CN111100529A - Ship coating capable of effectively preventing marine organisms from attaching and preparation method thereof - Google Patents
Ship coating capable of effectively preventing marine organisms from attaching and preparation method thereof Download PDFInfo
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- CN111100529A CN111100529A CN201911374112.2A CN201911374112A CN111100529A CN 111100529 A CN111100529 A CN 111100529A CN 201911374112 A CN201911374112 A CN 201911374112A CN 111100529 A CN111100529 A CN 111100529A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a marine coating capable of effectively preventing marine organisms from attaching and a preparation method thereof, which relate to the field of marine coatings and comprise a component A and a component B, wherein the component A comprises the following components in parts by weight: 30-50 parts of dimer acid modified epoxy resin, 10-20 parts of fluorosilicone resin, 5-12 parts of hydroxyl carbon nano tube, 4-8 parts of polydimethylsiloxane, 15-20 parts of tourmaline, 5-10 parts of functionalized graphene, 2-5 parts of bentonite, 1-2 parts of tributyl phosphate, 1-1.5 parts of capsaicin, 0.5-3 parts of composite sterilization component, 3-7 parts of liquid polysulfide rubber, 5-10 parts of hyperbranched polyether, 0.1-0.5 part of methyldiethanolamine, 0.1-0.5 part of dioctyl phthalate, 1-3 parts of hydrogen-terminated silicone oil, 5-10 parts of butyl acetate and 20-40 parts of xylene; the component B is a polyamide curing agent, the coating of the marine coating has excellent performance and high mechanical strength of the coating, can effectively protect a ship body from seawater corrosion, and can effectively prevent marine organisms from attaching through seawater hanging plate experimental verification.
Description
Technical Field
The invention relates to the field of marine coatings, in particular to a marine coating capable of effectively preventing marine organisms from attaching and a preparation method thereof.
Background
The marine coating is a general name of the coating which is used for various parts of ships and ocean engineering structures and meets the requirements of preventing seawater, ocean atmospheric corrosion, ocean organism adhesion and other special requirements. There are over eight thousand plants and over fifty thousand nine thousand marine animals in each territory of the world, of which there are over six hundred attached plants and over ten thousand attached animals. The larvae or the robes of the attached organisms can float or swim, and after the larvae or the robes develop to a certain stage, the larvae or the robes are attached to objects such as ship bottoms, underwater structures or shore rocks, settle and further propagate. When a large amount of marine organisms are attached to the bottom of the ship, the marine organisms can cause great harm to the ship, so that the marine organisms not only increase the dead weight of the ship and reduce the load of the ship, but also greatly increase the resistance of the ship body, and further reduce the navigational speed of the ship and increase the fuel consumption. Data show that when the ship bottom is seriously polluted, marine organism accumulated chips can reach more than ten centimeters in thickness, the weight of each square meter reaches more than twenty kilograms, and the weight of ships with the ship bottom of nearly ten thousand square meters can be increased by more than two hundred tons.
In marine environments, corrosion damage and biofouling of metal structures can be prevented by coating ships with marine paints, which is the simplest and feasible method. The required ship coating is constructed on the surface of a metal hull of a ship, concrete and other marine structures through simple processes of brushing, spraying, dipping and the like, and forms a tough protective and decorative coating through processes of natural drying, baking, solidification and the like. The marine coating can play a role by forming a sealing effect on the surface of metal or concrete and preventing a protected substrate from directly contacting with a marine corrosive environment, and after the marine coating is coated, the main effect mode of the marine coating embodies value through an interface effect, namely the marine coating has a special interface structure and interface components and can effectively inhibit biological adhesion.
Chinese patent CN107674469A discloses a water-resistant antibacterial marine coating and a preparation method thereof, wherein the marine coating comprises the following components in percentage by mass: 15-30% of ethyl methacrylate, 12-15% of butyl acrylate, 10-14% of triethylamine, 6-18% of polymer rubber powder, 11-14% of styrene-acrylic emulsion, 2.5-3.5% of zinc oxide, 6.5-8.5% of triallyl cyanurate, 20-25% of isooctyl dimethyldimercaptoacetate tin, 2-10% of glycol ether, 7-8% of diene epoxy resin, 1.5-2.5% of polyvinylpyrrolidone, 5.8-6.5% of nano silver particles, 3.5-5.8% of polyacrylamide and 12-24% of assistant. The water-resistant antibacterial marine coating improves the water resistance and antibacterial property of a coating formed after the coating by optimizing the components and the content of the components in the coating, so that the surface layer of a ship applying the coating is not easy to wear and damage, and the service life is longer.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a ship coating capable of effectively preventing marine organisms from attaching and a preparation method thereof.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
the marine coating capable of effectively preventing marine organisms from attaching comprises a component A and a component B, wherein the component A comprises the following components in parts by weight:
30-50 parts of dimer acid modified epoxy resin, 10-20 parts of fluorosilicone resin, 5-12 parts of hydroxyl carbon nano tube, 4-8 parts of polydimethylsiloxane, 15-20 parts of tourmaline, 5-10 parts of functionalized graphene, 2-5 parts of bentonite, 1-2 parts of tributyl phosphate, 1-1.5 parts of capsaicin, 0.5-3 parts of composite sterilization component, 3-7 parts of liquid polysulfide rubber, 5-10 parts of hyperbranched polyether, 0.1-0.5 part of methyldiethanolamine, 0.1-0.5 part of dioctyl phthalate, 1-3 parts of hydrogen-terminated silicone oil, 5-10 parts of butyl acetate and 20-40 parts of xylene;
the component B is a polyamide curing agent.
