C5 petroleum resin modified antifouling paint, coating and preparation method and application of C5 petroleum resin modified antifouling paint

Abstract

The invention discloses a C5 petroleum resin modified antifouling paint, a C5 petroleum resin modified antifouling coating and a preparation method and application of the C5 petroleum resin modified antifouling paint. The C5 petroleum resin modified antifouling paint comprises a C5 petroleum resin base solution serving as a first component and a fluorocarbon modified micron particle solution serving as a second component, the C5 petroleum resin base solution comprises C5 petroleum resin, epoxy resin, a curing agent, a defoaming agent, a coalescing agent and a first solvent; the fluorocarbon modified micron particle liquid comprises a dispersing agent, fluorocarbon modified micron particles and a second solvent, and the fluorocarbon modified micron particles are prepared from micron particles, a fluorocarbon-containing monomer and an initiator through a grafting reaction. A coating formed by the C5 petroleum resin modified antifouling paint has high adhesive force, chemical corrosion resistance and lasting self-cleaning performance, the performance of a base layer is optimized through compounding of C5 petroleum resin and epoxy resin, and efficient antifouling is achieved in combination with a fluorocarbon modified surface layer.

Description

Technical Field

[0001] The present invention relates to the technical field of antifouling coatings, and in particular to a C5 petroleum resin modified antifouling coating, a coating, and a preparation method and application thereof. Background Art

[0002] In modern society, with the continuous advancement of science and technology and the improvement of people's living standards, the concept of "self-cleaning" has gradually become a hot topic, attracting the attention and research of more and more scientists and researchers. In the field of coatings, in particular, self-cleaning coatings have become a research focus, and their products have been widely recognized and warmly welcomed in the market. As a key indicator of coating quality, stain resistance is closely related to the physical and chemical properties of the coating itself, such as surface energy and surface roughness. Coatings with low surface energy and superhydrophobic properties can effectively reduce the adhesion time of water and dust on the coating surface, thereby reducing the possibility of the coating surface reacting with chemicals in water or dirt, reducing resistance, and giving the coating a self-cleaning function.

[0003] In the field of modern building materials, while traditional waterproof coatings can meet basic waterproofing requirements to a certain extent, their self-cleaning properties are often unsatisfactory. Especially in outdoor applications such as building exteriors, these coatings are prone to accumulating dust, dirt, and other environmental pollutants on their surfaces, which not only affects the building's aesthetic appearance but can also negatively impact the coating's long-term service life. Given this, the development of a new coating that can provide both effective waterproofing protection and self-cleaning capabilities is particularly important and urgent. Summary of the Invention

[0004] The main purpose of the present invention is to provide a C5 petroleum resin modified antifouling paint, coating and preparation method and application thereof, so as to overcome the deficiencies in the prior art.

[0005] To achieve the aforementioned object of the invention, the technical solutions adopted by the present invention include:

[0006] One aspect of the present invention provides a C5 petroleum resin modified antifouling coating, which comprises a C5 petroleum resin base liquid as a first component and a fluorocarbon modified micron particle liquid as a second component;

[0007] The C5 petroleum resin base liquid includes C5 petroleum resin, epoxy resin, curing agent, defoaming agent, film-forming aid and first solvent;

[0008] The fluorocarbon modified micron particle liquid comprises a dispersant, fluorocarbon modified micron particles and a second solvent;

[0009] The fluorocarbon modified micron particles are prepared by grafting micron particles, fluorocarbon-containing monomers and initiators.

[0010] Another aspect of the present invention provides a method for preparing a C5 petroleum resin modified antifouling coating, comprising:

[0011] Prepare C5 petroleum resin base liquid and fluorocarbon modified micron particle liquid according to the aforementioned C5 petroleum resin modified antifouling coating;

[0012] Applying the C5 petroleum resin base liquid to the surface of the substrate and drying it to form a resin base layer;

[0013] The fluorocarbon modified micron particle liquid is applied to the surface of the resin base layer and solidified to form a surface layer, thereby preparing a C5 petroleum resin modified antifouling coating.

[0014] Another aspect of the present invention also provides a C5 petroleum resin modified antifouling coating prepared by the aforementioned preparation method, which includes a resin base layer and a surface layer containing fluorocarbon modified micron particles arranged on the surface of the resin base layer, wherein the surface layer completely covers the resin base layer to form a continuous low surface energy structure.

[0015] Another aspect of the present invention further provides the use of the aforementioned C5 petroleum resin modified antifouling paint or the aforementioned C5 petroleum resin modified antifouling coating in the field of waterproofing or antifouling.

[0016] Compared with the prior art, the technical solution of the present invention has at least the following advantages:

[0017] 1) The C5 petroleum resin modified antifouling coating provided by the present invention has fluorocarbon-modified microparticles in its components that are firmly bonded to the surface of the microparticles through a specific chemical grafting technology, effectively preventing the fluorocarbon segments from falling off during use, thereby ensuring the long-term self-cleaning performance of the coating. In addition, the coating has a simple preparation process and readily available raw materials, making it suitable for large-scale industrial production and having broad market application prospects.

