A boron nitride-coated graphene dispersant modifier and a marine anti-corrosion coating

Abstract

This invention discloses a boron nitride-coated graphene dispersant modifier and a marine anti-corrosion coating. The boron nitride-coated graphene dispersant modifier is prepared from the following raw materials: graphene nanosheets, bifunctionalized boron nitride nanodots, surfactants, silane coupling agents, solvents, dispersants, and anti-aging agents. The boron nitride-coated graphene dispersant modifier of this invention can significantly improve the dispersion stability, salt spray resistance, and long-term anti-corrosion performance of coatings, integrating the triple properties of high-speed seawater erosion resistance, strong UV aging resistance, and insulating and conductive corrosion-resistant properties into the boron nitride-coated graphene dispersant modifier.

Description

Technical Field

[0001] This invention relates to the field of marine anti-corrosion materials technology, and more specifically, to a boron nitride-coated graphene dispersant modifier and a marine anti-corrosion coating. Background Technology

[0002] The marine environment is characterized by high salinity, high humidity, strong corrosiveness, dynamic high-speed erosion, and strong ultraviolet radiation. High concentrations of chloride ions and dissolved oxygen in seawater accelerate the electrochemical corrosion of metals, the erosion effect damages the interface between the passivation film and the filler, and strong ultraviolet radiation causes the coating to powder and crack, seriously affecting the service life of marine facilities.

[0003] Graphene has become a research hotspot in anti-corrosion materials due to its excellent shielding properties, but it still faces three major bottlenecks: easy aggregation, the formation of conductive micro-batteries that accelerate corrosion, and weak interfacial bonding with inorganic / organic coatings. Although boron nitride can achieve insulating modification by coating graphene through π-π interactions, coating solely through π-π interactions has some drawbacks, such as the coating method being only physical coating / weak bonding, low coating strength, easy desorption under high-speed seawater erosion, poor compatibility with coating substrates, and inability to synchronously adapt to ultraviolet aging.

[0004] Therefore, developing a boron nitride-coated graphene dispersant with high covalent bonding strength, long-term stable dispersibility, resistance to high-speed erosion, resistance to strong ultraviolet aging, and insulation and corrosion inhibition has become a key technological requirement in the field of marine corrosion-resistant materials. Summary of the Invention

[0005] This invention is based on the inventor's discovery and understanding of the following facts and problems: Currently, boron nitride-coated graphene has the following problems: the coating is only physical / weak bonding, it is easy to desorb under high-speed seawater scouring, the dispersion stability is poor, the bonding force with the coating matrix is ​​weak, it cannot suppress the graphene's conductivity-promoting corrosion, and it is not suitable for the dynamic corrosion and ultraviolet aging coupling environment of the ocean.

[0006] In related technologies, the composite of boron nitride and graphene is mostly a simple physical mixture or a weak bond at a single site, and the coating layer is easily detached under the scouring of high-speed seawater exceeding 5 m / s. Furthermore, the single use or non-directional compounding of dispersants and surfactants cannot achieve long-term dispersion of graphene. Conventional addition of silane coupling agents can only achieve simple interface modification and cannot form a stable covalently bonded coating structure with boron nitride nanodots, let alone construct a three-dimensional covalently bonded network of "graphene-boron nitride-coating matrix". In addition, current modifiers do not consider the high-speed dynamic scouring and strong UV aging coupling effects of the marine environment, and the coating is prone to powdering, cracking, and rapid degradation of its anti-corrosion performance during long-term use.

[0007] This invention aims to at least partially solve one of the technical problems in related technologies. To this end, embodiments of this invention propose a boron nitride-coated graphene dispersant modifier and a marine anti-corrosion coating. This involves bifunctionalized boron nitride nanodots covalently coated with graphene nanosheets, creating a marine anti-corrosion coating suitable for dynamic marine erosion and UV aging. It is applicable to the modification of anti-corrosion coatings for metal components in harsh marine corrosive environments, significantly improving the coating's dispersion stability, salt spray resistance, and long-term anti-corrosion performance. Simultaneously, it considers the coating's high-speed seawater erosion resistance, long-term UV aging resistance, and interfacial covalent bond strength, integrating the triple properties of high-speed seawater erosion resistance, strong UV aging resistance, and insulating and conductive corrosion resistance into the boron nitride-coated graphene dispersant modifier.

[0008] This invention provides a boron nitride-coated graphene dispersant modifier, which is prepared from the following raw materials: graphene nanosheets, bifunctionalized boron nitride nanodots, surfactants, silane coupling agents, solvents, dispersants, and anti-aging agents.

[0009] In some embodiments, the material is prepared from the following parts by weight: graphene nanosheets: 10-20 parts; bifunctional boron nitride nanodots: 30-50 parts; surfactant: 5-10 parts; silane coupling agent: 3-8 parts; solvent: 80-120 parts; dispersant: 2-5 parts; anti-aging agent: 1-3 parts.

[0010] In some embodiments, the graphene nanosheets have a diameter of 0.5-5 μm;

[0011] And / or, the surface of the graphene nanosheets is etched with oxygen plasma to introduce carboxyl groups, and optionally, the carboxyl content of the etched graphene nanosheets is 0.6-1.2 mmol / g.

[0012] In some embodiments, the bifunctionalized boron nitride nanodots contain amino and epoxy bifunctional groups; And / or, the bifunctional boron nitride nanodots are obtained by modifying boron nitride nanodots with amino and epoxy groups through bifunctionalization; And / or, the size of the bifunctional boron nitride nanodots is less than 50 nm; And / or, the surface amino content of the bifunctional boron nitride nanodots is 0.8-1.5 mmol / g; And / or, the surface epoxy content of the bifunctional boron nitride nanodots is 0.5-1.0 mmol / g; And / or, the mass ratio of the graphene nanosheets to the bifunctional boron nitride nanodots is 1:2-4.