Further, the composition comprises a component A and a component B, wherein the component A comprises the following components in parts by weight:
38 parts of dimer acid modified epoxy resin, 15 parts of fluorosilicone resin, 10 parts of hydroxyl carbon nano tube, 5 parts of polydimethylsiloxane, 16 parts of tourmaline, 10 parts of functionalized graphene, 3 parts of bentonite, 1 part of tributyl phosphate, 1.2 parts of capsaicin, 2 parts of composite sterilization component, 6 parts of liquid polysulfide rubber, 10 parts of hyperbranched polyether, 0.2 part of methyldiethanolamine, 0.1 part of dioctyl phthalate, 3 parts of terminal hydrogen-containing silicone oil, 8 parts of butyl acetate and 3 parts of xylene;
the component B is a polyamide curing agent.
Further, the composition comprises a component A and a component B, wherein the component A comprises the following components in parts by weight:
40 parts of dimer acid modified epoxy resin, 12 parts of fluorosilicone resin, 12 parts of hydroxyl carbon nano tubes, 4 parts of polydimethylsiloxane, 15 parts of tourmaline, 10 parts of functionalized graphene, 2 parts of bentonite, 1 part of tributyl phosphate, 1 part of capsaicin, 1 part of composite sterilization component, 6 parts of liquid polysulfide rubber, 5 parts of hyperbranched polyether, 0.5 part of methyldiethanolamine, 0.1 part of dioctyl phthalate, 1 part of hydrogen-containing terminal silicone oil, 5 parts of butyl acetate and 40 parts of dimethylbenzene;
the component B is a polyamide curing agent.
Further, the preparation method of the dimer acid modified epoxy resin comprises the following steps:
adding bisphenol A epoxy resin, 1, 6-hexanediol diglycidyl ether and dimer acid into a reaction kettle, stirring at room temperature for 30-50min under the protection of nitrogen, heating to 50-60 ℃, slowly dropwise adding acetone solution of tetrabutylammonium bromide, heating to 110-120 ℃ after dropwise adding, reacting until the acid value is less than or equal to 1.5mgKOH/g, and cooling to finish the reaction.
Further, the mass ratio of 1, 6-hexanediol diglycidyl ether to bisphenol a epoxy resin was 1: 1.5-4.
Further, the preparation method of the functionalized graphene comprises the following steps:
crushing graphene oxide, adding the crushed graphene oxide into distilled water, dispersing for 1-3h by ultrasonic oscillation to obtain a suspension with a certain concentration, adding a certain amount of 1-naphthalene sulfanilic acid, continuing to disperse for 1-3h by ultrasonic oscillation, adding hydrazine hydrate, heating to 80-90 ℃, reacting for 30-40h, performing suction filtration, washing a solid to be neutral, and drying.
Furthermore, the compound sterilization component is compounded by a plurality of quaternary ammonium salts.
Further, the quaternary ammonium salts include dodecyl dimethyl phenoxyethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride and dimethyl benzyl ammonium chloride.
Further, the weight ratio of the component A to the component B is 10-12: 1.
The preparation method of the marine coating capable of effectively preventing marine organisms from attaching comprises the following steps:
mixing tourmaline, functionalized graphene and bentonite, ball-milling for 1-5h, adding the mixture, dimer acid modified epoxy resin, fluorosilicone resin, hydroxyl carbon nano tube, polydimethylsiloxane, butyl acetate and xylene into a dispersion tank, stirring and dispersing at the speed of 800-.
