WO2020186721A1 - Corrosion-resistant nanometer modified composite coating for use in ship - Google Patents

Corrosion-resistant nanometer modified composite coating for use in ship Download PDF

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Publication number
WO2020186721A1
WO2020186721A1 PCT/CN2019/108174 CN2019108174W WO2020186721A1 WO 2020186721 A1 WO2020186721 A1 WO 2020186721A1 CN 2019108174 W CN2019108174 W CN 2019108174W WO 2020186721 A1 WO2020186721 A1 WO 2020186721A1
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Prior art keywords
parts
nano
corrosion
mixture
modified composite
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PCT/CN2019/108174
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French (fr)
Chinese (zh)
Inventor
张强勇
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江苏海事职业技术学院
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Publication of WO2020186721A1 publication Critical patent/WO2020186721A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • 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
    • 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
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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

Definitions

  • the invention relates to the technical field of anticorrosive coatings, in particular to a corrosion-resistant nano-modified composite coating for ships.
  • the best anti-corrosion coating solution for steel structures is to use arc spraying zinc, aluminum and their alloy coatings plus a closed composite coating , Can obtain a long and effective anti-corrosion life.
  • the sealant applied on the surface of the spray coating can penetrate into the pores of the metal coating and anchor on the surface.
  • the bonding effect of the sealant on the surface of the metal spray coating is better than that on the surface of the sandblasting substrate.
  • the consumption rate of the sealed metal spray coating in a corrosive environment is significantly slower. Even if the surface sealing coating fails after some years, the metal coating underneath can still maintain a good condition, which is better than that of the unsealed metal coating.
  • the consumption rate of the metal coating is much slower and can effectively protect the structure for a longer time.
  • marine protective paint needs to be painted on the surface of ships to enhance the anti-corrosion effect and increase the service life.
  • primer and topcoat are used for spraying.
  • Most of the existing marine protective paints have poor corrosion resistance, poor adhesion, It is prone to brittle fall off during long-term use, especially when subjected to impact, its impact resistance is poor, which leads to the defect of paint falling off easily.
  • the present invention provides a corrosion-resistant nano-modified composite coating for ships, which includes a topcoat and a primer.
  • the primer is used to cover the surface of the ship, and the topcoat is used to cover the primer ,
  • the topcoat includes 140-160 parts of polyurethane prepolymer, 10-20 parts of organic silicon mixture, 12-18 parts of epoxy resin, 1-5 parts of nano oxides, 15-25 parts of organic additives, and the base
  • the paint includes nano-silica, which accounts for 1% or more of the total mass of the primer.
  • the topcoat includes 152 parts of polyurethane prepolymer, 16 parts of organic silicon mixture, 14 parts of epoxy resin, 3 parts of nano zinc oxide, and 18 parts of organic additives.
  • the primer further includes 25-33 parts of epoxy resin, 12-18 parts of mixed solvent, 2-5 parts of auxiliary agent, 15-30 parts of anti-rust pigment, 10-15 parts of filler, and 12-18 parts of curing agent.
  • the organic silicon mixture is composed of dimethyl silicone oil and polyether modified silicon, wherein the mass ratio of dimethyl silicone oil and polyether modified silicon is 3:1.
  • the polyether modified silicon is TEGO Foamex 810.
  • the nano oxide is one or a mixture of titanium oxide, zinc oxide, zirconium oxide, and iron oxide.
  • the organic additives include catalysts, chain extenders, crosslinkers and plasticizers.
  • dibutyltin dilaurate is used as catalyst
  • diethylene glycol is used as chain extender
  • trimethylolpropane is used as crosslinking agent
  • trimethylolpropane is used as plasticizer.
  • the mass ratio of dioctyl phthalate, catalyst, chain extender, crosslinker and plasticizer is 1:3:2:3.
  • the mixed solvent is a mixture of two or more of xylene, aromatic cyclohexanone, ethylene glycol butyl ether, and propylene glycol methyl ether
  • the auxiliary agent is a salt solution of unsaturated polyamine amide and a lower molecular weight acid polymer Or a copolymer solution with acidic groups.
  • the anti-rust pigment is a mixture of two or more of titanium dioxide, strontium chrome yellow, and zinc chrome yellow;
  • the filler is zinc phosphate, aluminum tripolyphosphate, iron titanium powder, barium sulfate, calcium carbonate, mica powder, and talc A mixture of two or more in the powder;
  • the curing agent is a mixture of a polyamide curing agent and a silane coupling agent, and the mass ratio of the polyamide curing agent to the silane coupling agent is 200:1.
  • the preparation method of the topcoat includes the following steps: Step S01: Preheat the polyether glycol in a constant temperature water bath for at least 30 minutes to complete the full dehydration, and add the fully dehydrated polyether glycol into the blender. Alcohol and toluene diisocyanate, and add solvent, the mass ratio of fully dehydrated polyether diol and toluene diisocyanate is 4:1, the solvent is methyl ethyl ketone solution, methyl ethyl ketone solution uses 1% mol methyl ethyl ketone solution, inside the stirrer Raise the temperature to 80°C and keep the temperature for 3 ⁇ 4h to obtain the polyurethane prepolymer; then prepare the silicone mixture, epoxy resin, nano oxide and organic additives in proportion; Step S02: Raise the temperature in the mixer to 95°C , Keep constant temperature, add organic silicon mixture, stir, add organic silicon mixture, continue to react for 5 min; Step S03: add epoxy resin in the stirrer, continue to react for 10 minutes
  • step S02 the method of adding the silicone mixture is to add dimethyl silicone oil and polyether modified silicon in sequence with an interval of 5 minutes; the method of adding organic additives in step S05 is: adding catalyst, chain extender, and crosslinking agent in sequence. Coupling agent and plasticizer, the interval should not exceed 5 minutes, keep stirring.
