Marine antifouling paint based on fluorosilicone low-surface-energy resin

Abstract

The invention provides a marine antifouling coating based on fluorine-silicon low-surface-energy resin. The marine antifouling coating comprises a fluorine-silicon low-surface-energy resin coating (1), an organic silicon epoxy floating coating (2) and an epoxy base coating (3), a ketoxime-removing curing agent is arranged between the fluorine-silicon low-surface-energy resin coating and the organic silicon epoxy floating coating; wherein the fluorine-silicon low-surface-energy resin coating is an antifouling coating; the epoxy prime coat layer is an epoxy resin polymer; the organic silicon epoxy floating coat adopts an organic silicon modified epoxy coating to form a coating system matched with the epoxy prime coat and the fluorosilicone low-surface-energy resin coating; the organic silicon modified epoxy coating contains a siloxy group and an epoxy group, so that the combination of the organic silicon epoxy floating coat coating, the epoxy prime coat coating and the fluorine-silicon low-surface-energy resin coating is realized; the deketoxime curing agent takes KH550, KH570, methyl diacetylmonoxime silane and ethyl diacetylmonoxime silane as raw materials, and the raw materials react with part of water under a heating condition, so that the multifunctional curing / tackifying agent is formed.

Description

Technical Field

[0001] The present invention relates to functional marine antifouling coatings with high added value, synthesis technology of new fluorosilicone resins, preparation technology of special coatings, coating construction process technology, coating performance evaluation method, and technical fields such as development and industrialization of matching primer and mid-coat coatings, resin synthesis, formula development, batch production, and engineering application, and specifically relates to a marine antifouling coating based on fluorosilicone low surface energy resin. Background Art

[0002] The ocean has 71% of the earth's surface area, and its effective utilization area is 5 to 10 times that of the land. It contains endless natural resources. With the gradual deepening of the global economic integration process and the sustained rapid development of my country's economy, the prospects of ocean development markets such as ocean shipping, offshore oil, offshore fishing, and marine minerals are attractive and have unlimited business opportunities. However, marine biofouling seriously restricts the development of the entire marine industry. Marine biofouling refers to the process in which marine organisms gather and grow in large numbers on the surface of marine facilities submerged in seawater. The formation of marine biofouling mainly goes through the following process: First, the surface of the substrate immersed in the water body is quickly covered by various proteins and dissolved organic matter in the ocean, and then the floating bacteria begin to attach and multiply in large numbers, and at the same time secrete extracellular polymers that can tightly connect to the substrate. In the following hours, a large number of algae spores and single-cell eukaryotic organisms begin to gather, and then a series of physical, chemical and biochemical changes occur on the surface of the substrate, and a layer of firm microbial mucosa is formed. The attached algae spores and invertebrate larvae grow rapidly into adults visible to the naked eye.

[0003] Marine fouling organisms are extremely harmful to ships and have always troubled human marine activities. The fouling objects are mainly marine organisms such as seaweed and barnacles. The attachment of these marine organisms greatly increases the deadweight and navigation resistance of the ship, thereby increasing the fuel cost. The fouling layer may further damage the anti-corrosion protective layer of the hull, accelerate the corrosion of metal hull components, and reduce the service life of ships and offshore buildings. According to statistics, the economic losses caused by biological fouling alone to various underwater engineering facilities and ship equipment in the world can reach tens of billions of dollars each year. Data show that for ships sailing far at sea, when the bottom of the ship is 5%, the fuel consumption increases by 10%, when the bottom of the ship is 10%, the fuel consumption increases by 20%, and when the bottom of the ship is more than 50%, the fuel consumption will increase by more than 40%. In addition, the costs of maintenance, cleaning, and repainting are required. The annual global ship maintenance cost is at least 3 billion US dollars. In addition, biological fouling is often associated with biological corrosion. The metabolic corrosive medium of the attached organisms will corrode the steel and cause damage to the material strength. When a large number of biofouling organisms are attached to the pillars of an offshore drilling platform, not only will the center of gravity shift, causing the risk of capsizing, but the pillars will also corrode, causing the material strength to decrease, and eventually causing the drilling platform to collapse. It can be seen that the economic losses caused by marine biofouling to the global shipping industry are immeasurable.

[0004] In recent years, my country has become one of the world's three largest shipbuilding countries. Marine fouling organisms are extremely harmful to ships. It takes 50 tons of antifouling paint to manufacture every 10,000 tons of new ships and 30 tons to repair old ships. With the increase in the number of ships and vessels in various countries, how to prevent marine biofouling and reduce economic losses is of great significance to the economic interests of various countries. The problem of marine fouling has become a global hot issue. Traditional antifouling coatings mainly use the slow release of toxic substances (such as cuprous oxide and organic tin) in the coating to kill nearby organisms to achieve the purpose of antifouling, which will have a bad impact on the marine ecological environment. With the formulation and entry into force of marine environmental protection laws and conventions, it is urgent to develop marine antifouling coatings that are pollution-free to the marine environment and have excellent performance. The vast majority of the antifouling coatings used for the bottom of ships are products of large foreign coating companies (IP, PPG, NIPPON, SIGMA, etc. The categories, names and specific market applications of the products are shown in Table 1.

[0005] Table 1:

[0006]

[0007] In recent years, the United States, Japan, Germany and my country have vigorously researched and developed non-toxic antifouling coatings. These methods can be divided into: Wuxi self-polishing type, low surface energy type, bionic antifouling coatings, etc.