(III) advantageous effects
The invention provides a ship coating capable of effectively preventing marine organisms from attaching and a preparation method thereof, and the ship coating has the following beneficial effects:
the dimer acid modified epoxy resin in the invention adopts the reaction of dimer acid, epoxy resin and 1, 6-hexanediol diglycidyl ether to prepare high-flexibility low-viscosity epoxy resin, on one hand, the flexibility of the epoxy resin is effectively increased by the internal plasticization effect of C23 aliphatic long chain in the dimer acid and C6 aliphatic long chain in the 1, 6-hexanediol diglycidyl ether, and the 1, 6-hexanediol diglycidyl ether has no rigid group, small steric hindrance, strong segment movement capability and small viscosity, and can effectively reduce the viscosity of the modified epoxy resin, further reduce the dosage of butyl acetate and xylene in the preparation process of the coating, improve the corrosion resistance of the coating, and the fluorine silicon resin has excellent anti-sticking property, contains a plurality of hydroxyl groups, can be self-crosslinked and can be crosslinked with the dimer acid modified epoxy resin, the surface tension of the coating formed by curing is low, the marine coating has the advantages that the coating has excellent performances, the mechanical strength of the coating is high, the ship can be effectively protected from seawater corrosion, and the marine organism can be effectively prevented from attaching to the coating through seawater hanging plate experiments, so that the marine organism is washed away by water flow caused by ship navigation before being firmly attached to the ship, and the smoothness of the ship can be maintained for a long time.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a marine coating capable of effectively preventing marine organisms from attaching comprises the following components in percentage by weight: 1, wherein the component A comprises the following components in parts by weight:
38 parts of dimer acid modified epoxy resin, 15 parts of fluorosilicone resin, 10 parts of hydroxy carbon nano tube, 5 parts of polydimethylsiloxane, 16 parts of tourmaline, 10 parts of functionalized graphene, 3 parts of bentonite, 1 part of tributyl phosphate, 1.2 parts of capsaicin, 2 parts of a composite sterilization component compounded by dodecyl dimethyl phenoxyethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride and dimethyl benzyl ammonium chloride, 6 parts of liquid polysulfide rubber, 10 parts of hyperbranched polyether, 0.2 part of methyl diethanolamine, 0.1 part of dioctyl phthalate, 3 parts of hydrogen-terminated silicone oil, 8 parts of butyl acetate and 3 parts of xylene;
the preparation method of the dimer acid modified epoxy resin comprises the following steps:
adding bisphenol A epoxy resin, 1, 6-hexanediol diglycidyl ether and dimer acid into a reaction kettle, wherein the mass ratio of the 1, 6-hexanediol diglycidyl ether to the bisphenol A epoxy resin is 1: 2, stirring at room temperature for 50min under the protection of nitrogen, heating to 60 ℃, slowly dropwise adding an acetone solution of tetrabutylammonium bromide, heating to 110 ℃ after dropwise adding, reacting until the acid value is less than or equal to 1.5mgKOH/g, and cooling to finish the reaction.
The preparation method of the functionalized graphene comprises the following steps:
crushing graphene oxide, adding the crushed graphene oxide into distilled water, performing ultrasonic oscillation dispersion for 2 hours to obtain a suspension with a certain concentration, adding a certain amount of 1-naphthalene sulfanilic acid, continuing ultrasonic dispersion for 1 hour, adding hydrazine hydrate, heating to 90 ℃, reacting for 40 hours, performing suction filtration, washing a solid to be neutral, and drying.
The preparation method of the marine coating capable of effectively preventing marine organisms from attaching comprises the following steps:
mixing tourmaline, functionalized graphene and bentonite, ball-milling for 2h, adding the mixture, dimer acid modified epoxy resin, fluorosilicone resin, hydroxyl carbon nano tubes, polydimethylsiloxane, butyl acetate and xylene into a dispersion tank, stirring and dispersing at the speed of 1000r/min for 40min, heating to 40 ℃, adding tributyl phosphate, capsaicin, a composite sterilization component, liquid polysulfide rubber, hyperbranched polyether, methyldiethanolamine, dioctyl phthalate and hydrogen-terminated silicone oil, changing the rotating speed to 1500r/min, dispersing at a high speed for 20min, cooling to room temperature, adding a polyamide curing agent, continuously stirring and dispersing for 5min, and standing for 50 min.
Example 2:
a marine coating capable of effectively preventing marine organisms from attaching comprises 12 parts by weight: 1, wherein the component A comprises the following components in parts by weight:
40 parts of dimer acid modified epoxy resin, 12 parts of fluorosilicone resin, 12 parts of hydroxyl carbon nano tube, 4 parts of polydimethylsiloxane, 15 parts of tourmaline, 10 parts of functionalized graphene, 2 parts of bentonite, 1 part of tributyl phosphate, 1 part of capsaicin, 1 part of dodecyl dimethyl phenoxy ethyl ammonium bromide, 1 part of dodecyl dimethyl benzyl ammonium chloride, 1 part of composite sterilization component compounded by dioctadecyl dimethyl ammonium chloride and dimethyl benzyl ammonium chloride, 6 parts of liquid polysulfide rubber, 5 parts of hyperbranched polyether, 0.5 part of methyl diethanolamine, 0.1 part of dioctyl phthalate, 1 part of hydrogen-terminated silicone oil, 5 parts of butyl acetate and 40 parts of xylene;
the preparation method of the dimer acid modified epoxy resin comprises the following steps:
adding bisphenol A epoxy resin, 1, 6-hexanediol diglycidyl ether and dimer acid into a reaction kettle, wherein the mass ratio of the 1, 6-hexanediol diglycidyl ether to the bisphenol A epoxy resin is 1: 1.5, stirring at room temperature for 50min under the protection of nitrogen, heating to 60 ℃, slowly dropwise adding an acetone solution of tetrabutylammonium bromide, heating to 120 ℃ after dropwise adding, reacting until the acid value is less than or equal to 1.5mgKOH/g, and cooling to finish the reaction.