  • the adhesion of the primer and the ship surface is increased, and the top paint formula is optimized at the same time, which can be well bonded with the primer, and has good impact strength, adhesion and corrosion resistance Sex.
  • the invention provides a corrosion-resistant nano-modified composite paint for ships, comprising a topcoat and a primer.
  • the primer is used to cover the surface of the ship, the topcoat is used to cover the primer, and the topcoat is It includes 140-160 parts of polyurethane prepolymer, 10-20 parts of organic silicon mixture, 12-18 parts of epoxy resin, 1-5 parts of nano oxides, 15-25 parts of organic additives, and the primer includes nano dioxide Silicon, the nano-silica accounts for more than 1% of the total mass of the primer.
  • the primer also includes 25-33 parts of epoxy resin, 12-18 parts of mixed solvent, 2-5 parts of auxiliary agent, 15-30 parts of anti-rust pigment, 10-15 parts of filler, and 12-18 parts of curing agent.
  • the mixed solvent in the primer is a mixture of two or more of xylene, aromatic cyclohexanone, ethylene glycol butyl ether, and propylene glycol methyl ether.
  • the auxiliary agent in the primer is a salt solution of unsaturated polyamine amide and a lower molecular weight acidic polymer or a copolymer solution with acidic groups.
  • the anti-rust pigment in the primer is a mixture of two or more of titanium dioxide, strontium chrome yellow, and zinc chrome yellow.
  • the filler in the primer is a mixture of two or more of zinc phosphate, aluminum tripolyphosphate, iron titanium powder, barium sulfate, calcium carbonate, mica powder, and talc.
  • the curing agent in the primer is a mixture of a polyamide curing agent and a silane coupling agent, and the mass ratio of the polyamide curing agent to the silane coupling agent is 200:1, and the curing agent is added to the silane coupling agent. Improve overall adhesion performance.
  • nano-silica uses a concentrated slurry with a viscosity of less than 100cp and a solid content of 22%.
  • the effect of different content of nano-silica on the bond strength of the epoxy primer is determined from 0.5% of nano-silica, its increased adhesion is only 0.2Mpa, while 1% of the content of nano-silica can increase by 1.2Mpa, and continue to increase the content of nano-silica, of which 1.5% of the content is
  • Nano silica can increase 1.5Mpa, 2.0% nano silica can increase 1.4Mpa, 3.0% nano silica can increase 1.3Mpa, 4.0% nano silica can increase Increase 1.4Mpa, therefore, it is preferable to use nano-silica to account for 1% of the total.
  • the bonding strength of the epoxy paint is increased, and at the same time it has good corrosion resistance.
  • the topcoat is preferably 152 parts of polyurethane prepolymer, 16 parts of organic silicon mixture, 14 parts of epoxy resin, 3 parts of nano zinc oxide, and 18 parts of organic additives.
  • the preparation method of the topcoat includes the following steps: Step S01: Preheat the polyether glycol in a constant temperature water bath for at least 30 minutes to complete the full dehydration, and add the fully dehydrated polyether glycol into the blender. Alcohol and toluene diisocyanate, and add solvent, the mass ratio of fully dehydrated polyether diol and toluene diisocyanate is 4:1, the solvent is methyl ethyl ketone solution, methyl ethyl ketone solution uses 1% mol methyl ethyl ketone solution, inside the stirrer Raise the temperature to 80°C and keep the temperature for 3 ⁇ 4 hours to obtain the polyurethane prepolymer, and then prepare the silicone mixture, epoxy resin, nano-oxide and organic additives in proportion; Step S02: Raise the temperature in the stirrer to 95°C, Keep at a constant temperature, add the silicone mixture, stir, add the silicone mixture, and continue to react for 5 min; Step S03: Add epoxy resin in the stirr
  • step S02 the method of adding the silicone mixture is to add dimethyl silicone oil and polyether modified silicon in sequence with an interval of 5 minutes; the method of adding organic additives in step S05 is: adding catalyst, chain extender, and crosslinking agent in sequence. Coupling agent and plasticizer, the interval should not exceed 5 minutes, keep stirring.
  • the advantage of the topcoat provided by the present invention is that the main chain skeleton of Si-O-Si is formed by using silicone, and the side groups of Si atoms react with the polyurethane prepolymer to generate Si-OC bond block-graft copolymer, and then Combining epoxy resin to form an interpenetrating network structure with the silicone-polyurethane copolymer, catalyzed by organic additives, to finally obtain a finished product.
  • the performance of the product of the present invention is higher than that of the prior art product in all aspects.
  • the reaction between silicone and polyurethane prepolymer is optimized, which is convenient for combining epoxy resin to form a staggered network structure, and is modified by nano-oxide Catalytic reaction with organic additives, thereby improving the impact strength, adhesion and corrosion resistance of the coating.