[0008] 1. Wuxi self-polishing antifouling coating

[0009] Wuxi self-polishing antifouling coatings not only overcome the disadvantage of high toxicity of the original organotin self-polishing coatings, but also have the advantages of energy saving of self-polishing antifouling coatings. The British International Coatings Company (IP) was the first to carry out research on Wuxi self-polishing antifouling coatings. Its three main products are Interclene 245, Interspeed 340 and Inters-mooth Ecoloflex self-polishing coatings. Recently, the international company has launched a new product, Interswift, on the market. This product is a hybrid technology product between controlled erosion (CDPs) and self-polishing (SPS) technology.

[0010] In order to solve the problems of resin cracking and peeling caused by the presence of metal salts, Nippon patented a resin technology, the side chain of which contains a metal structure, which can provide a certain hydrophilic group through appropriate hydrolysis. SIGMA and DEVOE have also carried out research in this area, and many products have been widely used on ships and related facilities.

[0011] The patents related to self-polishing antifouling technology have always been controlled by foreign coating companies or groups, such as Sigma in Belgium, IP in the UK, Kansai in Japan and Hempel in Denmark. The patents of related technologies independently developed by my country only appeared after 2000. Yu Liangmin et al. studied and synthesized an acrylic resin containing organic zinc or copper, and used it in the preparation of organic metal self-polishing antifouling coatings. The characteristics are that the basic salt of zinc or copper of organic acid is first synthesized, and then the acrylic resin containing carboxyl is synthesized, and the basic salt of zinc or copper of organic acid is reacted with the acrylic resin containing carboxyl to obtain the acrylic resin containing zinc or copper. In the actual sea experiment, it was found that its antifouling performance is comparable to that of international products. Later, the research group developed an alkaline polystyrene-pyridine resin as a self-polishing coating additive, which can catalyze the hydrolysis of acrylic resin and improve the self-polishing property of marine coating film-forming materials. Yu Liangmin et al. also synthesized capsaicin derivatives containing C=C double bond groups and organic acids containing indole functional structures. These two types of derivatives can be introduced as reactants into the above-mentioned zinc acrylate or metal salt resin and used as a coating base material for polishing. In seawater, after zinc and copper ions are hydrolyzed on the coating surface, the capsaicin structure with excellent antifouling ability is still present, so the coating has good antifouling performance.

[0012] However, self-polishing antifouling coatings rely on the hydrolysis of resins in seawater to remove the old surface, and therefore, are insufficient in terms of antifouling life.

[0013] 2. Low surface energy antifouling coating

[0014] Low surface energy antifouling coatings have certain advantages in all aspects. They mainly rely on the principle that marine organisms are not easy to adhere to the coating surface, and can be washed away by high-speed operation to achieve the purpose of antifouling. Low surface energy antifouling coatings use the low surface free energy of the paint film and the large contact angle with water to make it difficult for liquids to spread on its surface without wetting, thereby preventing the attachment of marine organisms. Even if organisms are attached to low surface free energy antifouling coatings, they are relatively easy to fall off automatically under the action of water flow or external force. Low surface energy antifouling coatings will become one of the most promising directions to replace toxic antifouling coatings. At present, low surface energy antifouling coatings mainly include organic fluorine low surface energy coatings and silicone low surface energy coatings.

[0015] With the in-depth study of organic fluorine, it is found that the ideal organic fluorine antifouling coating should have the following characteristics: very smooth surface, strong non-stickiness, large enough fluorinated groups on the surface, high enough fluorine content, as many -F- groups as possible, and high enough stability of the surface fluorinated groups to resist the molecular rearrangement induced by biological molecules. Since organic fluorine resin is a rigid polymer, once fouling organisms are attached to the surface, it takes a high energy to fall off, so there are many disadvantages in organic fluorine antifouling coating. In addition, the difficulty in the development of organic fluorine antifouling coating is also an important factor limiting the application of such coatings. For this reason, organic silicon and organic fluorine are combined, with silicon oxygen chain as the main chain, and a certain concentration of -F- groups are introduced into the side chain. The group is strictly oriented to the surface. The whole macromolecule not only maintains the high elasticity and high fluidity of linear polysiloxane, but also absorbs the ultra-low surface energy characteristics of -F- groups. This organic silicon-organic fluorine low surface energy antifouling coating has the characteristics of idealized organic silicon and organic fluorine antifouling coatings, so it has excellent antifouling performance. International Paint has developed and applied a series of silicone low surface energy antifouling coatings, such as Intersleek 425, 700, 900, etc. In addition, Chugoku, PPG, Hempel, Jotun, etc. have developed commercial products in the field of low surface energy antifouling coatings.