The preparation method of the functionalized graphene comprises the following steps:
crushing graphene oxide, adding the crushed graphene oxide into distilled water, performing ultrasonic oscillation dispersion for 3 hours to obtain a suspension with a certain concentration, adding a certain amount of 1-naphthalene sulfanilic acid, continuing ultrasonic dispersion for 3 hours, adding hydrazine hydrate, heating to 80 ℃, reacting for 40 hours, performing suction filtration, washing a solid to be neutral, and drying.
The preparation method of the marine coating capable of effectively preventing marine organisms from attaching comprises the following steps:
mixing tourmaline, functionalized graphene and bentonite, ball-milling for 5h, adding the mixture, dimer acid modified epoxy resin, fluorosilicone resin, hydroxyl carbon nano tubes, polydimethylsiloxane, butyl acetate and xylene into a dispersion tank, stirring and dispersing at the speed of 1000r/min for 30min, heating to 40 ℃, adding tributyl phosphate, capsaicin, a composite sterilization component, liquid polysulfide rubber, hyperbranched polyether, methyldiethanolamine, dioctyl phthalate and hydrogen-terminated silicone oil, changing the rotating speed to 1300r/min, dispersing at a high speed for 20min, cooling to room temperature, adding a polyamide curing agent, continuously stirring and dispersing for 5min, and standing for 30 min.
Example 3:
a marine coating capable of effectively preventing marine organisms from attaching comprises the following components in percentage by weight: 1, wherein the component A comprises the following components in parts by weight:
30 parts of dimer acid modified epoxy resin, 10 parts of fluorosilicone resin, 5 parts of hydroxy carbon nano tube, 5 parts of polydimethylsiloxane, 20 parts of tourmaline, 10 parts of functionalized graphene, 5 parts of bentonite, 1 part of tributyl phosphate, 1 part of capsaicin, 1.5 parts of a composite sterilization component compounded by dodecyl dimethyl phenoxyethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride and dimethyl benzyl ammonium chloride, 6 parts of liquid polysulfide rubber, 10 parts of hyperbranched polyether, 0.1 part of methyl diethanolamine, 0.1 part of dioctyl phthalate, 2 parts of hydrogen-terminated silicone oil, 10 parts of butyl acetate and 20 parts of xylene;
the preparation method of the dimer acid modified epoxy resin comprises the following steps:
adding bisphenol A epoxy resin, 1, 6-hexanediol diglycidyl ether and dimer acid into a reaction kettle, wherein the mass ratio of the 1, 6-hexanediol diglycidyl ether to the bisphenol A epoxy resin is 1: 1.5, stirring at room temperature for 50min under the protection of nitrogen, heating to 60 ℃, slowly dropwise adding an acetone solution of tetrabutylammonium bromide, heating to 110 ℃ after dropwise adding, reacting until the acid value is less than or equal to 1.5mgKOH/g, and cooling to finish the reaction.
The preparation method of the functionalized graphene comprises the following steps:
crushing graphene oxide, adding the crushed graphene oxide into distilled water, performing ultrasonic oscillation dispersion for 2 hours to obtain a suspension with a certain concentration, adding a certain amount of 1-naphthalene sulfanilic acid, continuing ultrasonic dispersion for 1 hour, adding hydrazine hydrate, heating to 80 ℃, reacting for 30 hours, performing suction filtration, washing a solid to be neutral, and drying.
The preparation method of the marine coating capable of effectively preventing marine organisms from attaching comprises the following steps:
mixing tourmaline, functionalized graphene and bentonite, ball-milling for 5h, adding the mixture, dimer acid modified epoxy resin, fluorosilicone resin, hydroxyl carbon nano tubes, polydimethylsiloxane, butyl acetate and xylene into a dispersion tank, stirring and dispersing at the speed of 1000r/min for 50min, heating to 40 ℃, adding tributyl phosphate, capsaicin, a composite sterilization component, liquid polysulfide rubber, hyperbranched polyether, methyldiethanolamine, dioctyl phthalate and hydrogen-terminated silicone oil, changing the rotating speed to 1300r/min, dispersing at a high speed for 20min, cooling to room temperature, adding a polyamide curing agent, continuously stirring and dispersing for 5min, and standing for 60 min.
Example 4:
a marine coating capable of effectively preventing marine organisms from attaching comprises the following components in parts by weight of 11: 1, wherein the component A comprises the following components in parts by weight:
40 parts of dimer acid modified epoxy resin, 10 parts of fluorosilicone resin, 12 parts of hydroxyl carbon nano tube, 4 parts of polydimethylsiloxane, 20 parts of tourmaline, 10 parts of functionalized graphene, 5 parts of bentonite, 1 part of tributyl phosphate, 1.2 parts of capsaicin, 3 parts of a composite sterilization component formed by compounding dodecyl dimethyl phenoxyethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride and dimethyl benzyl ammonium chloride, 3 parts of liquid polysulfide rubber, 8 parts of hyperbranched polyether, 0.1 part of methyl diethanolamine, 0.1 part of dioctyl phthalate, 2 parts of hydrogen-terminated silicone oil, 10 parts of butyl acetate and 30 parts of xylene;
the preparation method of the dimer acid modified epoxy resin comprises the following steps:
adding bisphenol A epoxy resin, 1, 6-hexanediol diglycidyl ether and dimer acid into a reaction kettle, wherein the mass ratio of the 1, 6-hexanediol diglycidyl ether to the bisphenol A epoxy resin is 1: 1.5, stirring at room temperature for 30min under the protection of nitrogen, heating to 60 ℃, slowly dropwise adding an acetone solution of tetrabutylammonium bromide, heating to 120 ℃ after dropwise adding, reacting until the acid value is less than or equal to 1.5mgKOH/g, and cooling to finish the reaction.