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  • Nanotechnology (AREA)
  • Paints Or Removers (AREA)

Abstract

A corrosion-resistant nanometer modified composite coating for use in a ship, comprising a topcoat and a basecoat, wherein the basecoat is used for covering the surface of the ship; the topcoat is used for covering the basecoat; the topcoat comprises 140-160 parts of a polyurethane prepolymer, 10-20 parts of an organic silicon mixture, 12-18 parts of an epoxy resin, 1-5 parts of a nano oxide, and 15-25 parts of an organic additive; the basecoat comprises 25-33 of the epoxy resin, 12-18 parts of a mixed solvent, 2-5 parts of an auxiliary agent, 15-30 parts of an antirust pigment, 1-3 parts of nano silica, 10-15 parts of a filler, and 12-18 parts of a curing agent, wherein the amount of the nano silica accounts for 1% or more of the total amount of the basecoat. By optimizing design and optimizing the formula of the basecoat, the present invention increases the adhesion of the basecoat on the surface of the ship, and meanwhile, the formula of the topcoat is optimized, so that the topcoat can well adhesively bond with the basecoat, and has good impact strength, adhesiveness, and corrosion resistance.

Description

一种船舶用耐腐蚀纳米改性复合涂料Corrosion-resistant nano-modified composite coating for ships 技术领域Technical field
本发明涉及防腐涂料技术领域，具体涉及一种船舶用耐腐蚀纳米改性复合涂料。 The invention relates to the technical field of anticorrosive coatings, in particular to a corrosion-resistant nano-modified composite coating for ships.
背景技术Background technique
在海洋环境、酸雨大气、工业大气和潮湿富氧的矿井环境等恶劣腐蚀环境下，钢铁结构的最佳防腐蚀涂层方案是采用电弧喷涂锌、铝及其合金涂层外加封闭的复合涂层，可以获得长久有效的防腐蚀寿命。涂刷在喷涂层表面的封闭剂能很好地渗透进金属涂层的孔隙中并锚固在其表面，封闭剂在金属喷涂层表面的结合效果比在喷砂基体表面的结合性还要好。而且经过封闭处理的金属喷涂层在腐蚀环境中的消耗速度明显减慢，即使在经过一些年表面封闭涂层失效了，但是其下面的金属涂层仍能够保持良好状态，比未经过封闭处理的金属涂层的消耗速度要慢得多，可以更长久有效的保护结构物。In harsh corrosive environments such as marine environment, acid rain atmosphere, industrial atmosphere and humid oxygen-rich mine environment, the best anti-corrosion coating solution for steel structures is to use arc spraying zinc, aluminum and their alloy coatings plus a closed composite coating , Can obtain a long and effective anti-corrosion life. The sealant applied on the surface of the spray coating can penetrate into the pores of the metal coating and anchor on the surface. The bonding effect of the sealant on the surface of the metal spray coating is better than that on the surface of the sandblasting substrate. Moreover, the consumption rate of the sealed metal spray coating in a corrosive environment is significantly slower. Even if the surface sealing coating fails after some years, the metal coating underneath can still maintain a good condition, which is better than that of the unsealed metal coating. The consumption rate of the metal coating is much slower and can effectively protect the structure for a longer time.
目前在船舶表面需要涂装船用防护漆，以增强防腐效果，提高使用寿命，通常是采用底漆面漆进行喷涂，而现有的船用防护漆大多具有防腐性能不佳、粘附力不好、长期使用过程中容易出现脆性脱落，特别是在受到冲击力时，其抗冲击强度较差，导致容易出现掉漆的缺陷。At present, marine protective paint needs to be painted on the surface of ships to enhance the anti-corrosion effect and increase the service life. Usually, primer and topcoat are used for spraying. Most of the existing marine protective paints have poor corrosion resistance, poor adhesion, It is prone to brittle fall off during long-term use, especially when subjected to impact, its impact resistance is poor, which leads to the defect of paint falling off easily.
技术问题technical problem
    现有的船用防护漆大多具有防腐性能不佳、粘附力不好、长期使用过程中容易出现脆性脱落，特别是在受到冲击力时，其抗冲击强度较差，导致容易出现掉漆的缺陷。... Most of the existing marine protective paints have poor anti-corrosion performance, poor adhesion, and brittleness and fall off during long-term use. Especially when subjected to impact, their impact strength is poor, resulting in the defect of paint falling off easily .
技术解决方案Technical solutions
为了解决以上问题，本发明提供了一种船舶用耐腐蚀纳米改性复合涂料，包括面漆和底漆，所述底漆用于覆盖于船舶表面，所述面漆用以覆盖所述底漆，所述面漆包括聚氨酯预聚体140-160份、有机硅混合物10-20份，环氧树脂12-18份，纳米氧化物1~5份、有机添加剂15~25份，所述的底漆包括纳米二氧化硅，所述的纳米二氧化硅占底漆质量总比例1%及以上。In order to solve the above problems, the present invention provides a corrosion-resistant nano-modified composite coating for ships, which includes a topcoat and a primer. The primer is used to cover the surface of the ship, and the topcoat is used to cover the primer , The topcoat includes 140-160 parts of polyurethane prepolymer, 10-20 parts of organic silicon mixture, 12-18 parts of epoxy resin, 1-5 parts of nano oxides, 15-25 parts of organic additives, and the base The paint includes nano-silica, which accounts for 1% or more of the total mass of the primer.
所述面漆包括聚氨酯预聚体152份、有机硅混合物16份、环氧树脂14份、纳米氧化锌3份、有机添加剂18份。The topcoat includes 152 parts of polyurethane prepolymer, 16 parts of organic silicon mixture, 14 parts of epoxy resin, 3 parts of nano zinc oxide, and 18 parts of organic additives.
所述底漆还包括环氧树脂25-33份、混合溶剂12-18份、助剂2-5份、防锈颜料15-30份，填料10~15份、固化剂12~18份。The primer further includes 25-33 parts of epoxy resin, 12-18 parts of mixed solvent, 2-5 parts of auxiliary agent, 15-30 parts of anti-rust pigment, 10-15 parts of filler, and 12-18 parts of curing agent.
