 30s, and placing at room temperature, and forming a siloxane oligomer molecular composite layer after the solvent on the surface of the wax layer naturally volatilizes.
Example 2
(1) Pretreatment of a material substrate:
Placing the substrate in an ultrasonic cleaning instrument, cleaning for 10min by deionized water, drying by nitrogen, cleaning for 10min by absolute ethyl alcohol, and drying by nitrogen for later use.
(2) Preparation of palm wax melt:
30.0g of flaky carnauba wax is weighed into a 100ml beaker, placed into a water bath kettle at 85 ℃ for heating, and heated and homogenized for 30min after all the solid carnauba wax is converted into liquid, so that bubbles in the liquid are completely discharged and then kept in the water bath kettle Wen Daiyong.
(3) Preparing a DMS prepolymer solution:
2.0mL of a dimethyldimethoxysilane solution was taken and mixed with 10.0mL of isopropanol, 100. Mu.L of concentrated sulfuric acid was added, and the mixture was stirred at room temperature on a magnetic stirrer at 4500rpm for 10 minutes. The prepolymer solution is ready-to-use.
(4) Preparation of DMS@CW composite coating
The surface of the ship plate substrate (2 cm multiplied by 2 cm) is coated and modified by a dip coating method, the pretreated ship plate is immersed into palm wax melt, and the ship plate is vertically lifted and rotated after being preheated until a uniform palm wax coating layer is formed. Taking out and naturally solidifying for 3 hours at room temperature. Immersing the solidified palm wax coated substrate into DMS prepolymer solution, directly taking out after 1min, and placing at room temperature, and forming a siloxane oligomer molecular composite layer after the solvent on the surface of the wax layer naturally volatilizes.
Example 3
(1) Pretreatment of a material substrate:
Placing the substrate in an ultrasonic cleaning instrument, cleaning for 10min by deionized water, drying by nitrogen, cleaning for 10min by absolute ethyl alcohol, and drying by nitrogen for later use.
(2) Preparation of palm wax melt:
30.0g of flaky carnauba wax is weighed into a 100ml beaker, placed into a water bath kettle at 85 ℃ for heating, and heated and homogenized for 30min after all the solid carnauba wax is converted into liquid, so that bubbles in the liquid are completely discharged and then kept in the water bath kettle Wen Daiyong.
(3) Preparing a DMS prepolymer solution:
2.0mL of a dimethyldimethoxysilane solution was taken and mixed with 10.0mL of isopropanol, 120. Mu.L of concentrated sulfuric acid was added, and the mixture was stirred at room temperature on a magnetic stirrer at 4500rpm for 20 minutes. The prepolymer solution is ready-to-use.
(4) Preparation of DMS@CW composite coating
The surface of the ship plate substrate (2 cm multiplied by 2 cm) is coated and modified by a dip coating method, the pretreated ship plate is immersed into palm wax melt, and the ship plate is vertically lifted and rotated after being preheated until a uniform palm wax coating layer is formed. Taking out and naturally solidifying for 3 hours at room temperature. Immersing the solidified palm wax coated substrate into DMS prepolymer solution, directly taking out after 1min, and placing at room temperature, and forming a siloxane oligomer molecular composite layer after the solvent on the surface of the wax layer naturally volatilizes.
Example 4
(1) Pretreatment of a material substrate:
Placing the substrate in an ultrasonic cleaning instrument, cleaning for 10min by deionized water, drying by nitrogen, cleaning for 10min by absolute ethyl alcohol, and drying by nitrogen for later use.
(2) Preparation of beeswax melt:
15.0g of massive beeswax is weighed into a 100ml beaker, placed into a water bath kettle at 75 ℃ for heating, and heated and homogenized for 30min after the beeswax is completely converted into liquid, so that bubbles in the melt are completely discharged and then kept in the water bath kettle Wen Daiyong.
(3) Preparing a DMS prepolymer solution:
2.0mL of a dimethyldimethoxysilane solution was taken and mixed with 10.0mL of isopropanol, 100. Mu.L of concentrated sulfuric acid was added, and the mixture was stirred at room temperature on a magnetic stirrer at 4500rpm for 20 minutes. The prepolymer solution is ready-to-use.