The preparation method of the functionalized graphene comprises the following steps:
crushing graphene oxide, adding the crushed graphene oxide into distilled water, performing ultrasonic oscillation dispersion for 1 hour to obtain a suspension with a certain concentration, adding a certain amount of 1-naphthalene sulfanilic acid, continuing ultrasonic dispersion for 3 hours, adding hydrazine hydrate, heating to 80 ℃, reacting for 30 hours, performing suction filtration, washing a solid to be neutral, and drying.
The preparation method of the marine coating capable of effectively preventing marine organisms from attaching comprises the following steps:
mixing tourmaline, functionalized graphene and bentonite, ball-milling for 5h, adding the mixture, dimer acid modified epoxy resin, fluorosilicone resin, hydroxyl carbon nano tubes, polydimethylsiloxane, butyl acetate and xylene into a dispersion tank, stirring and dispersing at the speed of 800r/min for 50min, heating to 40 ℃, adding tributyl phosphate, capsaicin, a composite sterilization component, liquid polysulfide rubber, hyperbranched polyether, methyldiethanolamine, dioctyl phthalate and hydrogen-terminated silicone oil, changing the rotating speed to 1300r/min, dispersing at a high speed for 22min, cooling to room temperature, adding a polyamide curing agent, continuously stirring and dispersing for 5min, and standing for 60 min.
Example 5:
a marine coating capable of effectively preventing marine organisms from attaching comprises 12 parts by weight: 1, wherein the component A comprises the following components in parts by weight:
40 parts of dimer acid modified epoxy resin, 10 parts of fluorosilicone resin, 5 parts of hydroxyl carbon nano tube, 5 parts of polydimethylsiloxane, 20 parts of tourmaline, 5 parts of functionalized graphene, 2 parts of bentonite, 1 part of tributyl phosphate, 1 part of capsaicin, 2 parts of dodecyl dimethyl phenoxy ethyl ammonium bromide, 2 parts of a composite sterilization component compounded by dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride and dimethyl benzyl ammonium chloride, 7 parts of liquid polysulfide rubber, 5 parts of hyperbranched polyether, 0.1 part of methyldiethanolamine, 0.1 part of dioctyl phthalate, 2 parts of hydrogen-terminated silicone oil, 10 parts of butyl acetate and 30 parts of xylene;
the preparation method of the dimer acid modified epoxy resin comprises the following steps:
adding bisphenol A epoxy resin, 1, 6-hexanediol diglycidyl ether and dimer acid into a reaction kettle, wherein the mass ratio of the 1, 6-hexanediol diglycidyl ether to the bisphenol A epoxy resin is 1: 1.5, stirring at room temperature for 50min under the protection of nitrogen, heating to 60 ℃, slowly dropwise adding an acetone solution of tetrabutylammonium bromide, heating to 120 ℃ after dropwise adding, reacting until the acid value is less than or equal to 1.5mgKOH/g, and cooling to finish the reaction.
The preparation method of the functionalized graphene comprises the following steps:
crushing graphene oxide, adding the crushed graphene oxide into distilled water, performing ultrasonic oscillation dispersion for 3 hours to obtain a suspension with a certain concentration, adding a certain amount of 1-naphthalene sulfanilic acid, continuing ultrasonic dispersion for 3 hours, adding hydrazine hydrate, heating to 80 ℃, reacting for 30 hours, performing suction filtration, washing a solid to be neutral, and drying.
The preparation method of the marine coating capable of effectively preventing marine organisms from attaching comprises the following steps:
mixing tourmaline, functionalized graphene and bentonite, ball-milling for 2h, adding the mixture, dimer acid modified epoxy resin, fluorosilicone resin, hydroxyl carbon nano tubes, polydimethylsiloxane, butyl acetate and xylene into a dispersion tank, stirring and dispersing at the speed of 1000r/min for 50min, heating to 50 ℃, adding tributyl phosphate, capsaicin, a composite sterilization component, liquid polysulfide rubber, hyperbranched polyether, methyldiethanolamine, dioctyl phthalate and hydrogen-terminated silicone oil, changing the rotating speed to 1300r/min, dispersing at a high speed for 25min, cooling to room temperature, adding a polyamide curing agent, continuing to stir and disperse for 5min, and standing for 50 min.