[0016] 3. Bionic antifouling coating

[0017] In addition to the above marine antifouling technologies, bionic antifouling coatings are also a hot topic of research at home and abroad. Bionic antifouling coatings are a new antifouling concept. It is to find antifouling polymer materials based on the attachment mechanism of marine organisms. From the perspective of marine biology and chemical ecology, the anti-adhesion mechanism of large marine animals and plants such as lotus leaves was studied, and their structure and epidermal morphology were simulated, and then bionic antifouling coatings were developed. For example, chemists at the University of Washington in the United States simulated the microstructure and mechanism of dolphin skin and developed a new type of antifouling coating. The coating is composed of two immiscible polymers, one is a highly branched fluorinated polymer and the other is linear polyvinyl chloride. These two polymers are cured by cross-linking to produce a special coating that simulates the epidermis of dolphins and prevents the attachment of marine organisms. Professor Christoph Baum of the School of Veterinary Medicine in Hannover, Germany, and his research team found that the skin of the pilot whale has a special fiber structure that can prevent the adsorption and adhesion of microorganisms such as arthropod larvae in the ocean. It is expected that an antifouling paint for ships will be developed based on the structure and principle of the pilot whale skin. Sweden has developed a marine antifouling paint called "Sheakte". Through the study of dolphin skin, it was found that there is a very unstable layer of villi on the surface of dolphin skin, which makes it difficult for marine organisms to attach to its surface. Based on this principle, surface flocking antifouling paint has been developed, but how to control the length, diameter and density of the villi remains to be solved. The self-cleaning principle of lotus leaves discovered by Dr. Barthlott, a botanist at the University of Bonn in Germany, has enabled bionics to be applied in coatings. Through the ultrastructure and properties of the lotus leaf surface, it was found that there is also a nanostructure on the papilla of the microstructure on the lotus leaf surface. This combination of micro and nanostructures is the fundamental reason for the super-hydrophobicity of the surface. Related studies have shown that in amphiphilic materials with microphase separation structures containing silicone, when the proportion of hydrophobic components in the total components is 10-20%, the material will show the lowest surface energy and the best antifouling performance. Gudipati et al. synthesized a hyperbranched fluoropolymer cross-linked by polyethylene glycol. Due to the incompatibility between the two components of polyethylene glycol and fluoropolymer, the synthesized material exhibits a microphase separation morphology, which makes this polymer have a better performance than polydimethylsiloxane in preventing spore adsorption. Similar amphiphilic cross-linked polymers, such as polyisobutylene / poly(hydroxyethyl methacrylate), also have a microphase separation morphology, which can prevent protein and cell adsorption. At present, the super-hydrophobic structure prepared by membrane preparation technology in China is mainly used in textile antifouling and building antifouling. There is no report on the research of super-hydrophobic coatings for the purpose of ship antifouling, and the current research is still in the laboratory research stage.

[0018] In summary, the current antifouling coatings have the following technical defects:

[0019] (1) Traditional antifouling coatings mainly use the slow release of toxic substances (such as cuprous oxide and organotin) in the coating to kill nearby organisms to achieve the purpose of antifouling, which will cause pollution to the marine environment and have average antifouling performance;

[0020] (2) The antifouling paints of the 1930s were based on asphalt, ethylene resin and chlorinated rubber, with Cu2O and HgO as antifouling agents, which easily caused the paint film to precipitate and prevented the toxic material from seeping out; the antifouling paints of the 1960s were organotin antifouling paints, which had an unstable toxic material seepage rate and a short antifouling period; the antifouling paints of the 1980s were organotin self-polishing antifouling paints, which released toxins that seriously polluted the marine ecological environment; Wuxi self-polishing antifouling paints were used in the early 21st century, which were environmentally friendly and had low surface energy, but the antifouling effect was average.

[0021] Therefore, it is necessary to develop new antifouling coatings that will not pollute the marine environment and have better antifouling performance. Summary of the invention

[0022] In order to overcome the deficiencies and shortcomings of this part in the prior art, a marine antifouling coating based on fluorosilicone low surface energy resin is provided. On the basis of preparing a new fluorosilicone resin, the structure of silicone oil and the type of filler are designed and screened, and then further component design and optimization are carried out. At the same time, in order to overcome the shortcomings of poor adhesion and general mechanical properties of traditional low surface energy antifouling coatings, the development of primer and mid-coat is coordinated, and primer and mid-coat suitable for the antifouling coating are further developed, thereby forming a complete antifouling coating product system.

[0023] Marine antifouling coatings mainly utilize the low surface energy of fluorosilicone resin and the migration of special silicone oil to achieve antifouling and prevent the attachment of marine microorganisms; the introduction of polyethanol structure is used to achieve resistance to the attachment of protein-like organisms; and through the adjustment of the mechanical properties of the solid, especially the strength and modulus, the coating can allow larger deformation under scouring conditions, thereby flushing away surface attachments.

[0024] Technical problems solved by the present invention:

[0025] 1. Synthesis and engineering preparation of fluorosilicone resin. Resin is the basis of coating performance. There have been many reports on the synthesis and preparation of fluorosilicone resin, but there are relatively few fluorosilicone resins used in coatings, especially antifouling coatings. From the reaction principle, organic silicon polymers and fluorine-containing compounds have poor compatibility and there are certain difficulties in reacting. At the same time, the fluorine content and the form of fluorine have a direct impact on the performance of the resin. Therefore, breaking through its synthesis and preparation technology and realizing engineering preparation is the key to the present invention.

[0026] 2. Research on fluorosilicone resin curing system. The introduction of organic fluorine structure will inevitably cause changes in the curing mechanism and process of organic silicon polymers. However, the construction of marine vessels inevitably requires a room temperature curing coating system. At the same time, the design of the curing system determines the mechanical properties of the resin. In the field of marine antifouling, the mechanical properties, modulus and other data of the coating have an important influence on the antifouling effect of the dynamic operation process of the ship. Therefore, screening and optimizing the curing system of the resin, realizing the rapid and room temperature curing of the resin, and controlling the mechanical properties play an important role in the design and implementation of the coating components, and is also one of the key technologies of the present invention.