[0018] 2) The C5 petroleum resin modified antifouling coating provided by the present invention has high adhesion, chemical corrosion resistance and long-lasting self-cleaning performance. By compounding C5 petroleum resin with epoxy resin to optimize the performance of the base layer, combined with a fluorocarbon modified surface layer, efficient antifouling is achieved, while reducing costs and simplifying the construction process. Through the composite spraying process, a synergistic effect is formed between the base layer and the surface layer, which not only enhances the overall mechanical strength of the coating, but also significantly improves the waterproof, antifouling and self-cleaning capabilities of the coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0020] Figure 1 The figure is a schematic structural diagram of a C5 petroleum resin modified antifouling coating in a typical embodiment of the present invention.

[0021] Reference numerals: 1 - substrate; 2 - resin base layer; 3 - fluorocarbon-modified microparticles. DETAILED DESCRIPTION

[0022] The present invention will be more fully understood by reading the following detailed description. However, it should be understood that the detailed description disclosed below is merely exemplary of the present invention, and that the present invention may be embodied in a variety of forms. Therefore, the specific functional details disclosed herein should not be construed as limiting, but rather as a basis for the claims and as a representative basis for teaching those skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.

[0023] As one aspect of the technical solution of the present invention, a C5 petroleum resin modified antifouling coating comprises a C5 petroleum resin base liquid as a first component and a fluorocarbon modified micron particle liquid as a second component;

[0024] The C5 petroleum resin base liquid includes C5 petroleum resin, epoxy resin, curing agent, defoaming agent, film-forming aid and first solvent;

[0025] The fluorocarbon modified micron particle liquid comprises a dispersant, fluorocarbon modified micron particles and a second solvent;

[0026] The fluorocarbon modified micron particles are prepared by grafting micron particles, fluorocarbon-containing monomers and initiators.

[0027] In some embodiments, the C5 petroleum resin base fluid comprises the following components, by weight: 20%-40% C5 petroleum resin, 10%-30% epoxy resin, 5%-15% curing agent, 0.1%-1% defoaming agent, and 1%-5% coalescing agent, with the remainder being the first solvent. As an emerging polymer material, C5 petroleum resin exhibits excellent weather resistance, chemical resistance, and mechanical strength, making it a preferred raw material for the preparation of high-performance waterproof coatings.

[0028] By incorporating C5 petroleum resin into traditional epoxy resin, this invention significantly improves the coating's water resistance and overall durability. Furthermore, by combining the low surface energy of fluorocarbon materials, the coating surface becomes super-hydrophobic, effectively achieving a self-cleaning function and maintaining the cleanliness and aesthetics of building surfaces.

[0029] In some embodiments, the fluorocarbon-modified micron particle liquid includes the following components by mass percentage: 0.5%-3% of a dispersant and 1%-3% of fluorocarbon-modified micron particles, with the balance being a second solvent.

[0030] In some embodiments, the volume ratio of the C5 petroleum resin base liquid to the fluorocarbon modified micron particle liquid is 2-10:1.

[0031] In some embodiments, the epoxy resin includes but is not limited to any one or a combination of two or more of bisphenol epoxy resin, novolac epoxy resin, and hydrogenated bisphenol epoxy resin.

[0032] In some embodiments, the curing agent includes but is not limited to any one or a combination of two or more of ethylenediamine, diethylenetriamine, triethanolamine, phthalic anhydride, and methyltetrahydrophthalic anhydride.

[0033] In some embodiments, the defoaming agent includes but is not limited to any one or a combination of two or more of polydimethylsiloxane, polyoxyethylene-polyoxypropylene block copolymer, and octanol.

[0034] In some embodiments, the film-forming aid includes but is not limited to any one or a combination of two or more of propylene glycol methyl ether acetate, ethylene glycol butyl ether, and cyclohexanone.

[0035] In some embodiments, the first solvent includes but is not limited to any one or a combination of two or more of acetone, methyl ethyl ketone, cyclohexane, dichloroethane, ethyl acetate, and toluene.

[0036] In some embodiments, the preparation method of the C5 petroleum resin base liquid includes: mixing and dissolving C5 petroleum resin and epoxy resin at 60-80°C, adding a defoamer, a film-forming aid and a first solvent, stirring evenly and then cooling to room temperature, and then adding a curing agent and dispersing evenly.

[0037] In some embodiments, the dispersant includes but is not limited to any one of sodium stearate, lauryltrimethylammonium chloride, and polyethylene glycol ether, or a combination of two or more thereof.

[0038] In some embodiments, the second solvent includes but is not limited to any one of ethanol, acetone, ethyl acetate, and toluene, or a combination of two or more thereof.

[0039] In some embodiments, the method for preparing the fluorocarbon-modified micron particles includes: mixing micron particles, a fluorocarbon-containing monomer, and an initiator to perform a grafting reaction to obtain the fluorocarbon-modified micron particles.

[0040] In some preferred embodiments, the particle size of the fluorocarbon-modified micronized particles is 1-100 μm, and the surface fluorine content is ≥15 wt %.

[0041] In some preferred embodiments, the micron particles include but are not limited to any one of silicon dioxide, diatomaceous earth, montmorillonite, kaolin, talc, and gypsum powder, or a combination of two or more thereof.

[0042] Furthermore, the particle size of the micron particles is 1-100 μm.

[0043] In some preferred embodiments, the fluorocarbon monomer includes but is not limited to a fluoroacrylate monomer, and the fluoroacrylate monomer includes but is not limited to any one or a combination of two or more of dodecafluoroheptyl methacrylate (DFMA), trifluoroethyl acrylate (TFEA), hexafluorobutyl methacrylate (HFMA), and perfluorooctyl ethyl acrylate (FAEE).