Example 6:
a marine coating capable of effectively preventing marine organisms from attaching comprises the following components in percentage by weight: 1, wherein the component A comprises the following components in parts by weight:
30 parts of dimer acid modified epoxy resin, 10 parts of fluorosilicone resin, 5 parts of hydroxyl carbon nano tube, 4 parts of polydimethylsiloxane, 15 parts of tourmaline, 5 parts of functionalized graphene, 2 parts of bentonite, 1 part of tributyl phosphate, 1 part of capsaicin, 0.5 part of a composite sterilization component compounded by dodecyl dimethyl phenoxyethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride and dimethyl benzyl ammonium chloride, 6 parts of liquid polysulfide rubber, 5 parts of hyperbranched polyether, 0.2 part of methyl diethanolamine, 0.5 part of dioctyl phthalate, 2 parts of hydrogen-terminated silicone oil, 8 parts of butyl acetate and 30 parts of xylene;
the preparation method of the dimer acid modified epoxy resin comprises the following steps:
adding bisphenol A epoxy resin, 1, 6-hexanediol diglycidyl ether and dimer acid into a reaction kettle, wherein the mass ratio of the 1, 6-hexanediol diglycidyl ether to the bisphenol A epoxy resin is 1: and 3, stirring at room temperature for 40min under the protection of nitrogen, heating to 60 ℃, slowly dropwise adding an acetone solution of tetrabutylammonium bromide, heating to 110 ℃ after dropwise adding, reacting until the acid value is less than or equal to 1.5mgKOH/g, and cooling to finish the reaction.
The preparation method of the functionalized graphene comprises the following steps:
crushing graphene oxide, adding the crushed graphene oxide into distilled water, performing ultrasonic oscillation dispersion for 2 hours to obtain a suspension with a certain concentration, adding a certain amount of 1-naphthalene sulfanilic acid, continuing ultrasonic dispersion for 1 hour, adding hydrazine hydrate, heating to 80 ℃, reacting for 40 hours, performing suction filtration, washing a solid to be neutral, and drying.
The preparation method of the marine coating capable of effectively preventing marine organisms from attaching comprises the following steps:
mixing tourmaline, functionalized graphene and bentonite, ball-milling for 2h, adding the mixture, dimer acid modified epoxy resin, fluorosilicone resin, hydroxyl carbon nano tubes, polydimethylsiloxane, butyl acetate and xylene into a dispersion tank, stirring and dispersing at the speed of 1000r/min for 40min, heating to 40 ℃, adding tributyl phosphate, capsaicin, a composite sterilization component, liquid polysulfide rubber, hyperbranched polyether, methyldiethanolamine, dioctyl phthalate and hydrogen-terminated silicone oil, changing the rotating speed to 1300r/min, dispersing at a high speed for 25min, cooling to room temperature, adding a polyamide curing agent, continuing to stir and disperse for 5min, and standing for 30 min.
Example 7:
a marine coating capable of effectively preventing marine organisms from attaching comprises the following components in percentage by weight: 1, wherein the component A comprises the following components in parts by weight:
30 parts of dimer acid modified epoxy resin, 10 parts of fluorosilicone resin, 5 parts of hydroxyl carbon nano tube, 4 parts of polydimethylsiloxane, 15 parts of tourmaline, 5 parts of functionalized graphene, 2 parts of bentonite, 1 part of tributyl phosphate, 1 part of capsaicin, 0.5 part of a composite sterilization component compounded by dodecyl dimethyl phenoxyethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride and dimethyl benzyl ammonium chloride, 3 parts of liquid polysulfide rubber, 5 parts of hyperbranched polyether, 0.1 part of methyl diethanolamine, 0.1 part of dioctyl phthalate, 1 part of hydrogen-terminated silicone oil, 5 parts of butyl acetate and 20 parts of xylene;
the preparation method of the dimer acid modified epoxy resin comprises the following steps:
adding bisphenol A epoxy resin, 1, 6-hexanediol diglycidyl ether and dimer acid into a reaction kettle, wherein the mass ratio of the 1, 6-hexanediol diglycidyl ether to the bisphenol A epoxy resin is 1: 1.5, stirring at room temperature for 30min under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding an acetone solution of tetrabutylammonium bromide, heating to 110 ℃ after dropwise adding, reacting until the acid value is less than or equal to 1.5mgKOH/g, and cooling to finish the reaction.
The preparation method of the functionalized graphene comprises the following steps:
crushing graphene oxide, adding the crushed graphene oxide into distilled water, performing ultrasonic oscillation dispersion for 1 hour to obtain a suspension with a certain concentration, adding a certain amount of 1-naphthalene sulfanilic acid, continuing ultrasonic dispersion for 1 hour, adding hydrazine hydrate, heating to 80 ℃, reacting for 30 hours, performing suction filtration, washing a solid to be neutral, and drying.
The preparation method of the marine coating capable of effectively preventing marine organisms from attaching comprises the following steps:
mixing tourmaline, functionalized graphene and bentonite, ball-milling for 1h, adding the mixture, dimer acid modified epoxy resin, fluorosilicone resin, hydroxyl carbon nano tubes, polydimethylsiloxane, butyl acetate and xylene into a dispersion tank, stirring and dispersing at the speed of 800r/min for 30min, heating to 40 ℃, adding tributyl phosphate, capsaicin, a composite sterilization component, liquid polysulfide rubber, hyperbranched polyether, methyldiethanolamine, dioctyl phthalate and hydrogen-terminated silicone oil, changing the rotating speed to 1300r/min, dispersing at a high speed for 20min, cooling to room temperature, adding a polyamide curing agent, continuously stirring and dispersing for 5min, and standing for 30 min.