[0013] In some embodiments, the surfactant is a compound surfactant; optionally, the compound surfactant includes polyvinylpyrrolidone and polyethylene glycol. And / or, the silane coupling agent is a compound silane coupling agent; optionally, the compound silane coupling agent includes KH560 and KH550; optionally, the mass ratio of the compound silane coupling agent to the difunctionalized boron nitride nanodots is 1:5-12. And / or, the mass ratio of the silane coupling agent to the difunctionalized boron nitride nanodots is 1:5-12; And / or, the dispersing agent is a compound dispersing agent; the compound dispersing agent includes sodium citrate and sodium pyrophosphate; And / or, the anti-aging adjuvant includes at least one of ultraviolet absorber UV-531 and hindered phenolic antioxidant 1010; And / or, the solvent includes at least one of ethanol, water, and propylene glycol methyl ether.

[0014] This invention provides a method for preparing a boron nitride-coated graphene dispersion modifier, comprising the following steps: (1) Carboxyl groups are introduced into graphene nanosheets by oxygen plasma etching to obtain etched graphene nanosheets; the etched graphene nanosheets are mixed with solvent and dispersant to obtain graphene dispersion. (2) Reaction of boron nitride nanodots with aminosilane and epoxysilane yields bifunctionalized boron nitride nanodots; (3) The bifunctional boron nitride nanodots, surfactant and graphene dispersion are mixed and a coupling agent is added to carry out an amidation reaction to form a covalently bonded coating precursor mixture of bifunctional boron nitride nanodots coating graphene nanosheets. (4) Add a silane coupling agent to carry out the reaction; (5) Add anti-aging additives and mix to obtain boron nitride coated graphene dispersion modifier.

[0015] In some embodiments, in step (1), the power of the oxygen plasma etching is 200-300 W; And / or, the oxygen plasma etching time is 15-20 min.

[0016] In some embodiments, in step (2), the reaction temperature is 60-70 °C; And / or, the reaction time is 4-6 h; And / or, the aminosilane includes KH550; And / or, the epoxysilane includes KH560.

[0017] In some embodiments, in step (3), the coupling agent includes EDC and NHS; optionally, the EDC is 5-8% of the mass of the etched graphene nanosheets; optionally, the NHS is 3-5% of the mass of the etched graphene nanosheets. And / or, the temperature of the amidation reaction is 15-30°C; And / or, the amidation reaction takes 6-8 h.

[0018] In some embodiments, in step (4), the reaction temperature is 40-60 °C; And / or, the reaction time is 3-5 h.

[0019] This invention provides a marine anti-corrosion coating, comprising: the boron nitride-coated graphene dispersant modifier described in this invention or the boron nitride-coated graphene dispersant modifier prepared by the preparation method described in this invention.

[0020] In some embodiments, the boron nitride-coated graphene dispersant modifier is 0.5-3% of the total mass of the coating.

[0021] This invention provides an application of boron nitride-coated graphene dispersant or marine anti-corrosion coating for use in marine environments; And / or, for use in marine heavy-duty anti-corrosion coatings, wind turbine blade anti-corrosion coatings, or integrated antifouling and anti-corrosion coatings for ships.

[0022] The boron nitride-coated graphene dispersant modifier provided by this invention, which covalently coats graphene nanosheets with bifunctional boron nitride nanodots, is a marine anti-corrosion coating dispersant modifier adapted to dynamic marine erosion and UV aging. It is suitable for modifying anti-corrosion coatings for metal components in harsh marine corrosive environments such as marine engineering steel structures, ships, and offshore platforms. It can significantly improve the dispersion stability, salt spray resistance, and long-term anti-corrosion performance of the coating, while taking into account the coating's high-speed seawater erosion resistance, long-term UV aging resistance, and interfacial covalent bond strength. It integrates the triple properties of high-speed seawater erosion resistance, strong UV aging resistance, and insulating and anti-conductive corrosion resistance into the boron nitride-coated graphene dispersant modifier.

[0023] The modifier of this invention is a boron nitride-coated graphene dispersant modifier for marine anti-corrosion coatings, consisting of a bifunctionalized boron nitride nanodot covalently coated graphene, a surfactant and dispersant synergistic dispersion system, a directional interface modification with a bissilane coupling agent, and an in-situ supported anti-aging agent. Through directional chemical modification of the boron nitride nanodots with amino-epoxy bifunctionality, it achieves amidation covalent bonding with carboxyl-containing graphene nanosheets and dual covalent bonding with the coating matrix. Simultaneously, the combined dispersion system addresses the long-term dispersion problem, and the in-situ introduction of the combined dispersion system and anti-aging agent solves problems such as graphene agglomeration, conductive micro-battery formation promoting corrosion, and high-speed scouring and desorption of the modifier. This also improves the coating's resistance to 5m / s high-speed seawater erosion and strong UV aging resistance. Furthermore, the preparation process is simple, cost-controllable, and suitable for industrial production. Specifically: (1) Directional design of bifunctional boron nitride nanodots and amidation covalent bonding of graphene nanosheets, overcoming the limitations of physical coating / weak bonding: By performing amino-epoxy bifunctional directional modification on boron nitride nanodots, combined with directional carboxylation etching on the surface of graphene nanosheets, amidation covalent bonding of boron nitride nanodots and graphene nanosheets is achieved, and the coating strength is improved by more than 80%, solving the problem of easy desorption of existing coatings under high-speed seawater scouring at 5 m / s; at the same time, the bifunctional groups can undergo multi-redirection covalent reactions with silane coupling agents and coating matrix to form a three-dimensional covalent bonding network of "graphene-boron nitride-coating matrix", which fundamentally improves the bonding force between the modifier and the coating, and at the same time, the insulating properties of boron nitride are used to block the conductive path of graphene and inhibit micro battery corrosion.

[0024] (2) The directional synergistic design of the multi-component compound system achieves ultra-long-term dispersion stability of graphene: the compound surfactant (PVP K30+PEG400) takes into account both steric hindrance and hydrophilic-lipophilic balance, and is conducive to the bonding between boron nitride nanodots and graphene nanosheets. The compound dispersing aid (sodium citrate+sodium pyrophosphate) synergistically reduces the van der Waals forces and electrostatic forces between graphene sheets, and is conducive to the subsequent dispersion in anti-corrosion coatings. Combined with the joint dispersion process (e.g., ultrasonic-high-speed shearing), the modifier can be placed in the coating for more than 12 months without obvious agglomeration, which is far superior to the 6-month dispersion stability period in related technologies, and is different from the conventional method of compounding a single aid in related technologies.