所述有机硅混合物由二甲基硅油和聚醚改性硅构成，其中二甲基硅油和聚醚改性硅质量比为3：1。The organic silicon mixture is composed of dimethyl silicone oil and polyether modified silicon, wherein the mass ratio of dimethyl silicone oil and polyether modified silicon is 3:1.
所述的聚醚改性硅为TEGO Foamex 810。The polyether modified silicon is TEGO Foamex 810.
所述纳米氧化物为氧化钛、氧化锌、氧化锆、氧化铁中的一种或几种的混合物。The nano oxide is one or a mixture of titanium oxide, zinc oxide, zirconium oxide, and iron oxide.
所述有机添加剂包括催化剂、扩链剂、交联剂和增塑剂，其中催化剂采用二月桂酸二丁基锡，扩链剂采用二甘醇，交联剂采用三羟甲基丙烷，增塑剂采用邻苯二甲酸二辛酯，催化剂、扩链剂、交联剂、增塑剂之间的质量比为1：3：2：3。The organic additives include catalysts, chain extenders, crosslinkers and plasticizers. Among them, dibutyltin dilaurate is used as catalyst, diethylene glycol is used as chain extender, trimethylolpropane is used as crosslinking agent, and trimethylolpropane is used as plasticizer. The mass ratio of dioctyl phthalate, catalyst, chain extender, crosslinker and plasticizer is 1:3:2:3.
所述混合溶剂为二甲苯、芳烃环己酮、乙二醇丁醚、丙二醇甲醚中两种及以上的混合物，所述助剂为不饱和多元胺酰胺和较低分子量酸性聚合物的盐溶液或具有酸性基团的共聚体溶液。The mixed solvent is a mixture of two or more of xylene, aromatic cyclohexanone, ethylene glycol butyl ether, and propylene glycol methyl ether, and the auxiliary agent is a salt solution of unsaturated polyamine amide and a lower molecular weight acid polymer Or a copolymer solution with acidic groups.
所述防锈颜料为钛白粉、锶铬黄、锌铬黄中两种及以上的混合物；所述填料为磷酸锌、三聚磷酸铝、铁钛粉、硫酸钡、碳酸钙、云母粉、滑石粉中的两种及以上的混合物；所述固化剂为聚酰胺固化剂和硅烷偶联剂的混合物，聚酰胺固化剂和硅烷偶联剂的质量比为200：1。The anti-rust pigment is a mixture of two or more of titanium dioxide, strontium chrome yellow, and zinc chrome yellow; the filler is zinc phosphate, aluminum tripolyphosphate, iron titanium powder, barium sulfate, calcium carbonate, mica powder, and talc A mixture of two or more in the powder; the curing agent is a mixture of a polyamide curing agent and a silane coupling agent, and the mass ratio of the polyamide curing agent to the silane coupling agent is 200:1.
所述的面漆的制备方法包括以下步骤：步骤S01：将聚醚二元醇在恒温水浴锅中预热至少30min，完成充分脱水，在搅拌器内加入完成冷却后并充分脱水的聚醚二元醇和甲苯二异氰酸酯，并加入溶剂，充分脱水的聚醚二元醇和甲苯二异氰酸酯质量比为4：1，其中溶剂为丁酮溶液，丁酮溶液采用1%摩尔的丁酮溶液，搅拌器内升温至80℃，恒温保持3~4h，获得聚氨酯预聚体；；然后按比例准备好有机硅混合物，环氧树脂，纳米氧化物、有机添加剂；步骤S02：将搅拌器内温度升温至95℃，恒温保持，加入有机硅混合物，搅拌，加入有机硅混合物，持续反应5min；步骤S03：在搅拌器内加入环氧树脂，持续反应10min，持续搅拌；步骤S04：在搅拌器内加入纳米氧化物，持续反应5min，持续搅拌；步骤S05：在搅拌器内加入有机添加剂，持续搅拌，恒温保持45min以上；步骤S06：降温，获得面漆。The preparation method of the topcoat includes the following steps: Step S01: Preheat the polyether glycol in a constant temperature water bath for at least 30 minutes to complete the full dehydration, and add the fully dehydrated polyether glycol into the blender. Alcohol and toluene diisocyanate, and add solvent, the mass ratio of fully dehydrated polyether diol and toluene diisocyanate is 4:1, the solvent is methyl ethyl ketone solution, methyl ethyl ketone solution uses 1% mol methyl ethyl ketone solution, inside the stirrer Raise the temperature to 80℃ and keep the temperature for 3~4h to obtain the polyurethane prepolymer; then prepare the silicone mixture, epoxy resin, nano oxide and organic additives in proportion; Step S02: Raise the temperature in the mixer to 95℃ , Keep constant temperature, add organic silicon mixture, stir, add organic silicon mixture, continue to react for 5 min; Step S03: add epoxy resin in the stirrer, continue to react for 10 minutes, continue to stir; Step S04: add nano oxide in the stirrer , Continue the reaction for 5 minutes and continue to stir; step S05: add organic additives in the mixer, continue to stir, and keep the constant temperature for more than 45 minutes; step S06: lower the temperature to obtain the top coat.
在步骤S02中，加入有机硅混合物的方法为依次加入二甲基硅油和聚醚改性硅，间隔时间为5min；在步骤S05中加入有机添加剂的方法为：依次加入催化剂、扩链剂、交联剂和增塑剂，间隔时间不超过5min，持续搅拌。In step S02, the method of adding the silicone mixture is to add dimethyl silicone oil and polyether modified silicon in sequence with an interval of 5 minutes; the method of adding organic additives in step S05 is: adding catalyst, chain extender, and crosslinking agent in sequence. Coupling agent and plasticizer, the interval should not exceed 5 minutes, keep stirring.
