CN109957317A - A kind of ship modified composite coating of anti-corrosion nano - Google Patents

A kind of ship modified composite coating of anti-corrosion nano Download PDF

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Publication number
CN109957317A
CN109957317A CN201910215511.8A CN201910215511A CN109957317A CN 109957317 A CN109957317 A CN 109957317A CN 201910215511 A CN201910215511 A CN 201910215511A CN 109957317 A CN109957317 A CN 109957317A
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Prior art keywords
parts
nano
priming paint
ship
mixture
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CN201910215511.8A
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Chinese (zh)
Inventor
张强勇
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Jiangsu Maritime Institute
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Jiangsu Maritime Institute
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Priority to CN201910215511.8A priority Critical patent/CN109957317A/en
Publication of CN109957317A publication Critical patent/CN109957317A/en
Priority to PCT/CN2019/108174 priority 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
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
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    • 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

Abstract

The invention discloses a kind of ship modified composite coatings of anti-corrosion nano, including finishing coat and priming paint, the priming paint is for being covered in marine surface, the finishing coat includes 140 ~ 160 parts of base polyurethane prepolymer for use as, 10 ~ 20 parts of organosilicon mixture, 12 ~ 18 parts of epoxy resin, 1 ~ 5 part of nano-oxide, 15 ~ 25 parts of organic additive to cover the priming paint, the finishing coat；The priming paint includes 25 ~ 33 parts of epoxy resin, 12 ~ 18 parts of mixed solvent, 2 ~ 5 parts of auxiliary agent, 15 ~ 30 parts of rust resisting pigment, 1 ~ 3 part of nano silica, 10 ~ 15 parts of filler, 12 ~ 18 parts of curing agent, wherein, the nano silica accounts for 1% or more of priming paint toatl proportion.The present invention optimizes base paint formulation, increases the adhesion of priming paint and marine surface, while optimizing topcoat formulation by optimization design, good can stick combination with priming paint, and have good impact strength, caking property and corrosion resistance.