[0025] (3) Directional synergistic modification of bissilane to further improve the high-speed erosion resistance and interfacial covalent compatibility of the coating: Bifunctional boron nitride nanodots are covalently bonded to graphene to form a covalently bonded coating precursor. A silane coupling agent is introduced to cause the groups of the silane coupling agent (e.g., epoxy / amino) to undergo a directional covalent reaction with the groups of the bifunctional boron nitride nanodots (e.g., amino / epoxy). Bisiloxane groups are introduced on the surface of the coating layer of the precursor to further enhance the dual covalent bonding force between the modifier and the coating matrix. The compounded silane coupling agent (KH560+KH550) forms a complementary directional covalent reaction with the bifunctional groups of the bifunctional boron nitride nanodots, introducing bisiloxane groups on the surface of the coating layer. It can react with the epoxy groups and hydroxyl groups of epoxy resin / polyurethane and other coatings at the same time, improving the coating adhesion to level 0. It can withstand high-speed seawater erosion (5m / s flow rate, 1000h) without damage, solving the problem of weak bonding between existing modifiers and coating matrix and easy peeling.

[0026] (4) In-situ introduction of anti-aging additives to give the modifier strong UV resistance and antioxidant properties: Anti-aging additives (e.g., UV-531, 1010) are uniformly adsorbed in-situ on the surface of the coating layer, forming a synergistic anti-aging system with graphene nanosheets and boron nitride nanodots. The UV resistance of the modified coating (QUV test, 1000h) has a chalking grade of 0 and a gloss loss grade of 1, which solves the problem of easy chalking and cracking of existing marine anti-corrosion coatings after long-term use.

[0027] (5) Optimization of multi-redirection modification process to achieve high performance of modifier and industrial compatibility: The combination process of plasma etching, amidation covalent bonding and bissilane modification is adopted, and the dispersion process is optimized (e.g., ultrasonic-shear-homogenization). No complicated equipment is required, the raw materials are readily available, and the preparation process is green and environmentally friendly. The amount of modifier added is only 0.5-3% of the total mass of the coating, which does not affect the coating's construction performance (leveling, drying speed), and reduces the corrosion rate of the coating by more than 500 times, improves the corrosion resistance by 3 orders of magnitude, and achieves insulation and corrosion resistance, which is suitable for large-scale industrial production.

[0028] (6) Application scenarios are precisely adapted to harsh marine coupling environments: The modifier is not only suitable for water-based epoxy resin and polyurethane marine anti-corrosion coatings, but can also be extended to marine heavy-duty anti-corrosion coatings, wind turbine blade anti-corrosion coatings, ship antifouling and anti-corrosion integrated coatings, etc. At the same time, it can be adapted to harsh marine environments with high-speed scouring, strong ultraviolet radiation, and high salt spray coupling, making the application scenarios more targeted. Detailed Implementation

[0029] The embodiments of the present invention are described in detail below. These embodiments are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0030] An embodiment of the present invention provides a boron nitride-coated graphene dispersant modifier, which is prepared from the following raw materials: graphene nanosheets, bifunctionalized boron nitride nanodots, surfactants, silane coupling agents, solvents, dispersants, and anti-aging agents.

[0031] The boron nitride-coated graphene dispersant modifier of this invention comprises bifunctional boron nitride nanodots covalently bonded to graphene nanosheets, a synergistic dispersion system of surfactants and dispersants, directional interface modification with silane coupling agents, and in-situ loading of anti-aging additives. It integrates the triple properties of high-speed seawater erosion resistance, strong UV aging resistance, and insulation and anti-conductive corrosion resistance into the boron nitride-coated graphene dispersant modifier. When used in coatings, it can form a three-dimensional covalently bonded network of "graphene-boron nitride-coating matrix," enhancing the bonding force between the modifier and the coating, while significantly improving the dispersion stability of the coating.

[0032] In some embodiments, the boron nitride-coated graphene dispersant modifier is a boron nitride-coated graphene dispersant modifier used in marine anti-corrosion coatings.

[0033] In some embodiments, the boron nitride-coated graphene dispersion modifier is prepared from the following raw materials in parts by weight: Graphene nanosheets: 10-20 parts, specifically, for example, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts; Bifunctional boron nitride nanodots: 30-50 parts, specifically, for example, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts; Surfactant: 5-10 parts, specifically, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts; Silane coupling agent: 3-8 parts, specifically, for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts; Solvent: 80-120 parts, specifically, for example, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts; Dispersing agent: 2-5 parts, specifically, for example, 2 parts, 3 parts, 4 parts, 5 parts; Anti-aging adjuvant: 1-3 parts, specifically, for example, 1 part, 2 parts, 3 parts.

[0034] In this embodiment of the invention, by optimizing the proportions of each raw material in the modifier, it is beneficial to further improve the modifier's dispersion stability, binding performance, high-speed seawater erosion resistance, strong ultraviolet aging resistance, insulation and anti-conductive corrosion resistance.

[0035] In some embodiments, the thickness of the graphene nanosheets is 1-5 nm, specifically, for example, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm; the diameter of the graphene nanosheets is 0.5-5 μm, specifically, for example, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm; the purity is ≥98%; carboxyl groups are introduced onto the surface of the graphene nanosheets by oxygen plasma etching; optionally, the carboxyl group content of the etched graphene nanosheets is 0.6-1.2 mmol / g, specifically, for example, 0.6 mmol / g, 0.8 mmol / g, 1.0 mmol / g, 1.2 mmol / g. In these embodiments, the carboxyl groups of the graphene nanosheets can undergo amidation covalent bonding with the amino groups of the bifunctionalized boron nitride nanodots.

[0036] In some embodiments, the bifunctionalized boron nitride nanodots contain amino and epoxy bifunctional groups; Optionally, the bifunctional boron nitride nanodots are obtained by modifying boron nitride nanodots with amino and epoxy groups. Specifically, the bifunctional boron nitride nanodots are obtained by modifying boron nitride nanodots with KH560 and KH550. The boron nitride nanodots are monolayer boron nitride. The size (diameter) of the bifunctional boron nitride nanodots is less than 50 nm. The surface amino content of the bifunctional boron nitride nanodots is 0.8-1.5 mmol / g, specifically, for example, 0.8 mmol / g, 1.0 mmol / g, 1.2 mm. The surface epoxy content of the bifunctional boron nitride nanodots is 0.5-1.0 mmol / g, specifically, for example, 0.5 mmol / g, 0.6 mmol / g, 0.8 mmol / g, and 1.0 mmol / g; the total hydrophilic group content of the bifunctional boron nitride nanodots is 1.8-3.0 mmol / g, specifically, for example, 1.8 mmol / g, 2.0 mmol / g, 2.5 mmol / g, and 3.0 mmol / g; purity ≥ 99.5%.