(4) Preparation of DMS@BW composite coating
The surface of the ship plate substrate (2 cm multiplied by 2 cm) is coated and modified by a dip coating method, the pretreated ship plate is immersed into beeswax melt, and the ship plate is vertically lifted and rotated after being preheated until a uniform palm wax coating layer is formed. Taking out and naturally solidifying for 3 hours at room temperature. Immersing the cured beeswax-coated substrate into DMS prepolymer solution, directly taking out after 1min, and placing at room temperature, and forming the siloxane oligomer molecular composite layer after the solvent on the surface of the wax layer naturally volatilizes.
In order to better explore the detergency performance of the lubricating coating provided by the application, the inventors conducted the following studies:
(1) Micro-nano structure and roughness graph comparison research
As shown in FIGS. 1a and 1b, the DMS@CW is prepared in example 1 and the DMS@BW is prepared in example 4.
The microscopic morphology of the DMS@CW coating layer is in a nano-scale fold shape, and the fold distribution is relatively uniform and dense. The average roughness of the coating was 0.99 μm (Ra), the mean square roughness (Rq) was 1.35 μm, and a smooth surface with a certain glossiness was formed in a macroscopic state with a thickness of 93.3. Mu.m.
The surface of the DMS@BW coating layer is provided with a plurality of uneven block-shaped protrusions, and the continuous block-shaped protrusions and the intermediate ravines form a corrugated-like structure. The bump-like projections had a diameter of about 10 μm to 25. Mu.m, the average roughness of the coating layer was 1.04 μm (Ra), and the mean square roughness (Rq) was 1.27. Mu.m. A smooth and flat surface is formed in a macroscopic state.
The average roughness of the base substrate was 1.31 μm (Ra), and the mean square roughness (Rq) was 1.6. Mu.m. Both coatings reduce the surface roughness of the substrate compared to the original substrate, allowing it to form a smoother surface.
(2) And (5) researching the surface energy, wettability and slidability of the surfaces of the substrates before and after the substrates of the ship plates are modified.
As shown in FIG. 2, the DMS@CW is prepared in example 2 and the DMS@BW is prepared in example 4.
As can be seen from FIG. 2, the uncoated boat deck substrate has a relatively high surface energy (36.09 mJ/m 2) and the droplets are in a viscous state on their surface. The surface energy of the ship plate substrate coated with the natural wax layer is greatly reduced, wherein the surface energy of the substrate coated with the palm wax layer is 21.08mJ/m 2, and the surface energy of the substrate coated with the beeswax is 18.18mJ/m 2. The surface energy of the coating layer was substantially unchanged (change value 2.00.+ -.1 mJ/m 2) after the wax layer was composited with the silicone polymer molecules, which gave excellent lubrication effect to the coating layer, wherein the Sliding Angle (SA) of the droplet on the DMS@CW coating layer was 18.16℃and the Sliding Angle (SA) on the DMS@CW coating layer was 18.37 ℃.
(3) Stability study of the bonding of DMS@CW coatings to substrates
The test was carried out using the dms@cw coating prepared in example 3.
The coatings were subjected to substrate adhesion testing using ASTM standards. Firstly, drawing a grid shape on the surface of a coating by using a blade, then adhering a 3M adhesive tape to a grid scratch, applying pressure by using tweezers to remove gaps between the adhesive tape and the coating, tearing off the 3M adhesive tape with horizontal upward force along two sides of the adhesive tape after staying for 1min, and observing whether the grid area and the scratch edge fall off under a scanning electron microscope.
As can be seen from FIG. 3, the grid area and the scratch edge of the coating are not fallen off when observed under a scanning electron microscope, which shows that the coating has good adhesion capability with the steel plate substrate and good bonding stability with the substrate.
(4) Investigation of the antifouling Effect of DMS@CW coating on proteins
The test was carried out using the dms@cw coating prepared in example 1.
Using FITC-labeled bovine serum albumin and human LgG protein as adhesion proteins, the proteins were dissolved in PBS buffer at ph=0.4 at a concentration of 1mg/mL. A region on the coating was marked with a knife blade, the prepared protein buffer was dropped into the test region, left at room temperature in the dark for 4h, and then washed out with PBS buffer. The adhesion of the proteins in the region was observed and recorded with a two-photon confocal microscope.