[0027] 3. Design and optimization of antifouling coating components. Resin is the basis of coating, and pigments, fillers, additives, etc. are boosters for coating performance. In particular, functional fillers play a key role in the mechanical properties and anticorrosive properties of coatings. The pigment system determines the application site of the coating. Additives have a direct impact on the construction of the coating, especially special silicone oils, special organic silicone ether copolymers, etc., which also have a direct impact on the antifouling properties of the coating. Therefore, based on the preparation of resins, the most critical technology of the present invention is to achieve the formulation design, optimization, and even evaluation of the coating.

[0028] 4. Formula design and optimization of primer and mid-coat coatings. The low surface energy characteristics of fluorosilicone resin determine that it has certain defects in adhesion and other aspects. The mature low surface energy antifouling coating technology abroad mostly adopts the idea of ​​matching primer and mid-coat to solve the adhesion problem with the substrate. This project also adopts the scheme of primer and mid-coat to cooperate with the construction of antifouling coatings, which is the guarantee for the practical application of the antifouling coating of the present invention.

[0029] The present invention provides a marine antifouling coating based on a fluorosilicone low surface energy resin, comprising:

[0030] The three-layer structure from top to bottom is, in order, a fluorosilicone low surface energy resin coating (1), an organosilicon epoxy mid-coat coating (2), and an epoxy primer coating (3); a deketoxime type curing agent is provided between the fluorosilicone low surface energy resin coating (1) and the organosilicon epoxy mid-coat coating (2);

[0031] The fluorosilicone low surface energy resin coating (1) is an antifouling coating; the epoxy primer coating (3) is an epoxy resin polymer; the organosilicon epoxy mid-coat coating (2) uses an organosilicon-modified epoxy coating to form a coating system that matches the epoxy primer coating (3) and the fluorosilicone low surface energy resin coating (1); the organosilicon-modified epoxy coating contains silane alkoxy groups and epoxy groups to achieve bonding between the organosilicon epoxy mid-coat coating (2), the epoxy primer coating (3) and the fluorosilicone low surface energy resin coating (1);

[0032] The deketoxime curing agent has the dual functions of curing and viscosity increasing. The deketoxime curing agent uses KH550, KH570, methyl butanone oxime silane and ethyl butanone oxime silane as raw materials, and reacts with part of water under heating conditions to form a multifunctional curing / tackifying agent.

[0033] Preferably, the coating in the fluorosilicone low surface energy resin coating (1) comprises a fluorosilicone low surface energy resin, and the design, synthesis and engineering of the fluorosilicone low surface energy resin comprises:

[0034] Based on the hydrosilylation reaction, the hydroxyl-terminated hydrogen-containing polysiloxane is initially reacted with the perfluoropolyether acrylate;

[0035] After repeatedly adjusting the molecular weight and ratio of the hydroxyl-terminated hydrogen-containing polysiloxane and the perfluoropolyether acrylate, the preliminary reaction is repeated to prepare a series of fluorosilicone low surface energy resins;

[0036] Adding a catalyst, under the action of the catalyst, the series of fluorosilicone low surface energy resins react with the hydroxyl-terminated polydimethylsiloxane and the crosslinking agent to form a coating corresponding to the series of fluorosilicone low surface energy resins;

[0037] The phase separation degree, surface energy change and hydrophobic and oleophobic properties of the coating corresponding to the series of fluorosilicone low surface energy resins are evaluated, and based on the evaluation results, the fluorosilicone low surface energy resin is optimized and prepared to form the fluorosilicone low surface energy resin used for the fluorosilicone low surface energy resin coating (1).

[0038] Preferably, the fluorosilicone low surface energy resin is further compounded with a special functional additive to improve the antifouling performance of the antifouling coating.

[0039] Preferably, the special functional additive is a special silicone oil, and the special silicone oil is a polyether-modified silicone oil or a hydrophilic amino silicone oil synthesized on the basis of methyl silicone oil.

[0040] Preferably, the special functional additive is a quaternary ammonium salt modified silicone resin.

[0041] Preferably, the fluorosilicone low surface energy resin is also filled with fillers and surface treatment agents.

[0042] Preferably, the filler is prepared based on fumed silica treated with hexamethyldisilazide.

[0043] Preferably, the surface treatment agent is a polytetrafluoroethylene surface treatment agent and / or a silica gel surface treatment agent.

[0044] Preferably, the fluorosilicone low surface energy resin is also filled with a solvent to form a solvent-based fluorosilicone coating.

[0045] Preferably, when the fluorosilicone low surface energy resin is also filled with a solvent, the surface treatment agent is a fluorinated acrylate surface treatment agent, and the preparation method of the fluorinated acrylate surface treatment agent includes:

[0046] Prepare raw materials, including: methyl methacrylate MMA, ethyl methacrylate EMA, butyl methacrylate BMA, isobutyl methacrylate IBMA, isooctyl methacrylate EHMA, isobornyl methacrylate IBOMA, lauryl methacrylate LMA, octadecyl methacrylate SMA, KH570, benzoyl peroxide BPO, dibutyltin dilaurate, solvent gasoline (mainly alkanes, excluding benzene);

[0047] Methacrylate monomers, 1.0% BPO and fluorine-containing methacrylate monomers and silane monomers are added to the solvent according to different feeding methods, with a total monomer mass percentage of 30%. The temperature is raised to 80-85 degrees Celsius for reaction for 3 hours, and then cooled to obtain a solution of a fluorine-containing acrylate copolymer surface treatment agent.