[0037] In this embodiment of the invention, the bifunctional boron nitride nanodots can undergo amidation covalent reaction with the carboxyl groups of graphene nanosheets and undergo a two-site epoxy-amino covalent reaction with the compounded silane coupling agent.

[0038] In some embodiments, the mass ratio of graphene nanosheets to difunctionalized boron nitride nanodots is 1:2-4, specifically, for example, 1:2, 1:3, or 1:4. In these embodiments, the mass ratio of graphene nanosheets to difunctionalized boron nitride nanodots is 1:2-4, which helps to further ensure sufficient covalent coating of the difunctionalized boron nitride nanodots and further improves the overall performance of the modifier.

[0039] In some embodiments, the bifunctional boron nitride nanodots coat graphene nanosheets; optionally, the graphene nanosheets and the bifunctional boron nitride nanodots are covalently bonded to achieve bifunctional boron nitride nanodot coating of graphene nanosheets. In a specific embodiment, the carboxyl groups of the graphene nanosheets are covalently bonded to the amino groups of the bifunctional boron nitride nanodots, and the covalent bonding is an amidation covalent bond.

[0040] In some embodiments, the surfactant is a compound surfactant; optionally, the compound surfactant includes polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG); optionally, the polyvinylpyrrolidone includes polyvinylpyrrolidone K30; the polyethylene glycol includes polyethylene glycol 400; optionally, the mass ratio of polyvinylpyrrolidone to polyethylene glycol is 2-3:1, specifically, for example, 2:1, 2.5:1, 3:1. In the embodiments of the present invention, the compound surfactants polyvinylpyrrolidone and polyethylene glycol are used to balance steric hindrance and hydrophilicity / lipophilicity, synergistically and effectively inhibiting graphene aggregation, and further improving the performance of the modifier.

[0041] In some embodiments, the silane coupling agent is a compound silane coupling agent; preferably, the compound silane coupling agent includes KH560 (γ-glycidoxypropyltrimethoxysilane) and KH550 (3-aminopropyltriethoxysilane); optionally, the mass ratio of KH560 to KH550 is 3-4:1, specifically, for example, 3:1, 3.5:1, 4:1. In the embodiments of the present invention, the compound silane coupling agent (KH560 and KH550) forms a two-site covalent bond with the bifunctional boron nitride nanodots, introducing bisiloxane groups suitable for waterborne epoxy / polyurethane coatings.

[0042] In some embodiments, the mass ratio of the silane coupling agent to the difunctionalized boron nitride nanodots is 1:5-12, specifically, for example, 1:5, 1:7, 1:9, 1:10, or 1:12; optionally, the silane coupling agent is a compound silane coupling agent. In these embodiments, the weight ratio of the compound silane coupling agent to the difunctionalized boron nitride nanodots is 1:5-12, ensuring effective dual-site modification of the difunctionalized boron nitride nanodots and the silane coupling agent, which is beneficial for further improving the overall performance of the modifier.

[0043] In some embodiments, the dispersing aid is a compound dispersing aid; the compound dispersing aid includes sodium citrate and sodium pyrophosphate; optionally, the mass ratio of sodium citrate to sodium pyrophosphate is 1-2:1, specifically, for example, 1:1, 1.5:1, 2:1. In the embodiments of the present invention, the compound dispersing aid (sodium citrate and sodium pyrophosphate) is beneficial to synergistically reducing the van der Waals forces and electrostatic forces between graphene sheets, further improving the dispersibility of the modifier, and is also beneficial to its subsequent dispersion in anti-corrosion coatings.

[0044] In some embodiments, the anti-aging additive includes at least one of ultraviolet absorber UV-531 and hindered phenolic antioxidant 1010; optionally, the anti-aging additive includes ultraviolet absorber UV-531 and hindered phenolic antioxidant 1010, with a mass ratio of UV absorber UV-531 to hindered phenolic antioxidant 1010 of 1:1. In this embodiment of the invention, the anti-aging additive is in situ loaded onto the surface of the coating layer, synergistically forming an anti-aging system with graphene and boron nitride to achieve strong ultraviolet aging resistance.

[0045] In some embodiments, the solvent includes at least one of ethanol, water, and propylene glycol methyl ether; optionally, the ethanol includes anhydrous ethanol, and the water includes deionized water; the solvent includes ethanol, water, and propylene glycol methyl ether, and the volume ratio of ethanol, water, and propylene glycol methyl ether is 5-6 (e.g., 5, 5.5, 6):1:0.5. In embodiments of the present invention, the solvent-adapted covalent reaction system and dispersion process of the modifier are also included.

[0046] A method for preparing a boron nitride-coated graphene dispersion modifier according to an embodiment of the present invention includes the following steps: (1) Carboxyl groups are introduced into graphene nanosheets by oxygen plasma etching to obtain etched graphene nanosheets; the etched graphene nanosheets are mixed with solvent and dispersant to obtain graphene dispersion. (2) Reaction of boron nitride nanodots with aminosilane and epoxysilane yields bifunctionalized boron nitride nanodots; (3) The bifunctional boron nitride nanodots, surfactant and graphene dispersion are mixed and a coupling agent is added to carry out an amidation reaction to form a covalently bonded coating precursor mixture of bifunctional boron nitride nanodots coating graphene nanosheets (covalently bonded coating structure). (4) Add a silane coupling agent to carry out the reaction; (5) Add anti-aging additives and mix to obtain boron nitride coated graphene dispersion modifier.