有益效果Beneficial effect
通过优化设计，优化底漆配方，增加了底漆与船舶表面的黏附性，同时优化面漆配方，其可以良好的与底漆黏附结合，并具有良好的抗冲击强度、粘结性和耐腐蚀性。By optimizing the design and optimizing the primer formula, the adhesion of the primer and the ship surface is increased, and the top paint formula is optimized at the same time, which can be well bonded with the primer, and has good impact strength, adhesion and corrosion resistance Sex.
本发明的最佳实施方式The best mode of the invention
下面对本发明进行详细说明。The present invention will be described in detail below.
本发明提供了一种船舶用耐腐蚀纳米改性复合涂料，包括面漆和底漆，所述底漆用于覆盖于船舶表面，所述面漆用以覆盖所述底漆，所述面漆包括聚氨酯预聚体140-160份、有机硅混合物10-20份，环氧树脂12-18份，纳米氧化物1-5份、有机添加剂15-25份，所述的底漆包括纳米二氧化硅，所述的纳米二氧化硅占底漆质量总比例1%以上。The invention provides a corrosion-resistant nano-modified composite paint for ships, comprising a topcoat and a primer. The primer is used to cover the surface of the ship, the topcoat is used to cover the primer, and the topcoat is It includes 140-160 parts of polyurethane prepolymer, 10-20 parts of organic silicon mixture, 12-18 parts of epoxy resin, 1-5 parts of nano oxides, 15-25 parts of organic additives, and the primer includes nano dioxide Silicon, the nano-silica accounts for more than 1% of the total mass of the primer.
所述底漆还包括环氧树脂25-33份、混合溶剂12-18份、助剂2-5份、防锈颜料15-30份，填料10-15份、固化剂12-18份。The primer also includes 25-33 parts of epoxy resin, 12-18 parts of mixed solvent, 2-5 parts of auxiliary agent, 15-30 parts of anti-rust pigment, 10-15 parts of filler, and 12-18 parts of curing agent.
其中，底漆中混合溶剂为二甲苯、芳烃环己酮、乙二醇丁醚、丙二醇甲醚中两种及以上的混合物。Among them, the mixed solvent in the primer is a mixture of two or more of xylene, aromatic cyclohexanone, ethylene glycol butyl ether, and propylene glycol methyl ether.
其中，底漆中助剂为不饱和多元胺酰胺和较低分子量酸性聚合物的盐溶液或具有酸性基团的共聚体溶液。Among them, the auxiliary agent in the primer is a salt solution of unsaturated polyamine amide and a lower molecular weight acidic polymer or a copolymer solution with acidic groups.
其中，底漆中防锈颜料为钛白粉、锶铬黄、锌铬黄中两种及以上的混合物。Among them, the anti-rust pigment in the primer is a mixture of two or more of titanium dioxide, strontium chrome yellow, and zinc chrome yellow.
其中，底漆中填料为磷酸锌、三聚磷酸铝、铁钛粉、硫酸钡、碳酸钙、云母粉、滑石粉中的两种及以上的混合物。Among them, the filler in the primer is a mixture of two or more of zinc phosphate, aluminum tripolyphosphate, iron titanium powder, barium sulfate, calcium carbonate, mica powder, and talc.
其中，底漆中固化剂为聚酰胺固化剂和硅烷偶联剂的混合物，聚酰胺固化剂和硅烷偶联剂的质量比为200：1，其中固化剂中配比增加硅烷偶联剂，可以提高整体的附着性能。Among them, the curing agent in the primer is a mixture of a polyamide curing agent and a silane coupling agent, and the mass ratio of the polyamide curing agent to the silane coupling agent is 200:1, and the curing agent is added to the silane coupling agent. Improve overall adhesion performance.
底漆中，纳米二氧化硅采用粘度小于100cp，固含量为22%的浓缩浆，通过不断试验，对于不同含量的纳米二氧化硅对环氧底漆粘结强度的影响，其从占比为0.5%的纳米二氧化硅，其所增加的粘结度只有0.2Mpa，而1%占比含量的纳米二氧化硅可以增加1.2Mpa，持续增加纳米二氧化硅含量，其中1.5%占比含量的纳米二氧化硅可以增加1.5Mpa，2.0%占比含量的纳米二氧化硅可以增加1.4Mpa，3.0%占比含量的纳米二氧化硅可以增加1.3Mpa，4.0%占比含量的纳米二氧化硅可以增加1.4Mpa，因此，优选的采用纳米二氧化硅占总比例为1%。In the primer, nano-silica uses a concentrated slurry with a viscosity of less than 100cp and a solid content of 22%. Through continuous experiments, the effect of different content of nano-silica on the bond strength of the epoxy primer is determined from 0.5% of nano-silica, its increased adhesion is only 0.2Mpa, while 1% of the content of nano-silica can increase by 1.2Mpa, and continue to increase the content of nano-silica, of which 1.5% of the content is Nano silica can increase 1.5Mpa, 2.0% nano silica can increase 1.4Mpa, 3.0% nano silica can increase 1.3Mpa, 4.0% nano silica can increase Increase 1.4Mpa, therefore, it is preferable to use nano-silica to account for 1% of the total.
通过优化底漆配方，采用纳米二氧化硅进行改性，增加了环氧漆的粘结强度，同时具有良好的耐腐蚀性能。By optimizing the primer formulation and using nano-silica for modification, the bonding strength of the epoxy paint is increased, and at the same time it has good corrosion resistance.