As can be seen from fig. 4, the two proteins fluoresce very strongly on the boat deck base, covering almost the entire area. And the protein adhesion amount on the surface of the DMS@CW coating is small, and only weak fluorescence is observed under a microscope. The fluorescence intensity in the region was quantified, and the fluorescence intensity of the control group was set to 100.00%, which was referred to as an adhesion rate of 100.00%. The bovine serum albumin attachment rate of the dms@cw coating was 37.70% and the human LgG protein attachment rate was only 0.16%. This shows that the DMS@CW coating can obviously reduce the protein adhesion rate and has good protein adhesion resistance.
(5) Research on antifouling effect of DMS@CW coating on marine microalgae
Experiments were performed using dms@cw prepared in example 1 and dms@bw prepared in example 4.
The algae type is Phaeophyta tsaoko, the body size is about several micrometers, the initial concentration of algae is about 104/mL, the algae is co-cultured with the sample on the 7 th day of breeding, the culture temperature is 20-28 ℃, the illumination time is 8-16 h each day, and the algae is shaken in the morning and evening.
As can be seen from FIG. 5a, the algae on the ship plate (Blank) is adhered to a serious extent, and the algae adhered to the ship plate in 15day is spread over almost the whole surface. The attachment amount of the flat algae is continuously increased from 15 days to 30 days. The pictures show that the density and thickness of the attached flat algae are increased, and the surface of the ship plate is seriously polluted by algae. The algae attachment amount of the DMS@CW coating is relatively low, the attachment amount of the flat algae is low within 15 days, and the attachment density is low. The attachment density and thickness of the flat algae on the surface of the coating are almost unchanged from 15 days to 30 days. The DMS@BW coating is slightly polluted by the flat algae within 15 days, and the attachment amount of the flat algae is gradually increased from 15 days to 30 days.
As can be seen from fig. 5b, when the attachment area of the flat algae is quantitatively treated and the attachment area of the flat algae in the control group is set to be 100.00%, the attachment area of the flat algae in the 15 th day of the dms@cw coating is 27.08%, and the attachment area of the flat algae in the 30 th day of the dms@cw coating is 43.06%, which indicates that the algae attachment speed of the coating in the static seawater environment is slow, and the coating has good static anti-algae capability. The algae attachment area of the DMS@BW coating layer at 15day is 73.26%, and the algae attachment area at 30day is almost 100%.
(6) Study of antifouling effect of DMS@CW coating on nanoparticles
The test was carried out using the dms@cw coating prepared in example 3.
The test was performed using titanium dioxide (TiO 2) nanoparticles having a diameter of 100nm, and 2g of nano TiO 2 was sufficiently dispersed in 20mL of ultra pure water to obtain nano TiO 2 suspension having a concentration of 2 g/mL. Square areas with a length and width of 0.5cm x 0.5cm were selected on the surface of the prepared coating and marked with a knife scribe. 20 mu L of the prepared nano TiO 2 suspension liquid is sucked by a liquid-transfering gun and is dripped in a square test area, after the liquid is remained for 1min, the liquid is sucked from the edge of the area by filter paper, the operation is repeated for 10 times, and then the sample is dried by nitrogen. The adhesion of the TiO 2 nanoparticles in the test area was observed and recorded under a scanning electron microscope.
As can be seen from fig. 6, there are a large number of nano TiO 2 particles remaining on the surface of the ship plate substrate, and a large number of nano TiO 2 particles are contained in the defect structure and depressions of the surface in addition to the nano TiO 2 particles stacked on the surface. On the relatively smooth surface of the DMS@CW coating, few nano TiO 2 particles remain. Quantifying the coverage area of the nano TiO 2 particles in the region, and setting the coverage area of the nano TiO 2 particles of the ship plate of the control group to be 100.00%. The coverage area of nano TiO 2 particles on the surface of the DMS@CW coating is only 1.88%, which shows that the coating has good anti-adhesion effect on inorganic nano particles.
(7) Underwater antifouling effect research of DMS@CW coating
The test was carried out using the dms@cw coating prepared in example 2.