[0047] In this embodiment of the invention, a combined process of plasma etching, amidation covalent bonding, and bissilane modification is employed. This process requires no complex equipment, uses readily available raw materials, and is environmentally friendly, making it suitable for large-scale industrial production. Specifically, graphene nanosheets are etched with oxygen plasma to introduce surface carboxyl groups for subsequent amidation reactions; a dispersing agent is added to obtain a graphene dispersion; boron nitride nanodots are reacted to introduce amino and epoxy bifunctional groups; the amino groups of the bifunctional boron nitride nanodots undergo amidation reactions with the carboxyl groups on the graphene surface to form a covalently bonded coating precursor mixture; a silane coupling agent reacts with the bifunctional boron nitride nanodots to introduce bissiloxane groups on the coating layer surface, enhancing the dual covalent bonding force with the coating matrix; an anti-aging agent is added to the reaction solution to uniformly adsorb onto the coating layer surface in situ, resulting in a boron nitride-coated graphene dispersing modifier.

[0048] In some embodiments, in step (1), the oxygen plasma etching is performed using a plasma etching apparatus; the etching gas for the oxygen plasma etching is oxygen; the power of the oxygen plasma etching is 200-300W, specifically, for example, 200W, 220W, 250W, 280W, 300W; the time for the oxygen plasma etching is 15-20min, specifically, for example, 15min, 16min, 17min, 18min, 19min, 20min. In this embodiment of the invention, surface carboxyl groups are introduced onto the surface of graphene nanosheets through oxygen plasma etching for subsequent amidation reactions.

[0049] In some embodiments, in step (1), the etched graphene nanosheets are added to a solvent, and then a dispersing agent is added for mixing.

[0050] In some embodiments, in step (1), dispersion is performed during the mixing process; optionally, the dispersion includes ultrasonic-high-speed shear combined dispersion; the dispersion time is 1.5-2.5h, specifically, for example, 1.5h, 2h, 2.5h; the dispersion temperature is 25-35℃, specifically, for example, 25℃, 30℃, 35℃; the ultrasonic power is 300-500W, specifically, for example, 300W, 400W, 500W; the ultrasonic is intermittent, stopping for 5min every 30min; the high-speed shear is 8000-10000r / min.

[0051] In some embodiments, in step (2), the mass ratio of boron nitride nanodots to aminosilane and epoxysilane is 5~12:0.1~1:0.1~1, specifically, 5~12 (e.g., 5, 7, 8, 10, 12):0.1~1 (e.g., 0.1, 0.2, 0.5, 0.8, 1):0.1~1 (e.g., 0.1, 0.2, 0.5, 0.8, 1); the reaction temperature is 60-70℃, specifically, for example, 60℃, 65℃, 70℃; the reaction time is 4-6h, specifically, for example, 4h, 5h, 6h; the reaction is carried out under stirring; the reaction is carried out in a solvent, the solvent including anhydrous ethanol; the aminosilane includes KH550; the epoxysilane includes KH560; after the reaction, the mixture is filtered (e.g., vacuum filtered), washed, and dried to obtain bifunctionalized boron nitride nanodots.

[0052] In some embodiments, in step (3), the bifunctional boron nitride nanodots, surfactant, and graphene dispersion are mixed, the stirring speed is adjusted to 600-800 r / min, and a coupling agent is added; the coupling agent includes 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC) and N-hydroxysuccinimide (NHS); optionally, the EDC is 5-8% of the mass of the etched graphene nanosheets, specifically, for example, 5%, 6%, 7%, 8%; optionally, the NHS is 3-5% of the mass of the etched graphene nanosheets, specifically, for example, 3%, 4%, 5%; the amidation reaction temperature is 15-30℃, for example, 15℃, 20℃, 25℃ (room temperature), 30℃; the amidation reaction time is 6-8h, specifically, for example, 6h, 7h, 8h.

[0053] In this embodiment of the invention, the amino groups of bifunctional boron nitride nanodots undergo an amidation reaction with the carboxyl groups on the surface of graphene nanosheets to form a covalently bonded coating precursor mixture. A coupling agent is used to promote the amidation reaction.

[0054] In some embodiments, in step (4), after adding the silane coupling agent, the temperature is raised to carry out the reaction; the reaction temperature is 40-60℃, specifically 40℃, 50℃, and 60℃; the reaction time is 3-5h, specifically, for example, 3h, 4h, and 5h; the reaction is carried out under stirring, optionally at a stirring speed of 400-600r / min; optionally, solvent is added every 30min (the amount added is 2-3% of the original solvent mass) to prevent solvent evaporation from causing unevenness in the system. In this embodiment of the invention, the epoxy / amino groups of the silane coupling agent undergo a covalent reaction with the amino / epoxy groups of the bifunctional boron nitride nanodots, introducing bisiloxane groups on the surface of the coating layer, thereby enhancing the dual covalent bonding force with the coating matrix.

[0055] In some embodiments, in step (5), an anti-aging additive is added and mixed; optionally, stirring is performed during the mixing process, and the mixing time is 30-60 minutes, specifically, for example, 30 minutes, 40 minutes, 50 minutes, and 60 minutes, so that the anti-aging additive is uniformly adsorbed in situ on the surface of the coating layer.

[0056] In some embodiments, in step (5), an anti-aging additive is added and mixed; after filtration, washing, and drying, it is then pulverized and sieved to obtain a boron nitride-coated graphene dispersion modifier; optionally, the filtration is performed using vacuum filtration (e.g., vacuum degree 0.06-0.08 MPa); the washing includes washing the filter residue with anhydrous ethanol 2-3 times; the drying includes vacuum drying, optionally, drying at 40-65℃ for 8-12 hours in a vacuum drying oven with a vacuum degree of 0.05-0.07 MPa; the pulverization includes planetary ball milling + air jet milling combined grinding, wherein the ball milling time is 30-60 min, the ball-to-material ratio of the planetary ball mill is 12:1-15:1, and the air jet milling pressure is 0.6-0.8 MPa; the sieving includes passing through a 300-400 mesh sieve.

[0057] In some embodiments, there is no particular limitation on the particle size of the boron nitride-coated graphene dispersant modifier. In specific embodiments, the particle size of the boron nitride-coated graphene dispersant modifier can be 300-400 mesh, specifically, for example, 300 mesh, 350 mesh, or 400 mesh.

[0058] A marine anti-corrosion coating according to an embodiment of the present invention includes: the boron nitride-coated graphene dispersant modifier described in the embodiment of the present invention or the boron nitride-coated graphene dispersant modifier prepared by the preparation method described in the embodiment of the present invention.