所述面漆优选为聚氨酯预聚体152份、有机硅混合物16份、环氧树脂14份、纳米氧化锌3份、有机添加剂18份。The topcoat is preferably 152 parts of polyurethane prepolymer, 16 parts of organic silicon mixture, 14 parts of epoxy resin, 3 parts of nano zinc oxide, and 18 parts of organic additives.
所述的面漆的制备方法包括以下步骤：步骤S01：将聚醚二元醇在恒温水浴锅中预热至少30min，完成充分脱水，在搅拌器内加入完成冷却后并充分脱水的聚醚二元醇和甲苯二异氰酸酯，并加入溶剂，充分脱水的聚醚二元醇和甲苯二异氰酸酯质量比为4：1，其中溶剂为丁酮溶液，丁酮溶液采用1%摩尔的丁酮溶液，搅拌器内升温至80℃，恒温保持3~4h，获得聚氨酯预聚体，然后按比例准备好有机硅混合物，环氧树脂，纳米氧化物、有机添加剂；步骤S02：将搅拌器内温度升温至95℃，恒温保持，加入有机硅混合物，搅拌，加入有机硅混合物，持续反应5min；步骤S03：在搅拌器内加入环氧树脂，持续反应10min，持续搅拌；步骤S04：在搅拌器内加入纳米氧化物，持续反应5min，持续搅拌；步骤S05：在搅拌器内加入有机添加剂，持续搅拌，恒温保持45min以上；步骤S06：降温，获得面漆。The preparation method of the topcoat includes the following steps: Step S01: Preheat the polyether glycol in a constant temperature water bath for at least 30 minutes to complete the full dehydration, and add the fully dehydrated polyether glycol into the blender. Alcohol and toluene diisocyanate, and add solvent, the mass ratio of fully dehydrated polyether diol and toluene diisocyanate is 4:1, the solvent is methyl ethyl ketone solution, methyl ethyl ketone solution uses 1% mol methyl ethyl ketone solution, inside the stirrer Raise the temperature to 80°C and keep the temperature for 3~4 hours to obtain the polyurethane prepolymer, and then prepare the silicone mixture, epoxy resin, nano-oxide and organic additives in proportion; Step S02: Raise the temperature in the stirrer to 95°C, Keep at a constant temperature, add the silicone mixture, stir, add the silicone mixture, and continue to react for 5 min; Step S03: Add epoxy resin in the stirrer, continue to react for 10 minutes, and continue to stir; Step S04: Add nano-oxide in the stirrer, Continue the reaction for 5 minutes and continue to stir; Step S05: Add organic additives in the mixer, continue to stir, and maintain the constant temperature for more than 45 minutes; Step S06: Cool down to obtain the top coat.
在步骤S02中，加入有机硅混合物的方法为依次加入二甲基硅油和聚醚改性硅，间隔时间为5min；在步骤S05中加入有机添加剂的方法为：依次加入催化剂、扩链剂、交联剂和增塑剂，间隔时间不超过5min，持续搅拌。In step S02, the method of adding the silicone mixture is to add dimethyl silicone oil and polyether modified silicon in sequence with an interval of 5 minutes; the method of adding organic additives in step S05 is: adding catalyst, chain extender, and crosslinking agent in sequence. Coupling agent and plasticizer, the interval should not exceed 5 minutes, keep stirring.
本发明提供的面漆的优势在于：利用有机硅形成的Si-O-Si的主链骨架，Si原子侧基通过与聚氨酯预聚体反应生成Si-O-C键嵌段-接枝共聚物，再结合环氧树脂，使其与有机硅-聚氨酯共聚物形成互穿网络结构，通过有机添加剂的催化，从而最终获得成品。The advantage of the topcoat provided by the present invention is that the main chain skeleton of Si-O-Si is formed by using silicone, and the side groups of Si atoms react with the polyurethane prepolymer to generate Si-OC bond block-graft copolymer, and then Combining epoxy resin to form an interpenetrating network structure with the silicone-polyurethane copolymer, catalyzed by organic additives, to finally obtain a finished product.
本发明提供的船舶用耐腐蚀纳米改性复合涂料和现有产品的参数对比见下表：The parameter comparison between the corrosion-resistant nano-modified composite coating for ships provided by the present invention and the existing products is shown in the following table:
检测项目Test items 未改性聚氨酯涂料（现有产品）Unmodified polyurethane coating (existing product) 纳米改性复合聚氨酯船舶面漆涂料Nano modified composite polyurethane marine topcoat paint 检测标准Testing standard
冲击强度kg·cmImpact strength kg·cm 1515 5050 GB/T 1732GB/T 1732
拉伸强度MpaTensile strength Mpa 1.551.55 8.48.4 GB/T 16421GB/T 16421
吸水率%Water absorption% 18.4518.45 1.321.32 GB/T 6753.3GB/T 6753.3
耐酸性15%HClAcid resistance 15% HCl 浸泡240h后涂层完好，360h后涂层有起皮The coating is intact after being soaked for 240h, and the coating is peeling after 360h 浸泡480h后涂层完好，540h后涂层有起皮The coating is intact after immersing for 480h, and the coating is peeling after 540h GB/T 1763GB/T 1763
耐碱性15%NaOHAlkali resistance 15%NaOH 浸泡720h后涂层完好，840h后涂层有起皮The coating is intact after immersing for 720h, and the coating is peeling after 840h 浸泡1080h后涂层完好，1350h后涂层有起皮The coating is intact after being immersed for 1080h, and the coating is peeling after 1350h GB/T 1763GB/T 1763
耐盐水性3.5%NaClSalt water resistance 3.5%NaCl 浸泡480h后涂层完好，720h后涂层有起皮The coating is intact after immersing for 480h, and the coating is peeling after 720h 浸泡840h后涂层完好，1080h后涂层有起皮The coating is intact after soaking for 840h, and the coating is peeling after 1080h GB/T 1763GB/T 1763
结合上表，通过对比，本发明产品各方面性能均高于现有技术产品，优化利用有机硅与聚氨酯预聚体的反应，便于结合环氧树脂形成交错网结构，并利用纳米氧化物改性和有机添加剂的催化反应，从而提高了涂料的抗冲击强度、粘结性和耐腐蚀性。In combination with the above table, through comparison, the performance of the product of the present invention is higher than that of the prior art product in all aspects. The reaction between silicone and polyurethane prepolymer is optimized, which is convenient for combining epoxy resin to form a staggered network structure, and is modified by nano-oxide Catalytic reaction with organic additives, thereby improving the impact strength, adhesion and corrosion resistance of the coating.