[0044] In some preferred embodiments, the initiator includes but is not limited to azobisisobutyronitrile (AIBN).

[0045] In some preferred embodiments, the mass ratio of the micron particles to the fluorocarbon-containing monomer is 10:0.5-3.

[0046] In some preferred embodiments, the mass of the initiator is 1-3% of the mass of the fluorocarbon-containing monomer.

[0047] In some preferred embodiments, the grafting reaction temperature is 60-75° C., and the grafting reaction time is 4-8 hours.

[0048] In some specific embodiments, the method for preparing the fluorocarbon-modified micronized particles comprises the following steps:

[0049] The dried micronized particles (10 g) were added to a 100 mL acetone solution of a fluorocarbon-containing monomer (0.5-3 g), followed by a dispersant (0.5-1 g). The suspension was ultrasonically dispersed for 30 minutes to form a uniform suspension. Nitrogen was then introduced for deoxygenation for 30 minutes. The mixture was heated to 60-75°C, and an AIBN initiator (1-3% of the monomer weight) was added. The reaction was continued for 4-8 hours, maintaining a nitrogen atmosphere and mechanically stirring at 300-500 rpm. After the reaction was completed, the mixture was cooled to room temperature, and the product was poured into a large amount of anhydrous ethanol for precipitation and centrifuged at 8000-10000 rpm for 15 minutes. The product was washed three times with acetone to remove unreacted monomer and homopolymer, and then vacuum dried at 50°C for 24 hours to prepare fluoropolymer-grafted micronized particles. The fluorocarbon-modified micronized particles had a particle size of 1-100 μm and a surface fluorine content of ≥15 wt%.

[0050] As another aspect of the technical solution of the present invention, a method for preparing a C5 petroleum resin modified antifouling coating comprises:

[0051] Prepare C5 petroleum resin base liquid and fluorocarbon modified micron particle liquid according to the aforementioned C5 petroleum resin modified antifouling coating;

[0052] Applying the C5 petroleum resin base liquid to the surface of the substrate and drying it to form a resin base layer;

[0053] The fluorocarbon modified micron particle liquid is applied to the surface of the resin base layer and solidified to form a surface layer, thereby preparing a C5 petroleum resin modified antifouling coating.

[0054] In some embodiments, the preparation method specifically includes: spraying the C5 petroleum resin base liquid onto the surface of the substrate, and the spraying process conditions include: spraying pressure of 0.3-0.5 MPa, and a distance between the spray gun and the substrate surface of 15-25 cm.

[0055] In some embodiments, the drying temperature is 25° C. and the drying time is 12-24 hours.

[0056] In some embodiments, the preparation method specifically includes: spraying the fluorocarbon modified micron particle liquid onto the surface of the resin base layer, and the spraying process conditions include: spraying pressure of 0.2-0.4 MPa, and the distance between the spray gun and the resin base layer surface is 20-30 cm.

[0057] In some more specific embodiments, the method for preparing the C5 petroleum resin modified antifouling coating comprises the following steps:

[0058] 1) Prepare C5 petroleum resin base liquid: Mix and dissolve C5 petroleum resin and epoxy resin at 60-80°C, add defoamer, film-forming agent and first solvent, stir evenly and cool to room temperature, then add curing agent and disperse evenly;

[0059] 2) preparing a fluorocarbon-modified micron particle liquid: adding the fluorocarbon-modified micron particles and a dispersant to a second solvent, and ultrasonically dispersing the particles for 30-60 minutes to form a uniform suspension;

[0060] 3) Double-layer spraying construction: First, spray the C5 petroleum resin base liquid on the surface of the substrate, dry it at 25°C for 12-24 hours to form a resin base layer, then spray the fluorocarbon modified micron particle liquid on the surface of the resin base layer, dry and solidify it to form a surface layer to obtain a C5 petroleum resin modified antifouling coating.

[0061] As another aspect of the technical solution of the present invention, the C5 petroleum resin modified antifouling coating prepared by the above-mentioned preparation method includes a resin base layer and a surface layer containing fluorocarbon modified micron particles arranged on the surface of the resin base layer, and the surface layer completely covers the resin base layer to form a continuous low surface energy structure.

[0062] Specifically, the structural diagram of the coating is shown in Figure 1 As shown, it includes a resin base layer 2 formed on a substrate 1, and a surface layer containing fluorocarbon modified micron particles 3 on the resin base layer 2, and the surface layer completely covers the resin base layer 2 to form a continuous low surface energy structure.

[0063] In some embodiments, the thickness of the resin base layer is 50-200 μm, and the thickness of the surface layer is 10-50 μm.

[0064] In some embodiments, the contact angle of the surface of the C5 petroleum resin modified antifouling coating with water is ≥150°, the rolling angle is ≤15°, the biological attachment area after immersion in a simulated marine environment for 7 days is ≤5%, and the contact angle decreases by ≤15% after friction under the conditions of an impact angle of 45° and a sand flow rate of 2 L / min.

[0065] As another aspect of the technical solution of the present invention, it relates to the application of the aforementioned C5 petroleum resin modified antifouling paint or the aforementioned C5 petroleum resin modified antifouling coating in the field of waterproofing or antifouling.