[0048] Beneficial effects of the present invention:

[0049] (1) The present invention utilizes the low surface energy of fluorosilicone resin to achieve antifouling, and utilizes the migration of special silicone oil to achieve the function of preventing marine microorganisms from attaching during marine operation;

[0050] (2) The present invention utilizes the introduction of a polyethanol structure to achieve adhesion resistance against proteinaceous organisms;

[0051] (3) The present invention utilizes the terminal hydroxyl groups and silaneoxy groups of fluorosilicone resin and organosilicon polymer to achieve room temperature curing under the action of curing agent and catalyst;

[0052] (4) The present invention adjusts the mechanical properties of the solidified material, especially the strength and modulus, so that the coating can be allowed to deform greatly under the flushing state, thereby flushing away the surface attachments.

[0053] (5) The base coating of the present invention is mainly composed of commonly used epoxy resin polymers, and the middle coating layer adopts silicone modified epoxy coating to achieve effective bonding with the base coating layer and the antifouling coating layer. The low surface energy coating means that its bonding force with other substrates is relatively weak. In order to avoid the influence on the low surface energy properties of the coating, the present invention adopts a middle coating method to solve the adhesion problem between the fluorosilicone coating and the substrate. Specifically, a silicone epoxy resin filler is used as the middle coating layer of the fluorosilicone low surface energy coating and the substrate. The middle coating layer contains silaneoxy groups, which can improve the bonding with the fluorosilicone resin. The epoxy groups in the structure can improve the adhesion with the substrate, thereby providing a way to improve the adhesion of the fluorosilicone resin, which undoubtedly lays a good foundation for the long life and high efficiency antifouling of the low surface coating.

[0054] Based on the following detailed description of specific embodiments of the present invention in conjunction with the accompanying drawings, those skilled in the art will become more aware of the above and other objects, advantages and features of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Hereinafter, some specific embodiments of the present invention will be described in detail in an exemplary and non-limiting manner with reference to the accompanying drawings. The same reference numerals in the accompanying drawings indicate the same or similar components or parts. It should be understood by those skilled in the art that these drawings are not necessarily drawn to scale. The objects and features of the present invention will become more apparent in view of the following description in conjunction with the accompanying drawings, in which:

[0056] Figure 1 Schematic diagram of the microstructure of a marine antifouling coating based on a fluorosilicone low surface energy resin according to an embodiment of the present invention.

[0057] Figure 2 (a)-(c) are three ways in which the attached matter falls off from the coating surface according to the embodiment of the present invention, wherein Figure 2 (a) is the peeling method, Figure 2 (b) is the shearing method, Figure 2 (c) is the non-planar shearing method.

[0058] Figure 3 : is a curve showing the change of relative adhesion with surface free energy according to an embodiment of the present invention - Baier curve.

[0059] Figure 4 Schematic diagram of the chemical molecular structure of the designed and synthesized novel fluorosilicone resin according to an embodiment of the present invention.

[0060] Figure 5 Schematic diagram of the synthesis route of polyether-modified silicone oil according to an embodiment of the present invention.

[0061] Figure 6 Schematic diagram of the principle of a filler processing method according to an embodiment of the present invention.

[0062] Figure 7 : is the H-NMR spectrum of the curing / adhesion enhancing agent according to an embodiment of the present invention.

[0063] Figure 8 Schematic diagram of the synthesis route of fluorosilicone resin according to an embodiment of the present invention.

[0064] Fig. 9 Schematic diagram of H NMR spectrum of the designed and synthesized fluorosilicone polymer according to an embodiment of the present invention.

[0065] Fig.10 Schematic diagram of the NMR fluorine spectrum of the fluorosilicone polymer designed and synthesized according to an embodiment of the present invention. DETAILED DESCRIPTION

[0066] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with the accompanying drawings and specific implementation methods.

[0067] like Figure 1 As shown, this embodiment provides a marine antifouling coating based on fluorosilicone low surface energy resin, comprising:

[0068] The three-layer structure from top to bottom is, in order, a fluorosilicone low surface energy resin coating (1), an organosilicon epoxy mid-coat coating (2), and an epoxy primer coating (3); a deketoxime type curing agent is provided between the fluorosilicone low surface energy resin coating (1) and the organosilicon epoxy mid-coat coating (2);

[0069] The fluorosilicone low surface energy resin coating (1) is an antifouling coating; the epoxy primer coating (3) is an epoxy resin polymer with good anti-corrosion performance and high adhesion; the organosilicon epoxy mid-coat coating (2) adopts an organosilicon-modified epoxy coating to form a coating system that matches the epoxy primer coating (3) and the fluorosilicone low surface energy resin coating (1), and the organosilicon-modified epoxy coating contains silaneoxy and epoxy groups to achieve the bonding between the organosilicon epoxy mid-coat coating (2), the epoxy primer coating (3) and the fluorosilicone low surface energy resin coating (1).

[0070] The deketoxime curing agent has the dual functions of curing and viscosity increasing. The deketoxime curing agent uses KH550, KH570, methyl butanone oxime silane and ethyl butanone oxime silane as raw materials, and reacts with part of water under heating conditions to form a multifunctional curing / tackifying agent.