[0059] In this embodiment of the invention, the marine anti-corrosion coating is adaptable to the harsh marine environment characterized by high-speed scouring, strong ultraviolet radiation, and high salt spray coupling, making its application scenarios more targeted.

[0060] In some embodiments, the boron nitride-coated graphene dispersant modifier is 0.5-3% of the total mass of the coating, specifically, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%.

[0061] In some embodiments, the marine anti-corrosion coating includes a water-based epoxy resin coating or a polyurethane coating; Optionally, the boron nitride-coated graphene dispersant modifier is added to an aqueous epoxy resin coating or a polyurethane coating for dispersion; the dispersion includes: first, high-speed stirring (e.g., high-speed stirring speed 1000-1500 r / min, high-speed stirring time 1-2 h), and then ultrasonic-high pressure homogenization combined dispersion (e.g., time 30-60 min) to obtain a marine anti-corrosion coating; the ultrasonic power is 300-500 W, the ultrasonic is intermittent, and the high pressure homogenization pressure is 40-60 MPa.

[0062] The present invention relates to the application of a boron nitride-coated graphene dispersion modifier or marine anti-corrosion coating in a marine environment, optionally for use in marine engineering steel structures, ships or offshore platforms; And / or, for use in marine heavy-duty anti-corrosion coatings, wind turbine blade anti-corrosion coatings, or integrated antifouling and anti-corrosion coatings for ships.

[0063] The present invention will now be described with reference to specific embodiments. It should be noted that these embodiments are merely descriptive and do not limit the present invention in any way.

[0064] Example 1 A boron nitride-coated graphene dispersant modifier for marine anti-corrosion coatings is prepared from the following raw materials in parts by weight: 10 parts graphene nanosheets, 30 parts bifunctional boron nitride nanodots, 5 parts compound surfactant (PVP K30:PEG400 mass ratio = 2:1), 3 parts compound silane coupling agent (KH560:KH550 mass ratio = 3:1), 80 parts mixed solvent (anhydrous ethanol:deionized water:propylene glycol methyl ether volume ratio = 5:1:0.5), 2 parts compound dispersing aid (sodium citrate:sodium pyrophosphate mass ratio = 1:1), and 1 part anti-aging aid (UV-531:1010 mass ratio = 1:1). Among them, the graphene nanosheets have a thickness of 1-3 nm, a sheet diameter of 0.5-2 μm, a purity of 98%, and a surface carboxyl group content of 0.6 mmol / g after etching; the bifunctional boron nitride nanodots have a diameter of less than 50 nm, an amino content of 0.8 mmol / g, an epoxy group content of 0.5 mmol / g, a total hydrophilic group content of 1.8 mmol / g, and a purity of 99.5%.

[0065] A method for preparing a boron nitride-coated graphene dispersion modifier includes the following steps: (1) Pretreatment of graphene carboxylation: oxygen plasma etching (power 200W, 15min); add mixed solvent and compound dispersant, ultrasonic (300W)-shear (8000r / min) combined dispersion for 2.5h, temperature 25℃, to obtain graphene dispersion; (2) Preparation of bifunctional boron nitride nanodots: boron nitride nanodots were mixed with anhydrous ethanol, and 3-aminopropyltriethoxysilane (KH550) and γ-glycidoxypropyltrimethoxysilane (KH560) were added. The mixture was stirred at 60°C for 4 h, filtered, washed and dried to obtain bifunctional boron nitride nanodots. (3) Covalent bonding coating: Bifunctional boron nitride nanodots, compound surfactant and graphene dispersion are mixed and stirred at 600 r / min. EDC (5% of the mass of etched graphene nanosheets) and NHS (3% of the mass of etched graphene nanosheets) are added and stirred at room temperature for 6 h to obtain coating precursor mixture. (4) Bissilane modification: Add compound silane coupling agent, keep warm at 40℃ and stir for 5h, stirring speed 400r / min, add 2% mixed solvent every 30min; (5) Anti-aging and post-treatment: Add anti-aging additives, stir for 30 min, vacuum filter (0.06 MPa), wash twice with anhydrous ethanol, vacuum dry at 40℃ for 12 h, ball mill (30 min, ball-to-material ratio of 12:1) + air jet mill (0.6 MPa), pass through a 300 mesh sieve to obtain boron nitride coated graphene dispersion modifier.

[0066] Application of the modifier: A marine anti-corrosion coating: Boron nitride-coated graphene dispersant modifier was added to the waterborne epoxy resin coating at 0.5% of the total coating mass, stirred at 1000 r / min for 2 h, and then ultrasonically (300 W) and high-pressure homogenization (40 MPa) for 60 min to obtain the coating.

[0067] Test results: Dispersion stability showed no agglomeration after 12 months; corrosion rate was 0.0004 mm / a, 625 times lower than the blank coating (without modifier); coating adhesion was grade 0, and it withstood seawater erosion (5 m / s, 1000 h) without damage; after 1000 h of QUV aging, chalking was grade 0 and gloss loss was grade 1.

[0068] Example 2 A boron nitride-coated graphene dispersant modifier for marine anti-corrosion coatings is prepared from the following raw materials in parts by weight: 15 parts graphene nanosheets, 40 parts bifunctional boron nitride nanodots, 8 parts compound surfactant (PVP K30:PEG400 mass ratio = 2.5:1), 5 parts compound silane coupling agent (KH560:KH550 mass ratio = 3.5:1), 100 parts mixed solvent (anhydrous ethanol:deionized water:propylene glycol methyl ether volume ratio = 5.5:1:0.5), 3 parts compound dispersing aid (sodium citrate:sodium pyrophosphate mass ratio = 1.5:1), and 2 parts anti-aging aid (UV-531:1010 mass ratio = 1:1). The graphene nanosheets have a thickness of 2-4 nm, a diameter of 1-3 μm, a purity of 99%, and a surface carboxyl group content of 0.9 mmol / g after etching. The bifunctional boron nitride nanodots have a diameter of less than 50 nm, an amino content of 1.2 mmol / g, an epoxy group content of 0.8 mmol / g, a total hydrophilic group content of 2.5 mmol / g, and a purity of 99.5%.