[0066] In some embodiments, the application includes applications in the fields of ship hulls, offshore platforms, cross-sea bridges, building exterior walls, industrial equipment, or municipal facilities.

[0067] In summary, the C5 petroleum resin-modified antifouling coating provided by the present invention achieves high adhesion and chemical resistance through a compounding of C5 petroleum resin and epoxy resin. Furthermore, a secondary spray-coated fluorinated surface layer introduces low-surface-energy modified micronized particles, further enhancing the coating's water-repellent properties. The coating is widely applicable to applications requiring antifouling and self-cleaning properties, such as ships, offshore platforms, bridges, and building exteriors. This coating not only effectively prevents the attachment of marine organisms, reduces cleaning frequency, and lowers maintenance costs, but also possesses self-cleaning properties that leverage natural conditions such as rain and wind to remove surface contaminants, maintaining the coating's aesthetic appeal and long-lasting antifouling performance.

[0068] The present invention is further illustrated by way of examples below, but the invention is not limited to the scope of the examples. The reagents and raw materials used in the following examples are commercially available, and the experimental methods where specific conditions are not specified are generally carried out under conventional conditions or according to the conditions recommended by the respective manufacturers.

[0069] Example 1

[0070] This embodiment provides a method for preparing a self-cleaning C5 petroleum resin modified antifouling coating, comprising the following steps:

[0071] a) Preparation of C5 petroleum resin mixture: 20 parts by mass of C5 petroleum resin; 10 parts by mass of bisphenol-type epoxy resin; 5 parts by mass of ethylenediamine; 0.1 parts by mass of polydimethylsiloxane; and 1 part by mass of propylene glycol methyl ether acetate were sequentially added to 63.9 parts by mass of acetone, and the mixture was stirred uniformly to obtain a C5 petroleum resin mixture.

[0072] b) Preparation of Fluorocarbon-Modified Microparticles: 10 g of dried silica microparticles (particle size 1-100 μm) and 0.5 g of dodecafluoroheptyl methacrylate were added to 100 ml of acetone solution. 0.5 g of sodium stearate was then added and ultrasonically dispersed for 30 minutes to form a uniform suspension. Nitrogen was then introduced for deoxygenation for 30 minutes. The temperature was raised to 60°C, and 1 g of AIBN initiator was added. The reaction was continued for 4 hours, maintaining a nitrogen atmosphere and mechanical stirring (300 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the product was precipitated in a large amount of anhydrous ethanol and centrifuged (8000 rpm for 15 minutes). The product was washed three times with acetone to remove unreacted monomer and homopolymer, and then dried in vacuo at 50°C for 24 hours to prepare fluoropolymer-grafted microparticles.

[0073] c) Preparation of fluorocarbon-modified micron particle liquid: 1 part by mass of fluorocarbon-modified micron particles and 1 part by mass of sodium stearate were added to 98 parts of ethanol and stirred at room temperature for 1 hour to prepare a fluorocarbon-modified micron particle liquid.

[0074] d) Preparation of a self-cleaning antifouling coating: 2 parts by volume of a C5 petroleum resin mixture was sprayed onto the surface of the substrate and dried at 25°C for 12 hours to form a base layer. 1 part of a fluorocarbon-modified micronized particle solution was then sprayed onto the surface of the base layer and dried and cured to form a surface layer to prepare a self-cleaning antifouling coating.

[0075] After testing, the coating surface formed by the paint has a water contact angle of 155° and a rolling angle of 13°. After immersion in an alkaline solution with a pH of 13 for 24 hours, the contact angle decreases by ≤2%; after immersion in a simulated marine environment (35g sea salt / liter of water) for 7 days, the biological attachment area is ≤3%; the contact angle of 500g quartz sand decreases by ≤10% after friction under the conditions of an impact angle of 45° and a sand flow rate of 2L / min.

[0076] Example 2

[0077] This embodiment provides a method for preparing a self-cleaning C5 petroleum resin modified antifouling coating, comprising the following steps:

[0078] a) Preparation of C5 petroleum resin mixed liquid: 24 parts by mass of C5 petroleum resin; 14 parts of phenolic epoxy resin; 7 parts of diethylenetriamine; 0.3 parts of polyoxyethylene-polyoxypropylene block copolymer; and 2 parts of ethylene glycol butyl ether were sequentially added to 52.7 parts of methyl ethyl ketone, and the mixture was stirred uniformly to obtain a C5 petroleum resin mixed liquid.

[0079] b) Preparation of Fluorocarbon-Modified Microparticles: 10 g of dried diatomaceous earth microparticles (particle size 1-100 μm) and 1.0 g of trifluoroethyl acrylate were added to 100 ml of acetone solution. 0.6 g of dodecyltrimethylammonium chloride was added and ultrasonically dispersed for 30 minutes to form a uniform suspension. Nitrogen was introduced for deoxygenation for 30 minutes. The temperature was raised to 63°C, and 1.4 g of AIBN initiator was added. The reaction was continued for 4.8 hours, maintaining a nitrogen atmosphere and mechanical stirring (340 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the product was poured into a large amount of anhydrous ethanol for precipitation and centrifuged (8400 rpm for 15 minutes). The product was washed three times with acetone to remove unreacted monomer and homopolymer, and then vacuum dried at 50°C for 24 hours to prepare fluoropolymer-grafted microparticles.