A self-made simulated hanging plate device is adopted to vertically hang a sample with the size of 3.0cm multiplied by 3.0cm at a position with the depth of about 30cm to 50cm from the water surface. The underwater hanging plate time is 3-4 months and 7-8 months each year, namely the vigorous period of aquatic organisms such as algae and snails, and the water temperature is about 15-25 ℃. After 30 days, the sample was removed and the contamination level of the sample was recorded after rinsing the surface contamination of the sample with pure water gently.
As can be seen from fig. 7, the macroscopic image shows that the pollution of the substrate surface of the ship board is serious within 30day, and the whole paint surface is almost completely covered by sludge, algae and the like in water. The pollution condition of the DMS@CW coating at the 30day is lighter, and the original appearance of the coating is not completely covered by pollutants. The microscopic morphology comparison shows that the pollutant attached to the surface of the ship plate reaches a certain thickness, almost completely covers the original morphology of the ship plate, the pollutant on the surface of the DMS@CW coating is sparsely covered, and only part of the area is adhered by the pollutant. And the DMS@CW coating is not foamed and falls off in one month of underwater soaking, which shows that the DMS@CW coating reduces the adhesion of pollutants on the surface of a ship board in a still water environment and has a certain application potential in underwater antifouling application.
The above is not relevant and is applicable to the prior art.
Although specific embodiments of the invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the foregoing examples are provided for illustration only and are not intended to limit the scope of the invention, and that various modifications or additions and substitutions are possible to the described specific embodiments without departing from the scope of the invention as defined in the accompanying claims. It should be understood by those skilled in the art that any modification, equivalent substitution, improvement, etc. made to the above embodiments according to the technical substance of the present invention should be included in the scope of protection of the present invention.
Claims (10)
1. A method for preparing an antifouling coating based on the composition of natural wax molecules and silicone polymer molecules, comprising the following specific steps:
S1, immersing a substrate into a melt of natural wax, and obtaining a coating layer with uniform thickness in a lifting and rotating mode, wherein a smooth and uniform wax layer is formed after the wax layer is completely solidified;
S2, mixing siloxane monomer molecules with isopropanol, adding concentrated sulfuric acid, and rapidly polycondensing to form a prepolymer solution;
s3, immersing the substrate coated with the wax layer into a prepolymer solution of siloxane monomer molecules to enable the siloxane molecules to be compounded with the wax layer, and forming a stable polysiloxane oligomer molecular layer.
2. The method according to claim 1, wherein the natural wax is melted to cover the substrate at least completely, and the natural wax layer on the surface of the substrate has a thickness of 0.1 μm to 100 μm.
3. The method of claim 2, wherein the volume ratio of the siloxane monomer molecules to the isopropyl alcohol is 1: (4-5), the volume ratio of the siloxane monomer molecules to the concentrated sulfuric acid is 2mL: (100-120) mu L.
4. The method of claim 1, wherein the natural wax comprises palm wax or beeswax.
5. The method of preparation of claim 1, wherein the siloxane monomer molecule comprises dimethyldimethoxysilane.
6. The preparation method of the natural wax according to claim 1, wherein in the step S1, the preparation process of the melt of the natural wax is that the natural wax is weighed in a beaker, and is heated in a water bath kettle at 80-85 ℃, and after the natural wax in solid state is completely converted into liquid, the natural wax is continuously heated and homogenized for 20-60 min, so that bubbles in the melt are completely discharged and then kept Wen Daiyong in the water bath kettle.
7. The method of claim 6, wherein the curing time in step S1 is 2 to 6 hours.
8. An antifouling coating layer produced by the production process according to any one of claims 1 to 7.
9. The anti-fouling coating of claim 8, wherein the droplet slip angle of the anti-fouling coating is: at 10 μl droplet, slip angle <40 0.
10. Use of an anti-fouling coating as claimed in claim 8 or 9 for the preparation of an underwater anti-fouling product.
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| CN202410270459.7A Pending CN118085722A (en) | 2023-09-04 | 2024-03-11 | Antifouling coating based on natural wax molecule and siloxane polymer molecule composite, and preparation method and application thereof |
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