Description

A kind of ship modified composite coating of anti-corrosion nano
Technical field
The present invention relates to anticorrosive paint technology fields, and in particular to a kind of ship modified composite coating of anti-corrosion nano.
Background technique
Under the severe corrosive environments such as marine environment, acid rain atmosphere, industrial atmosphere and moist oxygen-enriched Minepit environment, steel The best erosion shield scheme of structure is to use electric arc spraying zinc, aluminium and its additional closed composite coating of alloy coat, can To obtain the permanent effective anticorrosion service life.Brushing can penetrate into the hole of metal coating in the sealer of sprayed coating surface well In gap and be anchored at its surface, sealer metal spraying layer surface combination effect than sandblasting matrix surface associativity also It is better.And obviously slow down by depletion rate of the sprayed metal coating of Seal treatment in corrosive environment, even if passing through one A little year surface-closed coating failures, but metal coating below still is able to maintain a good state, at without closing The depletion rate of the metal coating of reason wants much slower, and works can be effectively protected more for a long time.
It needs coating protective paint peculiar to vessel to improve service life to enhance anti-corrosion effect in marine surface at present, is usually to adopt It is sprayed with priming paint finishing coat, and existing protective paint peculiar to vessel has mostly that antiseptic property is bad, adhesion strength is bad, is used for a long time It is easy to appear brittleness in the process to fall off, especially when by impact force, impact strength is poor, causes to be easy to appear paint Defect.
Summary of the invention
1, technical problem to be solved:
Existing protective paint peculiar to vessel has that antiseptic property is bad, adhesion strength is bad, it is crisp to be easy to appear in long-term use process mostly Property falls off, and especially when by impact force, impact strength is poor, leads to the defect for being easy to appear paint.
2, technical solution:
In order to solve problem above, the present invention provides a kind of ship modified composite coating of anti-corrosion nano, including finishing coat and Priming paint, for the priming paint for being covered in marine surface, the finishing coat includes that polyurethane is pre- to cover the priming paint, the finishing coat 140-160 parts of aggressiveness, 10-20 parts of organosilicon mixture, 12-18 parts of epoxy resin, 1 ~ 5 part of nano-oxide, organic additive 15 ~ 25 parts, the priming paint includes nano silica, the nano silica account for priming paint quality toatl proportion 1% and with On.
The finishing coat includes 152 parts of base polyurethane prepolymer for use as, 16 parts of organosilicon mixture, 14 parts of epoxy resin, nano oxidized 3 parts of zinc, 18 parts of organic additive.
The priming paint further includes 25-33 parts of epoxy resin, 12-18 parts of mixed solvent, 2-5 parts of auxiliary agent, rust resisting pigment 15-30 Part, 10 ~ 15 parts of filler, 12 ~ 18 parts of curing agent.
The organosilicon mixture is made of dimethicone and polyether-modified silicon, wherein dimethicone and polyether-modified Silicon mass ratio is 3:1.
The polyether-modified silicon is TEGO Foamex 810.
The nano-oxide is the mixture of one or more of titanium oxide, zinc oxide, zirconium oxide, iron oxide.
The organic additive includes catalyst, chain extender, crosslinking agent and plasticizer, and wherein catalyst uses tin dilaurate Dibutyl tin, chain extender use diethylene glycol (DEG), and crosslinking agent uses trimethylolpropane, and plasticizer uses dioctyl phthalate, Catalyst, chain extender, crosslinking agent, the mass ratio between plasticizer are 1:3:2:3.
The mixed solvent is dimethylbenzene, aromatic hydrocarbons cyclohexanone, butyl glycol ether, two kinds or more mixed in propylene glycol monomethyl ether Close object, the auxiliary agent is the salting liquid of unsaturated polynary amine amide and lower molecular weight acidic polymer or with acidic-group It is copolymerized liquid solution.
The rust resisting pigment is titanium dioxide, strontium chromate, two kinds or more of mixture in zinc yellow；The filler is phosphoric acid Zinc, aluminium triphosphate, ferrotitanium powder, barium sulfate, calcium carbonate, mica powder, two kinds or more of mixture in talcum powder；It is described solid Agent is the mixture of polyamide curing agent and silane coupling agent, and the mass ratio of polyamide curing agent and silane coupling agent is 200: 1。