[0080] c) Preparation of fluorocarbon-modified micron particle liquid: 3 parts by mass of fluorocarbon-modified micron particles and 0.5 parts of dodecyltrimethylammonium chloride were added to 96.5 parts of acetone and stirred at room temperature for 1 hour to prepare a fluorocarbon-modified micron particle liquid.

[0081] d) Preparation of a self-cleaning antifouling coating: 4 parts by volume of a C5 petroleum resin mixture was sprayed onto the surface of the substrate and dried at 25°C for 14 hours to form a base layer. 1 part of a fluorocarbon-modified micronized particle solution was then sprayed onto the surface of the base layer and dried and cured to form a surface layer to prepare a self-cleaning antifouling coating.

[0082] After testing, the coating surface formed by the paint has a water contact angle of 153° and a rolling angle of 14°. After immersion in an alkaline solution with a pH of 13 for 24 hours, the contact angle decreases by ≤2%; after immersion in a simulated marine environment (35g sea salt / liter of water) for 7 days, the biological attachment area is ≤4%; and the contact angle of 500g quartz sand decreases by ≤12% after friction under the conditions of an impact angle of 45° and a sand flow rate of 2L / min.

[0083] Example 3

[0084] This embodiment provides a method for preparing a self-cleaning C5 petroleum resin modified antifouling coating, comprising the following steps:

[0085] a) Preparation of C5 petroleum resin mixed liquid: 28 parts by mass of C5 petroleum resin; 18 parts of hydrogenated bisphenol-type epoxy resin; 9 parts of triethanolamine; 0.5 parts of octanol; and 3 parts of cyclohexanone were sequentially added to 41.5 parts of cyclohexane, and the mixture was stirred uniformly to obtain a C5 petroleum resin mixed liquid.

[0086] b) Preparation of Fluorocarbon-Modified Microparticles: 10 g of dried montmorillonite microparticles (particle size 1-100 μm) and 1.5 g of hexafluorobutyl methacrylate were added to 100 ml of acetone solution. 0.7 g of polyethylene glycol ether was then added and ultrasonically dispersed for 30 minutes to form a uniform suspension. Nitrogen was introduced for deoxygenation for 30 minutes. The temperature was raised to 66°C, and 1.8 g of AIBN initiator was added. The reaction was continued for 5.6 hours, maintaining a nitrogen atmosphere and mechanical stirring at 380 rpm. After the reaction was completed, the mixture was cooled to room temperature, and the product was poured into a large amount of anhydrous ethanol for precipitation and centrifuged (8800 rpm for 15 minutes). The product was washed three times with acetone to remove unreacted monomer and homopolymer, and then dried in vacuo at 50°C for 24 hours to prepare fluoropolymer-grafted microparticles.

[0087] c) Preparation of fluorocarbon-modified micron particle liquid: 2 parts by mass of fluorocarbon-modified micron particles and 2 parts of polyethylene glycol ether were added to 96 parts of ethanol and stirred at room temperature for 1 hour to prepare a fluorocarbon-modified micron particle liquid.

[0088] d) Preparation of a self-cleaning antifouling coating: 5 parts by volume of a C5 petroleum resin mixture was sprayed onto the surface of the substrate and dried at 25°C for 17 hours to form a base layer. 1 part of a fluorocarbon-modified micronized particle solution was then sprayed onto the surface of the base layer and dried and cured to form a surface layer to prepare a self-cleaning antifouling coating.

[0089] After testing, the coating surface formed by the paint has a water contact angle of 155° and a rolling angle of 13°. After immersion in an alkaline solution with a pH of 13 for 24 hours, the contact angle decreases by ≤2%; after immersion in a simulated marine environment (35g sea salt / liter of water) for 7 days, the biological attachment area is 42%; the contact angle of 500g quartz sand decreases by ≤8% after friction under the conditions of an impact angle of 45° and a sand flow rate of 2L / min.

[0090] Example 4

[0091] This embodiment provides a method for preparing a self-cleaning C5 petroleum resin modified antifouling coating, comprising the following steps:

[0092] a) Preparation of C5 petroleum resin mixed liquid: 32 parts by mass of C5 petroleum resin; 22 parts of bisphenol-type epoxy resin; 11 parts of phthalic anhydride; 0.7 parts of polydimethylsiloxane; and 4 parts of propylene glycol methyl ether acetate were sequentially added to 30.3 parts of ethyl acetate, and the mixture was stirred uniformly to obtain a C5 petroleum resin mixed liquid.

[0093] b) Preparation of Fluorocarbon-Modified Microparticles: 10 g of dried kaolin microparticles (particle size 1-100 μm) and 2.0 g of perfluorooctyl ethyl acrylate were added to 100 ml of acetone solution. 0.8 g of sodium stearate was then added and ultrasonically dispersed for 30 minutes to form a uniform suspension. Nitrogen was then introduced for deoxygenation for 30 minutes. The mixture was heated to 69°C and 2.2 g of AIBN initiator was added. The reaction was continued for 6.4 hours, maintaining a nitrogen atmosphere and mechanical stirring at 420 rpm. After the reaction was completed, the mixture was cooled to room temperature and the product was precipitated in a large amount of anhydrous ethanol and centrifuged at 9200 rpm for 15 minutes. The product was washed three times with acetone to remove unreacted monomer and homopolymer, and then dried in vacuo at 50°C for 24 hours to prepare fluoropolymer-grafted microparticles.