[0071] The middle coating contains silaneoxy groups, which can improve the bonding with fluorosilicone resin; while the epoxy groups in the structure can improve the adhesion with the substrate, thus providing a way to improve the adhesion of fluorosilicone resin.

[0072] As a preferred embodiment, the coating in the fluorosilicone low surface energy resin coating (1) comprises a fluorosilicone low surface energy resin. The principle of using this material is that the low surface energy antifouling coating removes marine organisms mainly by peeling, plane shearing, non-plane shearing and other methods from the coating surface (see Figure 2 (a) Figure 2 (b) and Figure 2 (c)), where the energy required for peeling is minimal. Therefore, an effective measure is to use a coating with low surface energy so that the fouling organisms have poor wettability with the surface of the coating, making it difficult for them to adhere or not adhere firmly. Such coatings should also have a low elastic modulus to facilitate the fouling organisms to fall off the coating by peeling. Since relative adhesion is also related to factors such as the elastic modulus of the coating, the relationship between surface energy and relative adhesion has a more classic Baier curve (such as Figure 3 The most notable feature of the curve is that the point with the lowest adhesion does not correspond to the point with the lowest surface energy. The adhesion first decreases and then increases with the decrease of surface free energy. The adhesion is the lowest when the surface energy reaches 23-25mj / m2. Therefore, it is not the case that the lower the surface energy of the coating, the lower the relative adhesion. The molecular structure of the fluorosilicone low surface energy resin of the present invention is as follows: Figure 4 shown.

[0073] As a preferred embodiment, the design, synthesis and engineering of the fluorosilicone low surface energy resin include:

[0074] Based on the hydrosilylation reaction, the hydroxyl-terminated hydrogen-containing polysiloxane is initially reacted with the perfluoropolyether acrylate;

[0075] After repeatedly adjusting the molecular weight and ratio of the hydroxyl-terminated hydrogen-containing polysiloxane and the perfluoropolyether acrylate, the preliminary reaction is repeated to prepare a series of fluorosilicone low surface energy resins;

[0076] Adding a catalyst, under the action of the catalyst, the series of fluorosilicone low surface energy resins react with the hydroxyl-terminated polydimethylsiloxane and the crosslinking agent to form a coating corresponding to the series of fluorosilicone low surface energy resins;

[0077] The phase separation degree, surface energy change and hydrophobic and oleophobic properties of the coating corresponding to the series of fluorosilicone low surface energy resins are evaluated, and based on the evaluation results, the fluorosilicone low surface energy resin is optimized and prepared to form the fluorosilicone low surface energy resin used for the fluorosilicone low surface energy resin coating (1).

[0078] Fluorosilicone resin is an important material. The viscosity and molecular weight of the resin itself determine the rheological properties of the coating. By selecting silicone polymers and fluorine-containing components, the viscosity of the polymer can be regulated within a certain range, thus laying the foundation for the preparation of antifouling coatings with high solid content. At the same time, through advanced mixing and dispersion technology, inorganic fillers are dispersed in the resin, so that the coating still has good rheological properties under low solvent content. This is not only conducive to storage, transportation and construction, but also meets the national requirements for environmentally friendly coatings, especially restrictions on VOC content.

[0079] As a preferred embodiment, the fluorosilicone low surface energy resin is further compounded with a special functional additive to improve the antifouling performance of the antifouling coating.

[0080] The reason for the application of special functional additives is that marine antifouling is a collection of various comprehensive factors. There are many types of marine microorganisms. It is difficult to achieve a comprehensive antifouling effect through the performance of a single material.

[0081] As a preferred embodiment, the special functional additive is a special silicone oil, and the special silicone oil is a polyether-modified silicone oil or a hydrophilic amino silicone oil synthesized on the basis of methyl silicone oil.

[0082] Special silicone oil is used because: the polyethanol structure can resist protein attachment, and the addition of water-absorbing materials can form a water molecule layer on the coating surface, reducing the attachment of microorganisms, thereby increasing the coating's ability to resist protein, bacteria, algae, etc. On the basis of low surface energy resin, polyethanol structure and hydrophilic structure are further introduced to further enhance the antifouling performance of the product, thereby achieving the best antifouling effect. This overcomes the characteristics of traditional methods that use "toxic resins" or "easily hydrolyzed resins" as the key to antifouling, and can effectively achieve the antifouling function and increase the antifouling life. The synthetic route of polyether modified silicone oil is as follows: Figure 5 shown.

[0083] As a preferred embodiment, the special functional additive is a quaternary ammonium salt modified silicone resin.

[0084] In this embodiment, a silicone resin containing a quaternary ammonium salt structure is compounded into the coating to achieve a bactericidal effect and resist the formation of biofilms by bacteria and diatoms on the coating surface. This will reduce the requirements of the surface coating for sailing speed and improve the antifouling effect to a greater extent.

[0085] As a preferred embodiment, the fluorosilicone low surface energy resin is also filled with fillers and surface treatment agents, so as to obtain an antifouling coating with excellent comprehensive performance.

[0086] like Figure 6 As shown, as a preferred embodiment, the filler is prepared based on fumed silica treated with hexamethyldisilazide to enhance its surface hydrophobicity, which can effectively improve the hydrophobicity of the formed coating while improving the storage stability of the coating.