The preparation method of the finishing coat is the following steps are included: step S01: polyether Glycols are pre- in thermostat water bath Heat at least 30min completes sufficiently dehydration, the polyether Glycols and toluene being dehydrated after addition completion is cooling in blender and sufficiently Diisocyanate, and solvent is added, the polyether Glycols and toluene di-isocyanate(TDI) mass ratio being sufficiently dehydrated are 4:1, wherein molten Agent is butanone solution, and butanone solution uses 1% mole of butanone solution, and 80 DEG C are warming up in blender, and constant temperature keeps 3 ~ 4h, obtains Obtain base polyurethane prepolymer for use as；；Then it gets out organosilicon mixture, epoxy resin, nano-oxide, organic additive in proportion； Step S02: being warming up to 95 DEG C for temperature in blender, and constant temperature is kept, and organosilicon mixture is added, and it is mixed that organosilicon is added in stirring Close object, sustained response 5min；Step S03: being added epoxy resin in blender, and sustained response 10min is lasting to stir；Step S04: being added nano-oxide in blender, and sustained response 5min is lasting to stir；Step S05: it is added in blender organic Additive, lasting to stir, constant temperature keeps 45min or more；Step S06: cooling obtains finishing coat.
In step S02, the method that organosilicon mixture is added is to sequentially add dimethicone and polyether-modified silicon, It is 5min every the time；In step S05 be added organic additive method are as follows: sequentially add catalyst, chain extender, crosslinking agent and Plasticizer, interval time is no more than 5min, lasting to stir.
3, the utility model has the advantages that
By optimization design, optimizes base paint formulation, increases the adhesion of priming paint and marine surface, while optimizing topcoat formulation, It good can stick combination with priming paint, and have good impact strength, caking property and corrosion resistance.
Specific embodiment
The present invention is described in detail below.
The present invention provides a kind of ship modified composite coating of anti-corrosion nano, including finishing coat and priming paint, the priming paint For being covered in marine surface, the finishing coat includes base polyurethane prepolymer for use as 140-160 to cover the priming paint, the finishing coat Part, 10-20 parts of organosilicon mixture, 12-18 parts of epoxy resin, 1-5 parts of nano-oxide, 15-25 parts of organic additive are described Priming paint include nano silica, the nano silica accounts for 1% or more priming paint quality toatl proportion.
The priming paint further includes 25-33 parts of epoxy resin, 12-18 parts of mixed solvent, 2-5 parts of auxiliary agent, rust resisting pigment 15-30 Part, 10-15 parts of filler, 12-18 parts of curing agent.
Wherein, in priming paint mixed solvent be dimethylbenzene, aromatic hydrocarbons cyclohexanone, butyl glycol ether, in propylene glycol monomethyl ether two kinds and Above mixture.
Wherein, auxiliary agent is the salting liquid of unsaturated polynary amine amide and lower molecular weight acidic polymer or has in priming paint The copolymerization liquid solution of acidic-group.
Wherein, rust resisting pigment is titanium dioxide, strontium chromate, two kinds or more of mixture in zinc yellow in priming paint.
Wherein, filler is trbasic zinc phosphate, aluminium triphosphate, ferrotitanium powder, barium sulfate, calcium carbonate, mica powder, talcum powder in priming paint In two kinds or more of mixture.
Wherein, in priming paint curing agent be polyamide curing agent and silane coupling agent mixture, polyamide curing agent and silicon The mass ratio of alkane coupling agent is 200:1, and wherein proportion increases silane coupling agent in curing agent, and whole adhesion can be improved Energy.
In priming paint, nano silica is less than 100cp, the thickened pulp that solid content is 22%, by constantly trying using viscosity It tests, influence of the nano silica to epoxy primer adhesion strength for different content, the nanometer two for being 0.5% from accounting Silica, the increased caking ability of institute only has 0.2Mpa, and the nano silica of 1% accounting content can increase 1.2Mpa, hold It is continuous to increase nanometer titanium dioxide silicone content, wherein the nano silica of 1.5% accounting content can increase 1.5Mpa, 2.0% accounting The nano silica of content can increase 1.4Mpa, and the nano silica of 3.0% accounting content can increase 1.3Mpa, The nano silica of 4.0% accounting content can increase 1.4Mpa, accordingly, it is preferred that accounting for toatl proportion using nano silica It is 1%.