[0094] c) Preparation of fluorocarbon-modified micron particle liquid: 1 part by mass of fluorocarbon-modified micron particles and 3 parts by mass of dodecyltrimethylammonium chloride were added to 96 parts of toluene and stirred at room temperature for 1 hour to prepare a fluorocarbon-modified micron particle liquid.

[0095] d) Preparation of a self-cleaning antifouling coating: 7 parts by volume of a C5 petroleum resin mixture was sprayed onto the surface of the substrate and dried at 25°C for 19 hours to form a base layer. 1 part of a fluorocarbon-modified micronized particle solution was then sprayed onto the surface of the base layer and dried and cured to form a surface layer to prepare a self-cleaning antifouling coating.

[0096] After testing, the coating surface formed by the paint has a water contact angle of 156° and a rolling angle of 12°. After immersion in an alkaline solution with a pH of 13 for 24 hours, the contact angle decreases by ≤2%. After immersion in a simulated marine environment for 7 days, the biological attachment area is 42%. The contact angle of 500g quartz sand decreases by ≤10% after friction under the conditions of an impact angle of 45° and a sand flow rate of 2L / min.

[0097] Example 5

[0098] This embodiment provides a method for preparing a self-cleaning C5 petroleum resin modified antifouling coating, comprising the following steps:

[0099] a) Preparation of C5 petroleum resin mixed liquid: 36 parts by mass of C5 petroleum resin; 26 parts of hydrogenated bisphenol-type epoxy resin; 13 parts of methyltetrahydrophthalic anhydride; 0.9 parts of polyoxyethylene-polyoxypropylene block copolymer; and 5 parts of ethylene glycol butyl ether were sequentially added to 19.1 parts of toluene, and the mixture was stirred uniformly to obtain a C5 petroleum resin mixed liquid.

[0100] b) Preparation of Fluorocarbon-Modified Microparticles: 10 g of dried talc microparticles (particle size 1-100 μm) and 2.5 g of dodecafluoroheptyl methacrylate were added to 100 ml of acetone solution. 0.9 g of dodecyltrimethylammonium chloride was added and ultrasonically dispersed for 30 minutes to form a uniform suspension. Nitrogen was then introduced for deoxygenation for 30 minutes. The temperature was raised to 72°C, and 2.6 g of AIBN initiator was added. The reaction was continued for 7.2 hours, maintaining a nitrogen atmosphere and mechanical stirring at 460 rpm. After the reaction was completed, the mixture was cooled to room temperature, and the product was precipitated in a large amount of anhydrous ethanol and centrifuged (9600 rpm for 15 minutes). The product was washed three times with acetone to remove unreacted monomer and homopolymer, and then dried in vacuo at 50°C for 24 hours to prepare fluoropolymer-grafted microparticles.

[0101] c) Preparation of fluorocarbon-modified micron particle liquid: 3 parts by mass of fluorocarbon-modified micron particles and 2 parts of polyethylene glycol ether were added to 95 parts of ethanol and stirred at room temperature for 1 hour to prepare a fluorocarbon-modified micron particle liquid.

[0102] d) Preparation of a self-cleaning antifouling coating: A C5 petroleum resin mixture of 8 parts by volume was sprayed onto the substrate surface and dried at 25°C for 21 hours to form a base layer. A fluorocarbon-modified micronized particle solution of 1 part was then sprayed onto the base layer surface and dried and cured to form a surface layer, thereby preparing a self-cleaning antifouling coating.

[0103] After testing, the coating surface formed by the paint has a water contact angle of 154° and a rolling angle of 13°. After immersion in an alkaline solution with a pH of 13 for 24 hours, the contact angle decreases by ≤2%; and the biological attachment area is ≤4% after immersion in a simulated marine environment (35g sea salt / liter of water) for 7 days. The contact angle of 500g quartz sand decreases by ≤15% after friction under the conditions of an impact angle of 45° and a sand flow rate of 2L / min.

[0104] Example 6

[0105] This embodiment provides a method for preparing a self-cleaning C5 petroleum resin modified antifouling coating, comprising the following steps:

[0106] a) Preparation of C5 petroleum resin mixed liquid: 40 parts by mass of C5 petroleum resin, 30 parts by mass of phenolic epoxy resin, 15 parts by mass of triethanolamine, 1 part by mass of octanol, and 2 parts by mass of propylcyclohexanone were sequentially added to 12 parts by mass of ethylene dichloride, and the mixture was stirred uniformly to obtain a C5 petroleum resin mixed liquid.

[0107] b) Preparation of fluorocarbon-modified microparticles: 10 g of dry gypsum powder microparticles (particle size 1-100 μm) and 3.0 g of trifluoroethyl acrylate were added to 100 ml of acetone solution. 1.0 g of polyethylene glycol ether was then added and ultrasonically dispersed for 30 minutes to form a uniform suspension. Nitrogen was introduced for deoxygenation for 30 minutes. The temperature was raised to 75°C, and 3 g of AIBN initiator was added. The reaction was continued for 8 hours, maintaining a nitrogen atmosphere and mechanical stirring at 500 rpm. After the reaction was completed, the mixture was cooled to room temperature, and the product was poured into a large amount of anhydrous ethanol for precipitation and centrifuged (10,000 rpm for 15 minutes). The product was washed three times with acetone to remove unreacted monomer and homopolymer, and then vacuum dried at 50°C for 24 hours to prepare fluoropolymer-grafted microparticles.