[0087] As a preferred embodiment, the surface treatment agent is a polytetrafluoroethylene surface treatment agent and / or a silicone surface treatment agent; the polytetrafluoroethylene surface treatment agent is used to overcome the disadvantage that the filler surface is extremely smooth and difficult to bond with other materials; the silicone surface treatment agent is used to improve the surface polarity of the filler and greatly improve the bonding performance.

[0088] As a preferred embodiment, the fluorosilicone low surface energy resin is also filled with a solvent to form a solvent-based fluorosilicone coating. Since the base material of the fluorosilicone coating is a fluorine value and the fluorine-silicon bond length is small, the fluorosilicone coating has far better acid resistance, alkali resistance, corrosion resistance, weather resistance, and oil repellency, water repellency, anti-sticking and anti-pollution properties than general coatings. In this embodiment, the solvent-based fluorosilicone coating is a room temperature drying solvent-based fluorosilicone coating, including a room temperature drying single-component solvent-based fluorosilicone coating and a room temperature curing two-component solvent-based fluorosilicone coating. The biggest feature is fast drying and the performance is much higher than that of water-based coatings.

[0089] As a preferred embodiment, when the fluorosilicone low surface energy resin is also filled with a solvent, the surface treatment agent is a fluorinated acrylate surface treatment agent. The fluorinated acrylate surface treatment agent is a polymer. Based on the low surface energy of the fluoroalkyl group and the long fluoroalkyl side bonds of the fluorinated acrylate polymer, the reaction enthalpy and Qe value of the fluorinated methyl acrylate monomer are similar to those of methyl acrylate, the polymerization conditions are mild, and it can be copolymerized with many vinyl monomers. By changing the type and amount of the copolymerized monomer, the copolymer is easily soluble in environmentally friendly solvent gasoline that does not contain benzene, forming a high-performance and environmentally friendly fluorinated acrylate surface treatment agent.

[0090] As a preferred embodiment, the preparation method of the fluoroacrylate surface treatment agent comprises:

[0091] Prepare raw materials, including: methyl methacrylate MMA, ethyl methacrylate EMA, butyl methacrylate BMA, isobutyl methacrylate IBMA, isooctyl methacrylate EHMA, isobornyl methacrylate IBOMA, lauryl methacrylate LMA, octadecyl methacrylate SMA, KH570, benzoyl peroxide BPO, dibutyltin dilaurate, solvent gasoline (mainly alkanes, excluding benzene);

[0092] Methacrylate monomers, 1.0% BPO and fluorine-containing methacrylate monomers and silane monomers are added to the solvent according to different feeding methods, with a total monomer mass percentage of 30%. The temperature is raised to 80-85 degrees Celsius for reaction for 3 hours, and then cooled to obtain a solution of a fluorine-containing acrylate copolymer surface treatment agent.

[0093] Application examples:

[0094] 1. Technical indicators of the marine antifouling coating based on fluorosilicone low surface energy resin in this embodiment:

[0095] (1) The water contact angle is not less than 100 degrees;

[0096] (2) The oil contact angle is not less than 50 degrees;

[0097] (3) Dynamic hanging board test: the test contamination rate is no more than 50%;

[0098] (4) Tensile strength not less than 1.5 MPa;

[0099] (5) Hardness not greater than 70 (Shore A).

[0100] 2. Development of Fluorosilicone Resin-Based Antifouling Coatings

[0101] (a) Component design and optimization of silicone polymers

[0102] Taking 1100SR as a reference, hydroxyl-terminated organopolysiloxane 107 with different molecular weights was screened, and white carbon black, iron red, etc. were selected, focusing on the rationality of the component through viscosity, system stability, etc. On this basis, silicone oil was screened and the following ratio was finally determined as shown in Table 1.

[0103] Table 1 Component design of silicone polymer

[0104] Component name Proportion 107 glue 100 White Carbon Black 10 Iron Red 1.8 Methyl silicone oil 0.8 Xylene 5

[0105] (b) Design and synthesis of curing / adhesive agents

[0106] The current 1100SR is a three-component system, which is not only inconvenient to use but also has low adhesion. For this reason, the dealcoholization curing system was abandoned and a new type of dealktoximine curing agent was designed and synthesized, which has the dual functions of curing and viscosity enhancement.

[0107] Specifically, KH550, KH570, methyl butyl ketone oxime silane and ethyl butyl ketone oxime silane are used as main raw materials, which react with part of water under heating conditions to form a multifunctional curing / adhesive agent.

[0108] The H NMR spectrum of the designed and synthesized curing / adhesion enhancer is as follows Figure 7 shown.

[0109] (c) Design and synthesis of fluorosilicone resin

[0110] This is the difficulty of the present invention. In order to ensure that the low surface energy and oleophobic characteristics of the fluorinated polymer can be utilized without causing phase separation problems in the coating due to its poor compatibility with the organosilicon compound, a reactive fluorine-silicon hybrid polymer is designed and synthesized. The specific reaction process is as follows: Figure 8 As shown, its structure was confirmed by nuclear magnetic hydrogen spectrum, fluorine spectrum, etc. Fig. 9 and Fig.10 shown.

[0111] (d) Preliminary evaluation of the performance of antifouling coatings

[0112] Based on the above work, a preliminary comparison was made between the performance of the self-designed fluorosilicone low surface energy antifouling coating and 1100SR. The specific results are shown in Table 2 below.