虽然本发明已以较佳实施例公开如上，但它们并不是用来限定本发明的，任何熟习此技艺者，在不脱离本发明之精神和范围内，自当可作各种变化或润饰，因此本发明的保护范围应当以本申请的权利要求保护范围所界定的为准。Although the present invention has been disclosed as above in the preferred embodiments, they are not used to limit the present invention. Anyone familiar with the art can make various changes or modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be defined by the protection scope of the claims of this application.

Claims (10)

  1. 一种船舶用耐腐蚀纳米改性复合涂料，包括面漆和底漆，所述底漆用于覆盖于船舶表面，所述面漆用以覆盖所述底漆，其特征在于：所述面漆包括聚氨酯预聚体140-160份、有机硅混合物10-20份，环氧树脂12-18份，纳米氧化物1~5份、有机添加剂15~25份，所述的底漆包括纳米二氧化硅，所述的纳米二氧化硅占底漆质量总比例1%及以上。A corrosion-resistant nano-modified composite paint for ships, comprising a top paint and a primer. The primer is used to cover the surface of the ship, and the top paint is used to cover the primer, and is characterized in that: the top paint Including 140-160 parts of polyurethane prepolymer, 10-20 parts of organic silicon mixture, 12-18 parts of epoxy resin, 1~5 parts of nano-oxide, 15-25 parts of organic additives, and the primer includes nano-dioxide Silicon, the nano-silica accounts for 1% or more of the total mass of the primer.
  2. 如权利要求1所述的船舶用耐腐蚀纳米改性复合涂料，其特征在于：所述面漆包括聚氨酯预聚体152份、有机硅混合物16份、环氧树脂14份、纳米氧化锌3份、有机添加剂18份。The corrosion-resistant nano-modified composite coating for ships according to claim 1, wherein the topcoat comprises 152 parts of polyurethane prepolymer, 16 parts of organic silicon mixture, 14 parts of epoxy resin, and 3 parts of nano zinc oxide. , 18 parts of organic additives.
  3. 如权利要求1所述的船舶用耐腐蚀纳米改性复合涂料，其特征在于：所述底漆还包括环氧树脂25~33份、混合溶剂12~18份、助剂2~5份、防锈颜料15~30份，填料10~15份、固化剂12~18份。The corrosion-resistant nano-modified composite coating for ships according to claim 1, wherein the primer further comprises 25 to 33 parts of epoxy resin, 12 to 18 parts of mixed solvent, 2 to 5 parts of additives, and 15-30 parts of rust pigment, 10-15 parts of filler, 12-18 parts of curing agent.
  4. 如权利1所述的船舶用耐腐蚀纳米改性复合涂料，其特征在于：所述有机硅混合物由二甲基硅油和聚醚改性硅构成，其中二甲基硅油和聚醚改性硅质量比为3：1。The corrosion-resistant nano-modified composite coating for ships according to claim 1, wherein the organic silicon mixture is composed of dimethyl silicone oil and polyether modified silicon, wherein the quality of the dimethyl silicone oil and polyether modified silicon is The ratio is 3:1.
  5. 如权利要求1所述的船舶用耐腐蚀纳米改性复合涂料，其特征在于：所述纳米氧化物为氧化钛、氧化锌、氧化锆、氧化铁中的一种或几种的混合物。The corrosion-resistant nano-modified composite coating for ships according to claim 1, wherein the nano-oxide is one or a mixture of titanium oxide, zinc oxide, zirconium oxide, and iron oxide.
  6. 如权利要求1所述的船舶用耐腐蚀纳米改性复合涂料，其特征在于：所述有机添加剂包括催化剂、扩链剂、交联剂和增塑剂，其中催化剂采用二月桂酸二丁基锡，扩链剂采用二甘醇，交联剂采用三羟甲基丙烷，增塑剂采用邻苯二甲酸二辛酯，催化剂、扩链剂、交联剂、增塑剂之间的质量比为1：3：2：3。The corrosion-resistant nano-modified composite coating for ships according to claim 1, wherein the organic additives include a catalyst, a chain extender, a crosslinking agent and a plasticizer, and the catalyst is dibutyltin dilaurate, which Diethylene glycol is used as the chain agent, trimethylolpropane is used as the cross-linking agent, and dioctyl phthalate is used as the plasticizer. The mass ratio of catalyst, chain extender, cross-linking agent, and plasticizer is 1: 3: 2: 3.