Example 8:
a marine coating capable of effectively preventing marine organisms from attaching comprises 12 parts by weight: 1, wherein the component A comprises the following components in parts by weight:
50 parts of dimer acid modified epoxy resin, 20 parts of fluorosilicone resin, 12 parts of hydroxyl carbon nano tube, 8 parts of polydimethylsiloxane, 20 parts of tourmaline, 10 parts of functionalized graphene, 5 parts of bentonite, 2 parts of tributyl phosphate, 1.5 parts of capsaicin, 3 parts of a composite sterilization component formed by compounding dodecyl dimethyl phenoxyethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride and dimethyl benzyl ammonium chloride, 7 parts of liquid polysulfide rubber, 10 parts of hyperbranched polyether, 0.5 part of methyl diethanolamine, 0.5 part of dioctyl phthalate, 3 parts of hydrogen-terminated silicone oil, 10 parts of butyl acetate and 40 parts of xylene;
the preparation method of the dimer acid modified epoxy resin comprises the following steps:
adding bisphenol A epoxy resin, 1, 6-hexanediol diglycidyl ether and dimer acid into a reaction kettle, wherein the mass ratio of the 1, 6-hexanediol diglycidyl ether to the bisphenol A epoxy resin is 1: and 4, stirring at room temperature for 50min under the protection of nitrogen, heating to 60 ℃, slowly dropwise adding an acetone solution of tetrabutylammonium bromide, heating to 120 ℃ after dropwise adding, reacting until the acid value is less than or equal to 1.5mgKOH/g, and cooling to finish the reaction.
The preparation method of the functionalized graphene comprises the following steps:
crushing graphene oxide, adding the crushed graphene oxide into distilled water, performing ultrasonic oscillation dispersion for 3 hours to obtain a suspension with a certain concentration, adding a certain amount of 1-naphthalene sulfanilic acid, continuing ultrasonic dispersion for 3 hours, adding hydrazine hydrate, heating to 90 ℃, reacting for 40 hours, performing suction filtration, washing a solid to be neutral, and drying.
The preparation method of the marine coating capable of effectively preventing marine organisms from attaching comprises the following steps:
mixing tourmaline, functionalized graphene and bentonite, ball-milling for 5h, adding the mixture, dimer acid modified epoxy resin, fluorosilicone resin, hydroxyl carbon nano tubes, polydimethylsiloxane, butyl acetate and xylene into a dispersion tank, stirring and dispersing at the speed of 1000r/min for 50min, heating to 50 ℃, adding tributyl phosphate, capsaicin, a composite sterilization component, liquid polysulfide rubber, hyperbranched polyether, methyldiethanolamine, dioctyl phthalate and hydrogen-terminated silicone oil, changing the rotating speed to 1500r/min, dispersing at a high speed for 25min, cooling to room temperature, adding a polyamide curing agent, continuing to stir and disperse for 10min, and standing for 60 min.
And (3) performance testing:
table 1 below shows the results of various performance tests of the marine paint according to examples 1 to 3 of the present invention.
Table 1:
as can be seen from table 1 above, the ship coating of the present invention has excellent properties of the coating, high mechanical strength of the coating, and can effectively protect the ship hull from seawater corrosion, and the seawater hanging plate experiments prove that the coating can effectively prevent marine organisms from attaching to the ship hull, and the marine organisms are washed away by the water flow caused by ship navigation before firmly attaching to the ship hull, so as to maintain the ship hull smooth for a long time.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The marine coating capable of effectively preventing marine organisms from attaching is characterized by comprising a component A and a component B, wherein the component A comprises the following components in parts by weight:
30-50 parts of dimer acid modified epoxy resin, 10-20 parts of fluorosilicone resin, 5-12 parts of hydroxyl carbon nano tube, 4-8 parts of polydimethylsiloxane, 15-20 parts of tourmaline, 5-10 parts of functionalized graphene, 2-5 parts of bentonite, 1-2 parts of tributyl phosphate, 1-1.5 parts of capsaicin, 0.5-3 parts of composite sterilization component, 3-7 parts of liquid polysulfide rubber, 5-10 parts of hyperbranched polyether, 0.1-0.5 part of methyldiethanolamine, 0.1-0.5 part of dioctyl phthalate, 1-3 parts of hydrogen-terminated silicone oil, 5-10 parts of butyl acetate and 20-40 parts of xylene;
the component B is a polyamide curing agent.