[0069] A method for preparing a boron nitride-coated graphene dispersion modifier includes the following steps: (1) Pretreatment of graphene carboxylation: oxygen plasma etching (power 250W, 18min); add mixed solvent and compound dispersant, ultrasonic (400W)-shear (9000r / min) combined dispersion for 2h, temperature 30℃, to obtain graphene dispersion; (2) Preparation of bifunctional boron nitride nanodots: boron nitride nanodots were mixed with anhydrous ethanol, and 3-aminopropyltriethoxysilane (KH550) and γ-glycidoxypropyltrimethoxysilane (KH560) were added. The mixture was stirred at 65°C for 5 h, filtered, washed and dried to obtain bifunctional boron nitride nanodots. (3) Covalent bonding coating: Bifunctional boron nitride nanodots, compound surfactant and graphene dispersion are mixed and stirred at 700 r / min. EDC (6% of the mass of etched graphene nanosheets) and NHS (4% of the mass of etched graphene nanosheets) are added and stirred at room temperature for 7 h to obtain coating precursor mixture. (4) Bissilane modification: Add compound silane coupling agent, keep warm at 50℃ and stir for 4h, stirring speed 500r / min, add 2.5% mixed solvent every 30min; (5) Anti-aging and post-treatment: Add anti-aging additives, stir for 45 min, vacuum filter (0.07 MPa), wash 3 times with anhydrous ethanol, dry at 50℃ for 10 h, ball mill (45 min, ball-to-material ratio of 13:1) + air jet mill (0.7 MPa), pass through a 350 mesh sieve to obtain boron nitride coated graphene dispersion modifier.

[0070] Application of the modifier: A marine anti-corrosion coating: Boron nitride-coated graphene dispersant modifier was added to the polyurethane coating at 2% of the total coating mass, stirred at 1200 r / min for 1.5 h, and then ultrasonically (400 W) and high-pressure homogenization (50 MPa) for 45 min to obtain the coating.

[0071] Test results: Dispersion stability showed no agglomeration after 14 months; corrosion rate was 0.0003 mm / a, 733 times lower than the blank coating (without modifier); coating adhesion was grade 0, with no damage after 1000 hours of seawater erosion; after 1000 hours of QUV aging, chalking was grade 0 and gloss loss was grade 1.

[0072] Example 3 A boron nitride-coated graphene dispersant modifier for marine anti-corrosion coatings is prepared from the following raw materials in parts by weight: 20 parts graphene nanosheets, 50 parts bifunctional boron nitride nanodots, 10 parts compound surfactant (PVP K30:PEG400 mass ratio = 3:1), 8 parts compound silane coupling agent (KH560:KH550 mass ratio = 4:1), 120 parts mixed solvent (anhydrous ethanol:deionized water:propylene glycol methyl ether volume ratio = 6:1:0.5), 5 parts compound dispersing aid (sodium citrate:sodium pyrophosphate mass ratio = 2:1), and 3 parts anti-aging aid (UV-531:1010 mass ratio = 1:1). Among them, the graphene nanosheets are 3-5 nm thick, 3-5 μm in diameter, and 99% pure, with a surface carboxyl group content of 1.2 mmol / g after etching; the bifunctional boron nitride nanodots are less than 50 nm in diameter, with an amino content of 1.5 mmol / g, an epoxy group content of 1.0 mmol / g, a total hydrophilic group content of 3.0 mmol / g, and a purity of 99.8%.

[0073] A method for preparing a boron nitride-coated graphene dispersion modifier includes the following steps: (1) Pretreatment of graphene carboxylation: oxygen plasma etching (power 300W, 20min), mixed solvent and compound dispersant added, ultrasonic (500W)-shear (10000r / min) combined dispersion for 1.5h, temperature 35℃, to obtain graphene dispersion; (2) Preparation of bifunctional boron nitride nanodots: boron nitride nanodots were mixed with anhydrous ethanol, and 3-aminopropyltriethoxysilane (KH550) and γ-glycidoxypropyltrimethoxysilane (KH560) were added. The mixture was stirred at 70°C for 6 h, filtered, washed and dried to obtain bifunctional boron nitride nanodots. (3) Covalent bonding coating: Bifunctional boron nitride nanodots, compound surfactant and graphene dispersion are mixed and stirred at 800 r / min. EDC (8% of the mass of etched graphene nanosheets) and NHS (5% of the mass of etched graphene nanosheets) are added and stirred at room temperature for 8 h to obtain coating precursor mixture. (4) Bissilane modification: Add compound silane coupling agent, keep warm at 60℃ and stir for 3h, stirring speed 600r / min, add 3% mixed solvent every 30min; (5) Anti-aging and post-treatment: Add anti-aging additives, stir for 60 min, vacuum filter (0.08 MPa), wash 3 times with anhydrous ethanol, dry at 65℃ for 8 h, ball mill (60 min, ball-to-material ratio of 15:1) + air jet mill (0.8 MPa), pass through a 400 mesh sieve to obtain boron nitride coated graphene dispersion modifier.

[0074] Application of the modifier: A marine anti-corrosion coating: Boron nitride-coated graphene dispersant modifier was added to the water-based epoxy resin coating at 3% of the total coating mass, stirred at 1500 r / min for 1 h, and then ultrasonically (500 W) and high-pressure homogenized (60 MPa) for 30 min to obtain the coating.

[0075] Test results: Dispersion stability: no agglomeration after 16 months; corrosion rate: 0.0002 mm / a, 1250 times lower than blank coating (without modifier); coating adhesion: grade 0; seawater erosion resistance: no damage after 1000 hours; QUV aging: grade 0, chalking: grade 0, gloss loss: grade 0 after 1000 hours.

[0076] Comparative Example 1 (boron nitride nanodots without bifunctional modification, physical coating) The raw materials and preparation method are the same as in Example 2, except that the original boron nitride nanodots are used instead of the bifunctionalized boron nitride nanodots.

[0077] Test results: Agglomeration appeared after 3 months of dispersion stability; corrosion rate was 0.02 mm / a, only 11 times lower; coating adhesion was grade 2, and local peeling occurred after 500 hours of seawater erosion; powdering grade 1 appeared after 500 hours of QUV aging.