  7. 如权利要求2所述的船舶用耐腐蚀纳米改性复合涂料，其特征在于：所述混合溶剂为二甲苯、芳烃环己酮、乙二醇丁醚、丙二醇甲醚中两种及以上的混合物，所述助剂为不饱和多元胺酰胺和较低分子量酸性聚合物的盐溶液或具有酸性基团的共聚体溶液。The corrosion-resistant nano-modified composite coating for ships according to claim 2, wherein the mixed solvent is a mixture of two or more of xylene, aromatic cyclohexanone, ethylene glycol butyl ether, and propylene glycol methyl ether. The auxiliary agent is a salt solution of unsaturated polyamine amide and a lower molecular weight acidic polymer or a copolymer solution with acidic groups.
  8. 如权利要求2所述的船舶用耐腐蚀纳米改性复合涂料，其特征在于：所述防锈颜料为钛白粉、锶铬黄、锌铬黄中两种及以上的混合物；所述填料为磷酸锌、三聚磷酸铝、铁钛粉、硫酸钡、碳酸钙、云母粉、滑石粉中的两种及以上的混合物；所述固化剂为聚酰胺固化剂和硅烷偶联剂的混合物，聚酰胺固化剂和硅烷偶联剂的质量比为200：1。The corrosion-resistant nano-modified composite paint for ships according to claim 2, wherein the anti-rust pigment is a mixture of two or more of titanium dioxide, strontium chrome yellow, and zinc chrome yellow; and the filler is phosphoric acid A mixture of two or more of zinc, aluminum tripolyphosphate, iron titanium powder, barium sulfate, calcium carbonate, mica powder, and talc; the curing agent is a mixture of polyamide curing agent and silane coupling agent, polyamide The mass ratio of curing agent and silane coupling agent is 200:1.
  9. 如权利要求1-8任一权利要求所述的船舶用耐腐蚀纳米改性复合涂料，其特征在于：所述的面漆的制备方法包括以下步骤：步骤S01：将聚醚二元醇在恒温水浴锅中预热至少30min，完成充分脱水，在搅拌器内加入完成冷却后并充分脱水的聚醚二元醇和甲苯二异氰酸酯，并加入溶剂，充分脱水的聚醚二元醇和甲苯二异氰酸酯质量比为4：1，其中溶剂为丁酮溶液，丁酮溶液采用1%摩尔的丁酮溶液，搅拌器内升温至80℃，恒温保持3~4h，获得聚氨酯预聚体；然后按比例准备好有机硅混合物，环氧树脂，纳米氧化物、有机添加剂；步骤S02：将搅拌器内温度升温至95℃，恒温保持，加入有机硅混合物，搅拌，加入有机硅混合物，持续反应5min；步骤S03：在搅拌器内加入环氧树脂，持续反应10min，持续搅拌；步骤S04：在搅拌器内加入纳米氧化物，持续反应5min，持续搅拌；步骤S05：在搅拌器内加入有机添加剂，持续搅拌，恒温保持45min以上；步骤S06：降温，获得面漆。The corrosion-resistant nano-modified composite coating for ships according to any one of claims 1-8, wherein the preparation method of the topcoat comprises the following steps: Step S01: Put the polyether glycol at a constant temperature Preheat in a water bath for at least 30 minutes to complete full dehydration. Add the fully dehydrated polyether diol and toluene diisocyanate into the blender, and add a solvent. The mass ratio of fully dehydrated polyether diol and toluene diisocyanate It is 4:1, in which the solvent is methyl ethyl ketone solution, the methyl ethyl ketone solution adopts 1% mol methyl ethyl ketone solution, the temperature in the stirrer is raised to 80 ℃, and the constant temperature is maintained for 3 to 4 hours to obtain the polyurethane prepolymer; and then prepare the organic Silicon mixture, epoxy resin, nano-oxide, organic additives; Step S02: Raise the temperature in the stirrer to 95°C, keep at constant temperature, add the silicone mixture, stir, add the silicone mixture, and continue to react for 5 minutes; Step S03: Add epoxy resin into the stirrer, continue to react for 10 minutes, and continue to stir; Step S04: Add nano-oxide in the stirrer, continue to react for 5 minutes, and continue to stir; Step S05: Add organic additives in the stirrer, continue to stir, and keep constant temperature Over 45 minutes; Step S06: Cool down to obtain a top coat.
  10. 如权利要求9所述的船舶用耐腐蚀纳米改性复合涂料，其特征在于：在步骤S02中，加入有机硅混合物的方法为依次加入二甲基硅油和聚醚改性硅，间隔时间为5min，在步骤S05中加入有机添加剂的方法为：依次加入催化剂、扩链剂、交联剂和增塑剂，间隔时间不超过5min，持续搅拌。The corrosion-resistant nano-modified composite coating for ships according to claim 9, characterized in that: in step S02, the method of adding the silicone mixture is adding dimethyl silicone oil and polyether modified silicone in sequence, with an interval of 5 min. , The method of adding organic additives in step S05 is: adding catalyst, chain extender, crosslinking agent and plasticizer in sequence, with an interval of no more than 5 minutes, and stirring continuously.
PCT/CN2019/108174 2019-03-21 2019-09-26 Corrosion-resistant nanometer modified composite coating for use in ship WO2020186721A1 (en)

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CN113416487A (en) * 2021-06-18 2021-09-21 中国船舶重工集团公司第七二五研究所 High-weather-resistance finish paint for ship composite material protection and preparation method thereof
CN114196279B (en) * 2021-12-17 2022-07-29 浙江鱼童新材料股份有限公司 Low-surface-energy ship primer and preparation method thereof

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