By optimizing base paint formulation, it is modified using nano silica, increases the adhesion strength of epoxy-based lacquers, simultaneously With good corrosion resistance.
The finishing coat is preferably 152 parts of base polyurethane prepolymer for use as, 16 parts of organosilicon mixture, 14 parts of epoxy resin, nano oxygen Change 3 parts of zinc, 18 parts of organic additive.
The preparation method of the finishing coat is the following steps are included: step S01: polyether Glycols are pre- in thermostat water bath Heat at least 30min completes sufficiently dehydration, the polyether Glycols and toluene being dehydrated after addition completion is cooling in blender and sufficiently Diisocyanate, and solvent is added, the polyether Glycols and toluene di-isocyanate(TDI) mass ratio being sufficiently dehydrated are 4:1, wherein molten Agent is butanone solution, and butanone solution uses 1% mole of butanone solution, and 80 DEG C are warming up in blender, and constant temperature keeps 3 ~ 4h, obtains Base polyurethane prepolymer for use as is obtained, then gets out organosilicon mixture, epoxy resin, nano-oxide, organic additive in proportion；Step Rapid S02: being warming up to 95 DEG C for temperature in blender, and constant temperature is kept, and organosilicon mixture is added, and organosilicon mixing is added in stirring Object, sustained response 5min；Step S03: being added epoxy resin in blender, and sustained response 10min is lasting to stir；Step S04: being added nano-oxide in blender, and sustained response 5min is lasting to stir；Step S05: it is added in blender organic Additive, lasting to stir, constant temperature keeps 45min or more；Step S06: cooling obtains finishing coat.
In step S02, the method that organosilicon mixture is added is to sequentially add dimethicone and polyether-modified silicon, It is 5min every the time；In step S05 be added organic additive method are as follows: sequentially add catalyst, chain extender, crosslinking agent and Plasticizer, interval time is no more than 5min, lasting to stir.
The advantage of finishing coat provided by the invention is: utilizing the main chain backbone for the Si-O-Si that organosilicon is formed, Si atom side Base by with polyurethane prepolymer precursor reactant generate Si-O-C key block-graft copolymer, in conjunction with epoxy resin, make its with it is organic Silicone polyurethane copolymer forms inierpeneirating network structure, by the catalysis of organic additive, to finally obtain finished product.
Ship provided by the invention see the table below with the parameter comparison of the modified composite coating of anti-corrosion nano and existing product:
Detection project Unmodified polyurethane coating (existing product) Nano modification composite polyurethane ship topcoat paint Examination criteria
Impact strength kgcm 15 50 GB/T 1732
Tensile strength Mpa 1.55 8.4 GB/T 16421
Water absorption rate % 18.45 1.32 GB/T 6753.3
Acid resistance 15%HCl Coating is intact after impregnating 240h, and coating has peeling after 360h Coating is intact after impregnating 480h, and coating has peeling after 540h GB/T 1763
Alkali resistance 15%NaOH Coating is intact after impregnating 720h, and coating has peeling after 840h Coating is intact after impregnating 1080h, and coating has peeling after 1350h GB/T 1763
Resistance to salt water 3.5%NaCl Coating is intact after impregnating 480h, and coating has peeling after 720h Coating is intact after impregnating 840h, and coating has peeling after 1080h GB/T 1763
In conjunction with upper table, by comparison, product of the present invention various aspects of performance is above prior art products, Optimum utilization organosilicon with The reaction of base polyurethane prepolymer for use as, convenient for combining epoxy resin to form the web frame that interlocks, and it is modified and organic using nano-oxide The catalysis of additive is reacted, to improve the impact strength of coating, caking property and corrosion resistance.
Although the present invention has been described by way of example and in terms of the preferred embodiments, they be not it is for the purpose of limiting the invention, it is any ripe This those skilled in the art is practised, without departing from the spirit and scope of the invention, can make various changes or retouch from working as, therefore guarantor of the invention Shield range should be subject to what claims hereof protection scope was defined.