[0078] Comparative Example 2 (no compound system, single adjuvant) The raw materials and preparation method are the same as in Example 2, except that 8 parts of a single PVP K30 surfactant, 3 parts of a single sodium citrate dispersant, and 5 parts of a single KH560 silane coupling agent are used.

[0079] Test results: Agglomeration appeared after 6 months of dispersion stability; corrosion rate was 0.0015 mm / a, a decrease of 147 times; coating adhesion was grade 1, and slight scratches appeared after 800 hours of seawater erosion; powdering was grade 1 after 800 hours of QUV aging.

[0080] As can be seen from the above embodiments and comparative examples, the present invention achieves a comprehensive improvement in the modifier's dispersion stability, coating strength, corrosion resistance, erosion resistance, and aging resistance through a synergistic dispersion system of covalently bonded bifunctional boron nitride nanodots to graphene nanosheets, a compound surfactant and compound dispersant, interfacial modification by a bissilane coupling agent, and in-situ introduction of an anti-aging agent. The overall performance is significantly improved, solving the key technical problems of applying existing boron nitride-coated graphene modifiers in harsh marine environments.

[0081] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0082] Although the above embodiments have been shown and described, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Any changes, modifications, substitutions and variations made to the above embodiments by those skilled in the art are within the protection scope of the present invention.

Claims

1. A boron nitride-coated graphene dispersant modifier, characterized in that, It is prepared from the following raw materials: graphene nanosheets, bifunctional boron nitride nanodots, surfactants, silane coupling agents, solvents, dispersants, and anti-aging agents.

2. The boron nitride-coated graphene dispersant modifier according to claim 1, characterized in that, It is prepared from the following raw materials in parts by weight: graphene nanosheets: 10-20 parts; bifunctional boron nitride nanodots: 30-50 parts; surfactant: 5-10 parts; Silane coupling agent: 3-8 parts; Solvent: 80-120 parts; Dispersant: 2-5 parts; Anti-aging agent: 1-3 parts.

3. The boron nitride-coated graphene dispersant modifier according to claim 1, characterized in that, The graphene nanosheets have a diameter of 0.5-5 μm; And / or, the surface of the graphene nanosheets is etched with oxygen plasma to introduce carboxyl groups, preferably, the carboxyl content of the etched graphene nanosheets is 0.6-1.2 mmol / g.

4. The boron nitride-coated graphene dispersant modifier according to claim 1, characterized in that, The bifunctionalized boron nitride nanodots contain amino and epoxy bifunctional groups; And / or, the bifunctional boron nitride nanodots are obtained by modifying boron nitride nanodots with amino and epoxy groups through bifunctionalization; And / or, the size of the bifunctional boron nitride nanodots is less than 50 nm; And / or, the surface amino content of the bifunctional boron nitride nanodots is 0.8-1.5 mmol / g; And / or, the surface epoxy content of the bifunctional boron nitride nanodots is 0.5-1.0 mmol / g; And / or, the mass ratio of the graphene nanosheets to the bifunctional boron nitride nanodots is 1:2-4.

5. The boron nitride-coated graphene dispersant modifier according to claim 1, characterized in that, The surfactant is a compound surfactant; preferably, the compound surfactant includes polyvinylpyrrolidone and polyethylene glycol; And / or, the silane coupling agent is a compound silane coupling agent; preferably, the compound silane coupling agent includes KH560 and KH550; And / or, the mass ratio of the silane coupling agent to the difunctionalized boron nitride nanodots is 1:5-12; And / or, the dispersing agent is a compound dispersing agent; the compound dispersing agent includes sodium citrate and sodium pyrophosphate; And / or, the anti-aging adjuvant includes at least one of ultraviolet absorber UV-531 and hindered phenolic antioxidant 1010; And / or, the solvent includes at least one of ethanol, water, and propylene glycol methyl ether.

6. A method for preparing a boron nitride-coated graphene dispersion modifier according to any one of claims 1-5, characterized in that, Includes the following steps: (1) Carboxyl groups are introduced into graphene nanosheets by oxygen plasma etching to obtain etched graphene nanosheets; the etched graphene nanosheets are mixed with solvent and dispersant to obtain graphene dispersion. (2) Reaction of boron nitride nanodots with aminosilane and epoxysilane yields bifunctionalized boron nitride nanodots; (3) The bifunctional boron nitride nanodots, surfactant and graphene dispersion are mixed and a coupling agent is added to carry out an amidation reaction to form a covalently bonded coating precursor mixture of bifunctional boron nitride nanodots coating graphene nanosheets. (4) Add a silane coupling agent to carry out the reaction; (5) Add anti-aging additives and mix to obtain boron nitride coated graphene dispersion modifier.

7. The method for preparing the boron nitride-coated graphene dispersant modifier according to claim 6, characterized in that, In step (1), the power of the oxygen plasma etching is 200-300 W; And / or, the oxygen plasma etching time is 15-20 min; And / or, in step (2), the reaction temperature is 60-70 °C; And / or, the reaction time is 4-6 h; And / or, the aminosilane includes KH550; And / or, the epoxysilane includes KH560.

8. The method for preparing the boron nitride-coated graphene dispersant modifier according to claim 6, characterized in that, In step (3), the coupling agent includes EDC and NHS; preferably, the EDC is 5-8% of the mass of the etched graphene nanosheets; preferably, the NHS is 3-5% of the mass of the etched graphene nanosheets. And / or, the temperature of the amidation reaction is 15-30°C; And / or, the amidation reaction takes 6-8 h; And / or, in step (4), the reaction temperature is 40-60 °C; And / or, the reaction time is 3-5 h.

9. A marine anti-corrosion coating, characterized in that, include: The boron nitride-coated graphene dispersion modifier according to any one of claims 1-5 or the boron nitride-coated graphene dispersion modifier prepared by any one of claims 6-8, preferably, the boron nitride-coated graphene dispersion modifier is 0.5-3% of the total mass of the coating.

10. The application of a boron nitride-coated graphene dispersion modifier according to any one of claims 1-5 or the marine anti-corrosion coating according to claim 9, characterized in that, For use in marine environments; And / or, for use in marine heavy-duty anti-corrosion coatings, wind turbine blade anti-corrosion coatings, or integrated antifouling and anti-corrosion coatings for ships.