2. The marine coating capable of effectively preventing marine organisms from attaching as claimed in claim 1, which comprises a component A and a component B, wherein the component A comprises the following components in parts by weight:
38 parts of dimer acid modified epoxy resin, 15 parts of fluorosilicone resin, 10 parts of hydroxyl carbon nano tube, 5 parts of polydimethylsiloxane, 16 parts of tourmaline, 10 parts of functionalized graphene, 3 parts of bentonite, 1 part of tributyl phosphate, 1.2 parts of capsaicin, 2 parts of composite sterilization component, 6 parts of liquid polysulfide rubber, 10 parts of hyperbranched polyether, 0.2 part of methyldiethanolamine, 0.1 part of dioctyl phthalate, 3 parts of terminal hydrogen-containing silicone oil, 8 parts of butyl acetate and 3 parts of xylene;
the component B is a polyamide curing agent.
3. The marine coating capable of effectively preventing marine organisms from attaching as claimed in claim 1, which comprises a component A and a component B, wherein the component A comprises the following components in parts by weight:
40 parts of dimer acid modified epoxy resin, 12 parts of fluorosilicone resin, 12 parts of hydroxyl carbon nano tubes, 4 parts of polydimethylsiloxane, 15 parts of tourmaline, 10 parts of functionalized graphene, 2 parts of bentonite, 1 part of tributyl phosphate, 1 part of capsaicin, 1 part of composite sterilization component, 6 parts of liquid polysulfide rubber, 5 parts of hyperbranched polyether, 0.5 part of methyldiethanolamine, 0.1 part of dioctyl phthalate, 1 part of hydrogen-containing terminal silicone oil, 5 parts of butyl acetate and 40 parts of dimethylbenzene;
the component B is a polyamide curing agent.
4. The marine coating capable of effectively preventing marine organisms from attaching as claimed in claim 1, wherein the dimer acid-modified epoxy resin is prepared by the following method:
adding bisphenol A epoxy resin, 1, 6-hexanediol diglycidyl ether and dimer acid into a reaction kettle, stirring at room temperature for 30-50min under the protection of nitrogen, heating to 50-60 ℃, slowly dropwise adding acetone solution of tetrabutylammonium bromide, heating to 110-120 ℃ after dropwise adding, reacting until the acid value is less than or equal to 1.5mgKOH/g, and cooling to finish the reaction.
5. The marine coating composition effective for inhibiting marine organism adhesion according to claim 4, wherein the mass ratio of 1, 6-hexanediol diglycidyl ether to bisphenol A epoxy resin is 1: 1.5-4.
6. The marine coating capable of effectively preventing marine organisms from attaching as claimed in claim 1, wherein the preparation method of the functionalized graphene is as follows:
crushing graphene oxide, adding the crushed graphene oxide into distilled water, dispersing for 1-3h by ultrasonic oscillation to obtain a suspension with a certain concentration, adding a certain amount of 1-naphthalene sulfanilic acid, continuing to disperse for 1-3h by ultrasonic oscillation, adding hydrazine hydrate, heating to 80-90 ℃, reacting for 30-40h, performing suction filtration, washing a solid to be neutral, and drying.
7. The marine coating material of claim 1, wherein the biocidal composition is a mixture of quaternary ammonium salts.
8. The marine coating of claim 7, wherein said quaternary ammonium salts comprise dodecyldimethylbenzyloxyethyl ammonium bromide, dodecyldimethylbenzyl ammonium chloride, dioctadecyldimethylammonium chloride, and dimethylbenzyl ammonium chloride.
9. The marine coating composition effective for inhibiting marine organism adhesion of claim 1, wherein the weight ratio of said a-component to said B-component is 10-12: 1.
10. The method for preparing marine coating capable of effectively preventing marine organisms from attaching according to any one of claims 1 to 9, is characterized by comprising the following steps:
mixing tourmaline, functionalized graphene and bentonite, ball-milling for 1-5h, adding the mixture, dimer acid modified epoxy resin, fluorosilicone resin, hydroxyl carbon nano tube, polydimethylsiloxane, butyl acetate and xylene into a dispersion tank, stirring and dispersing at the speed of 800-.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113604130A (en) * | 2021-06-24 | 2021-11-05 | 湖南航天三丰科工有限公司 | Seawater-resistant oil-resistant elastic epoxy ballast tank coating and preparation method thereof |
CN114605892A (en) * | 2022-03-22 | 2022-06-10 | 厦门双瑞船舶涂料有限公司 | Organosilicon quaternary ammonium salt modified epoxy anticorrosive paint and preparation method thereof |
-
2019
- 2019-12-27 CN CN201911374112.2A patent/CN111100529A/en not_active Withdrawn
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113604130A (en) * | 2021-06-24 | 2021-11-05 | 湖南航天三丰科工有限公司 | Seawater-resistant oil-resistant elastic epoxy ballast tank coating and preparation method thereof |
CN114605892A (en) * | 2022-03-22 | 2022-06-10 | 厦门双瑞船舶涂料有限公司 | Organosilicon quaternary ammonium salt modified epoxy anticorrosive paint and preparation method thereof |
CN114605892B (en) * | 2022-03-22 | 2022-12-23 | 厦门双瑞船舶涂料有限公司 | Organosilicon quaternary ammonium salt modified epoxy anticorrosive paint and preparation method thereof |
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