Claims (10)

1. a kind of ship modified composite coating of anti-corrosion nano, including finishing coat and priming paint, the priming paint is for being covered in ship Surface, the finishing coat is to cover the priming paint, it is characterised in that: the finishing coat includes 140-160 parts of base polyurethane prepolymer for use as, has 10-20 parts of machine silicon mixture, 12-18 parts of epoxy resin, 1 ~ 5 part of nano-oxide, 15 ~ 25 parts of organic additive, the bottom Enamel-cover includes nano silica, and the nano silica accounts for 1% or more priming paint quality toatl proportion.
2. the ship as described in claim 1 modified composite coating of anti-corrosion nano, it is characterised in that: the finishing coat includes poly- 152 parts of urethane performed polymer, 16 parts of organosilicon mixture, 14 parts of epoxy resin, 3 parts of nano zine oxide, 18 parts of organic additive.
3. the ship as described in claim 1 modified composite coating of anti-corrosion nano, it is characterised in that: the priming paint further includes 25 ~ 33 parts of epoxy resin, 12 ~ 18 parts of mixed solvent, 2 ~ 5 parts of auxiliary agent, 15 ~ 30 parts of rust resisting pigment, 10 ~ 15 parts of filler, curing agent 12 ~ 18 parts.
4. ship as described in the right 1 modified composite coating of anti-corrosion nano, it is characterised in that: the organosilicon mixture by Dimethicone and polyether-modified silicon are constituted, and wherein dimethicone and polyether-modified silicon mass ratio are 3:1.
5. the ship as described in claim 1 modified composite coating of anti-corrosion nano, it is characterised in that: the nano-oxide For the mixture of one or more of titanium oxide, zinc oxide, zirconium oxide, iron oxide.
6. the ship as described in claim 1 modified composite coating of anti-corrosion nano, it is characterised in that: the organic additive Including catalyst, chain extender, crosslinking agent and plasticizer, wherein catalyst uses dibutyl tin dilaurate, and chain extender uses two Glycol, crosslinking agent use trimethylolpropane, plasticizer use dioctyl phthalate, catalyst, chain extender, crosslinking agent, Mass ratio between plasticizer is 1:3:2:3.
7. the ship as claimed in claim 2 modified composite coating of anti-corrosion nano, it is characterised in that: the mixed solvent is Dimethylbenzene, aromatic hydrocarbons cyclohexanone, butyl glycol ether, two kinds or more of mixture in propylene glycol monomethyl ether, the auxiliary agent is unsaturation The salting liquid of polynary amine amide and lower molecular weight acidic polymer or copolymerization liquid solution with acidic-group.
8. the ship as claimed in claim 2 modified composite coating of anti-corrosion nano, it is characterised in that: the rust resisting pigment is Titanium dioxide, strontium chromate, two kinds or more of mixture in zinc yellow；The filler be trbasic zinc phosphate, aluminium triphosphate, ferrotitanium powder, Barium sulfate, calcium carbonate, mica powder, two kinds or more of mixture in talcum powder；The curing agent be polyamide curing agent and The mass ratio of the mixture of silane coupling agent, polyamide curing agent and silane coupling agent is 200:1.
9. the ship modified composite coating of anti-corrosion nano as described in claim 1-8 any claim, it is characterised in that: The preparation method of the finishing coat is the following steps are included: step S01: polyether Glycols are preheated at least in thermostat water bath 30min completes sufficiently dehydration, the polyether Glycols and toluene diisocyanate being dehydrated after addition completion is cooling in blender and sufficiently Acid esters, and solvent is added, the polyether Glycols and toluene di-isocyanate(TDI) mass ratio being sufficiently dehydrated are 4:1, and wherein solvent is fourth Ketone solution, butanone solution use 1% mole of butanone solution, and 80 DEG C are warming up in blender, and constant temperature keeps 3 ~ 4h, obtains poly- ammonia Ester performed polymer；Then it gets out organosilicon mixture, epoxy resin, nano-oxide, organic additive in proportion；Step S02: Temperature in blender is warming up to 95 DEG C, constant temperature is kept, and organosilicon mixture is added, and organosilicon mixture is added in stirring, is continued React 5min；Step S03: being added epoxy resin in blender, and sustained response 10min is lasting to stir；Step S04: it is stirring Nano-oxide is added in device, sustained response 5min is lasting to stir；Step S05: being added organic additive in blender, holds Continuous stirring, constant temperature keep 45min or more；Step S06: cooling obtains finishing coat.
10. the ship as claimed in claim 9 modified composite coating of anti-corrosion nano, it is characterised in that: in step S02, The method that organosilicon mixture is added is to sequentially add dimethicone and polyether-modified silicon, interval time 5min, in step The method of organic additive is added in S05 are as follows: sequentially add catalyst, chain extender, crosslinking agent and plasticizer, interval time does not surpass 5min is crossed, it is lasting to stir.
CN201910215511.8A 2019-03-21 2019-03-21 A kind of ship modified composite coating of anti-corrosion nano Pending CN109957317A (en)

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Application publication date: 20190702