[0108] c) Preparation of fluorocarbon-modified micron particle liquid: 1 part by mass of fluorocarbon-modified micron particles and 2 parts by mass of sodium stearate were added to 97 parts of ethyl acetate and stirred at room temperature for 1 hour to prepare a fluorocarbon-modified micron particle liquid.

[0109] d) Preparation of a self-cleaning antifouling coating: 10 parts by volume of a C5 petroleum resin mixture was sprayed onto the surface of the substrate and dried at 25°C for 24 hours to form a base layer. 1 part of a fluorocarbon-modified micronized particle solution was then sprayed onto the surface of the base layer and dried and cured to form a surface layer to prepare a self-cleaning antifouling coating.

[0110] After testing, the coating surface formed by the paint has a water contact angle of 152° and a rolling angle of 14°. After immersion in an alkaline solution with a pH of 13 for 24 hours, the contact angle decreases by ≤2%; after immersion in a simulated marine environment (35g sea salt / liter of water) for 7 days, the biological attachment area is ≤3%; and the contact angle of 500g quartz sand decreases by ≤8% after friction under the conditions of an impact angle of 45° and a sand flow rate of 2L / min.

[0111] Comparative Example 1

[0112] The difference between this comparative example and Example 1 is that the micron particles are not subjected to fluorocarbon grafting modification.

[0113] After the coating obtained in this comparative example was sprayed into a coating, the coating failed to achieve a superhydrophobic effect. The prepared coating had a water contact angle of 143° and a rolling angle of 72° at room temperature. After immersion in an alkaline solution with a pH of 13 for 24 hours, the contact angle decreased by 3%. After immersion in a simulated marine environment for 7 days, the biological attachment area was 9%. The contact angle of 500 g of quartz sand decreased by 20% after friction under the conditions of an impact angle of 45° and a sand flow rate of 2 L / min.

[0114] Comparative Example 2

[0115] The difference between this comparative example and Example 1 is that the fluorocarbon-modified micron particle liquid was not sprayed when preparing the coating.

[0116] After the coating obtained in this comparative example was sprayed into a coating, the coating failed to achieve a superhydrophobic effect. The prepared coating had a water contact angle of 112° at room temperature. After immersion in an alkaline solution with a pH of 13 for 24 hours, the contact angle decreased by ≤2%. The biological attachment area after immersion in a simulated marine environment (35g sea salt / liter of water) for 7 days was 34%, and the contact angle of 500g quartz sand decreased by 15% after friction under the conditions of an impact angle of 45° and a sand flow rate of 2L / min.

[0117] Comparative Example 3

[0118] The difference between this comparative example and Example 1 is that the C5 petroleum resin mixture was not sprayed when preparing the coating.

[0119] After the coating obtained in this comparative example was sprayed into a coating, the coating failed to achieve a superhydrophobic effect. The prepared coating had a water contact angle of 143° at room temperature. After immersion in an alkaline solution with a pH of 13 for 24 hours, the contact angle decreased by 5%, and the coating had poor adhesion and fell off. The biological attachment area after immersion in a simulated marine environment (35g sea salt / liter of water) for 7 days was 32%, and the contact angle of 500g quartz sand decreased by 50% after friction under the conditions of an impact angle of 45° and a sand flow rate of 2L / min.

[0120] Comparative Example 4

[0121] The difference between this comparative example and Example 1 is that no fluorocarbon-modified micron particles are added.

[0122] After the coating obtained in this comparative example was sprayed into a coating, the coating failed to achieve a superhydrophobic effect. The prepared coating had a water contact angle of 130° at room temperature. After immersion in an alkaline solution with a pH of 13 for 24 hours, the contact angle decreased by 5%. The biological attachment area after immersion in a simulated marine environment (35g sea salt / liter of water) for 7 days was 23%, and the contact angle of 500g quartz sand decreased by 20% after friction under the conditions of an impact angle of 45° and a sand flow rate of 2L / min.

[0123] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments using other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0124] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A C5 petroleum resin modified antifouling coating, characterized in that: The invention comprises a C5 petroleum resin base liquid as a first component and a fluorocarbon modified micron particle liquid as a second component; The C5 petroleum resin base liquid includes C5 petroleum resin, epoxy resin, curing agent, defoaming agent, film-forming aid and first solvent; The fluorocarbon modified micron particle liquid comprises a dispersant, fluorocarbon modified micron particles and a second solvent; The fluorocarbon modified micron particles are prepared by grafting micron particles, fluorocarbon-containing monomers and initiators.

2. The C5 petroleum resin modified antifouling coating according to claim 1, characterized in that: The C5 petroleum resin base liquid comprises the following components by mass percentage: 20%-40% C5 petroleum resin, 10%-30% epoxy resin, 5%-15% curing agent, 0.1%-1% defoaming agent and 1%-5% film-forming aid, with the balance being the first solvent; And / or, the fluorocarbon modified micron particle liquid comprises the following components by mass percentage: 0.5%-3% of a dispersant and 1%-3% of fluorocarbon modified micron particles, with the balance being a second solvent; And / or, the volume ratio of the C5 petroleum resin base liquid to the fluorocarbon modified micron particle liquid is 2-10:

1.