[0113] Table 2 Performance comparison between homemade samples and 1100SR

[0114]

[0115] Although preferred embodiments of the present invention have been described, additional changes and modifications may be made to these embodiments by those skilled in the art once the basic inventive concepts are known. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention. Obviously, those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A marine antifouling coating based on fluorosilicone low surface energy resin, characterized in that: include: The three-layer structure from top to bottom is, in order, a fluorosilicone low surface energy resin coating (1), an organosilicon epoxy mid-coat coating (2), and an epoxy primer coating (3); a deketoxime type curing agent is provided between the fluorosilicone low surface energy resin coating (1) and the organosilicon epoxy mid-coat coating (2); The fluorosilicone low surface energy resin coating (1) is an antifouling coating; the epoxy primer coating (3) is an epoxy resin polymer; the organosilicon epoxy mid-coat coating (2) uses an organosilicon-modified epoxy coating to form a coating system that matches the epoxy primer coating (3) and the fluorosilicone low surface energy resin coating (1); the organosilicon-modified epoxy coating contains silane alkoxy groups and epoxy groups to achieve bonding between the organosilicon epoxy mid-coat coating (2), the epoxy primer coating (3) and the fluorosilicone low surface energy resin coating (1); The deketoxime curing agent has the dual functions of curing and viscosity increasing. The deketoxime curing agent uses KH550, KH570, methyl butanone oxime silane and ethyl butanone oxime silane as raw materials, and reacts with part of water under heating conditions to form a multifunctional curing / tackifying agent.

2. A marine antifouling coating based on fluorosilicone low surface energy resin according to claim 1, characterized in that: The coating in the fluorosilicone low surface energy resin coating (1) comprises a fluorosilicone low surface energy resin, and the preparation method of the fluorosilicone low surface energy resin comprises: Based on the hydrosilylation reaction, the hydroxyl-terminated hydrogen-containing polysiloxane is initially reacted with the perfluoropolyether acrylate; After repeatedly adjusting the molecular weight and ratio of the hydroxyl-terminated hydrogen-containing polysiloxane and the perfluoropolyether acrylate, the preliminary reaction is repeated to prepare a series of fluorosilicone low surface energy resins; Adding a catalyst, under the action of the catalyst, the series of fluorosilicone low surface energy resins react with the hydroxyl-terminated polydimethylsiloxane and the crosslinking agent to form a coating corresponding to the series of fluorosilicone low surface energy resins; The phase separation degree, surface energy change and hydrophobic and oleophobic properties of the coating corresponding to the series of fluorosilicone low surface energy resins are evaluated, and based on the evaluation results, the fluorosilicone low surface energy resin is optimized and prepared to form the fluorosilicone low surface energy resin used for the fluorosilicone low surface energy resin coating (1).

3. A marine antifouling coating based on fluorosilicone low surface energy resin according to claim 2, characterized in that: The fluorosilicone low surface energy resin is further compounded with a special functional additive to improve the antifouling performance of the antifouling coating.

4. A marine antifouling coating based on fluorosilicone low surface energy resin according to claim 3, characterized in that: The special functional additive is a special silicone oil, and the special silicone oil is a polyether-modified silicone oil or a hydrophilic amino silicone oil synthesized on the basis of methyl silicone oil.

5. A marine antifouling coating based on fluorosilicone low surface energy resin according to claim 3, characterized in that: The special functional additive is a quaternary ammonium salt modified silicone resin.

6. A marine antifouling coating based on fluorosilicone low surface energy resin according to claim 4 or 5, characterized in that: The fluorosilicone low surface energy resin is also filled with fillers and surface treatment agents.

7. A marine antifouling coating based on fluorosilicone low surface energy resin according to claim 6, characterized in that: The filler is prepared based on fumed silica treated with hexamethyldisilazide.

8. A marine antifouling coating based on fluorosilicone low surface energy resin according to claim 6, characterized in that: The surface treatment agent is a polytetrafluoroethylene surface treatment agent and / or a silica gel surface treatment agent.

9. A marine antifouling coating based on fluorosilicone low surface energy resin according to claim 6, characterized in that: The fluorosilicone low surface energy resin is also filled with a solvent to form a solvent-based fluorosilicone coating.

10. A marine antifouling coating based on fluorosilicone low surface energy resin according to claim 9, characterized in that: When the fluorosilicone low surface energy resin is also filled with a solvent, the surface treatment agent is a fluorinated acrylate surface treatment agent, and the preparation method of the fluorinated acrylate surface treatment agent includes: Prepare raw materials, including: methyl methacrylate MMA, ethyl methacrylate EMA, butyl methacrylate BMA, isobutyl methacrylate IBMA, isooctyl methacrylate EHMA, isobornyl methacrylate IBOMA, lauryl methacrylate LMA, octadecyl methacrylate SMA, KH570, benzoyl peroxide BPO, dibutyltin dilaurate, solvent gasoline (mainly alkanes, excluding benzene); Methacrylate monomers, 1.0% BPO and fluorine-containing methacrylate monomers and silane monomers are added to the solvent according to different feeding methods, with a total monomer mass percentage of 30%. The temperature is raised to 80-85 degrees Celsius for reaction for 3 hours, and then cooled to obtain a solution of a fluorine-containing acrylate copolymer surface treatment agent.

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