3. The C5 petroleum resin modified antifouling coating according to claim 1, characterized in that: The epoxy resin includes any one or a combination of two or more of bisphenol epoxy resin, novolac epoxy resin, and hydrogenated bisphenol epoxy resin; And / or, the curing agent includes any one or a combination of two or more of ethylenediamine, diethylenetriamine, triethanolamine, phthalic anhydride, and methyltetrahydrophthalic anhydride; And / or, the defoaming agent includes any one or a combination of two or more of polydimethylsiloxane, polyoxyethylene-polyoxypropylene block copolymer, and octanol; And / or, the film-forming aid includes any one or a combination of two or more of propylene glycol methyl ether acetate, ethylene glycol butyl ether, and cyclohexanone; And / or, the first solvent includes any one or a combination of two or more of acetone, methyl ethyl ketone, cyclohexane, dichloroethane, ethyl acetate, and toluene; And / or, the preparation method of the C5 petroleum resin base liquid includes: mixing and dissolving C5 petroleum resin and epoxy resin at 60-80° C., adding a defoamer, a film-forming aid and a first solvent, stirring evenly and then cooling to room temperature, and then adding a curing agent and dispersing evenly.

4. The C5 petroleum resin modified antifouling coating according to claim 1, characterized in that: The dispersant includes any one or a combination of two or more of sodium stearate, lauryl trimethyl ammonium chloride, and polyethylene glycol ether; And / or, the second solvent includes any one of ethanol, acetone, ethyl acetate, and toluene, or a combination of two or more thereof.

5. The C5 petroleum resin modified antifouling paint according to claim 1, characterized in that: The preparation method of the fluorocarbon modified micron particles comprises: mixing micron particles, fluorocarbon-containing monomers and an initiator to carry out a grafting reaction to prepare fluorocarbon modified micron particles; Preferably, the particle size of the fluorocarbon modified micron particles is 1-100 μm, and the surface fluorine content is ≥15 wt%; Preferably, the micron particles include any one or a combination of two or more of silicon dioxide, diatomaceous earth, montmorillonite, kaolin, talc, and gypsum powder; particularly preferably, the particle size of the micron particles is 1-100 μm; Preferably, the fluorine-containing carbon monomer includes a fluorine-containing acrylate monomer, and the fluorine-containing acrylate monomer includes any one or a combination of two or more of dodecafluoroheptyl methacrylate, trifluoroethyl acrylate, hexafluorobutyl methacrylate, and perfluorooctylethyl acrylate; Preferably, the initiator comprises azobisisobutyronitrile; Preferably, the mass ratio of the micron particles to the fluorocarbon-containing monomer is 10:0.5-3; Preferably, the mass of the initiator is 1-3% of the mass of the fluorocarbon-containing monomer; Preferably, the grafting reaction temperature is 60-75° C., and the grafting reaction time is 4-8 hours.

6. A method for preparing a C5 petroleum resin modified antifouling coating, characterized in that: include: The C5 petroleum resin modified antifouling coating according to any one of claims 1 to 5 is prepared with a C5 petroleum resin base liquid and a fluorocarbon modified micron particle liquid; Applying the C5 petroleum resin base liquid to the surface of the substrate and drying it to form a resin base layer; The fluorocarbon modified micron particle liquid is applied to the surface of the resin base layer and solidified to form a surface layer, thereby preparing a C5 petroleum resin modified antifouling coating.

7. The preparation method according to claim 6, characterized in that Specifically include: Spraying the C5 petroleum resin base liquid onto the surface of the substrate, wherein the spraying process conditions include: a spraying pressure of 0.3-0.5 MPa, and a distance between the spray gun and the substrate surface of 15-25 cm; And / or, the drying temperature is 25° C. and the drying time is 12-24 hours.

8. The preparation method according to claim 6, characterized in that Specifically include: The fluorocarbon modified micron particle liquid is sprayed onto the surface of the resin base layer. The process conditions of the spraying include: a spraying pressure of 0.2-0.4 MPa, and a distance between the spray gun and the surface of the resin base layer of 20-30 cm.

9. A C5 petroleum resin modified antifouling coating prepared by the preparation method according to any one of claims 6 to 8, comprising a resin base layer and a surface layer containing fluorocarbon-modified micronized particles disposed on the surface of the resin base layer, wherein the surface layer completely covers the resin base layer to form a continuous low surface energy structure; Preferably, the thickness of the resin base layer is 50-200 μm, and the thickness of the surface layer is 10-50 μm; Preferably, the contact angle between the surface of the C5 petroleum resin modified antifouling coating and water is ≥150°, the rolling angle is ≤15°, the biological attachment area after immersion in a simulated marine environment for 7 days is ≤5%, and the contact angle decreases by ≤15% after friction under the conditions of an impact angle of 45° and a sand flow rate of 2 L / min.

10. Use of the C5 petroleum resin modified antifouling paint according to any one of claims 1 to 5 or the C5 petroleum resin modified antifouling coating according to claim 9 in the field of waterproofing or antifouling; Preferably, the application includes applications in the fields of ship hulls, offshore platforms, cross-sea bridges, building exterior walls, industrial equipment or municipal facilities.

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