CN103627286A - Water-based finishing coat for heavy-duty coating and preparation method of water-based finishing coat - Google Patents
Water-based finishing coat for heavy-duty coating and preparation method of water-based finishing coat Download PDFInfo
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- CN103627286A CN103627286A CN201310634078.4A CN201310634078A CN103627286A CN 103627286 A CN103627286 A CN 103627286A CN 201310634078 A CN201310634078 A CN 201310634078A CN 103627286 A CN103627286 A CN 103627286A
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Abstract
The invention belongs to the technical field of anti-corrosion coating, and discloses water-based finishing coat for heavy-duty coating and a preparation method of the water-based finishing coat. The water-based finishing coat comprises a water-based fluorinated siloxane-acrylate emulsion, a pigment and a filler, an additive, a thickener and water; the water-based fluorinated siloxane-acrylate emulsion accounts for 50-60 percent of the total weight of primer, and is obtained through reaction of styrene, a methacrylate monomer, an acrylic ester monomer, a fluorinated acrylate monomer, an organic silicon mixed monomer and a functional monomer; the organic silicon mixed monomer is a mixture of octamethyl cyclotetrasiloxane and vinyl alkoxy silane; the content of the organic silicon mixed monomer in the water-based fluorinated siloxane-acrylate emulsion is 15-25 percent; the functional monomer comprises an itaconic acid; the glass-transition temperature of the water-based fluorinated siloxane-acrylate emulsion is 45-60 DEG C. The invention further provides a preparation method of the water-based finishing coat. The water-based emulsion is prepared from an organic silicon modified acrylic acid and an organic fluorine modified acrylic acid, and the finishing coat for the heavy anti-corrosion coating is prepared from the water-based emulsion, and has the characteristics of low VOC emission and excellent anti-corrosion performance; the preparation method is simple, and the water-based finishing coat is wide in adaptability.
Description
Technical field
The present invention relates to a kind of aqueous heavy anti-corrosion paint technical field, be specifically related to a kind of water-based organosilicon crylic acid latex that adopts and as the heavy-duty coating of membrane-forming agent, use the preparation method of priming paint and this priming paint, and a kind of water-based fluorine organosilicon crylic acid latex that adopts is used the preparation method of finish paint and this finish paint as the heavy-duty coating of membrane-forming agent.
Background technology
Heavy-duty coating (Heavy-duty Coating) refers to relatively conventional protective system; can in relatively harsh corrosive environment, use; and there is the class protective system than the conventional longer protection period of protective system, be the matched coating that comprises priming paint, middle layer and finish paint.The heavy anticorrosion implication that has two aspects, one refers to that corrosive environment is severe; Two refer to that the protection life-span is long, if heavy-duty coating is under ocean environment and chemical atmosphere, at least can use more than 10 years; And in acid, alkali, salt and solvent medium, and have under the condition of certain temperature, conventionally also can use more than 5 years.Thereby the coating that can reach heavily requirement for anticorrosion has that film forming thickness is large, multi-layer paint films is compound and the exsertile feature of paint film erosion resistance conventionally, comprise marine finish, coating container, wind-powered electricity generation coating, coating, storage tin paint etc. for bridge.
Heavy-duty coating is generally comprised of membrane-forming agent, solvent, filler, pigment, existing heavy-duty coating is in order to obtain higher film forming thickness to improve preservative effect and to reduce running cost, the organic solvent systems that dissolving obtains to membrane-forming agent that adopt as the base-material of heavy-duty coating more, in use discharge a large amount of volatile organic gas (VOC), to environment.For the requirement of the protection that conforms, environmental protection is the main direction that is following heavy-duty coating, specifically comprise environment-friendly type coating resin modification, improve the solid content of heavy-duty coating, the development of aqueous heavy anti-corrosion paint etc.
Existing aqueous heavy anti-corrosion paint comprises aqueous epoxide resin paint, aqueous polyurethane coating and aqueous inorganic zinc silicate coating etc., wherein aqueous epoxide resin paint is good owing to having film-forming performance, strong adhesion, rete mechanical property is good, the advantages such as hardness is good, be used widely, but the character by epoxy resin itself determines that it exists time of drying long in practice, weathering resistance is not good enough, film-forming process requires the shortcomings such as high to construction environment, thereby development of new film-forming resin is to improve rete weathering resistance and to reduce construction cost, it is one of the developing direction in aqueous heavy anti-corrosion paint field.
Summary of the invention
The problem existing in order to solve above-mentioned prior art, the invention provides a kind of low VOC content, environmentally friendly, strong adhesion, salt spray corrosion resistance excellent, without solidifying, aqueous heavy anti-corrosion paint priming paint easy to use, and the preparation method of this priming paint.
The present invention also provide a kind of low VOC content, environmentally friendly, water-fast weather resistance outstanding, without curing aqueous heavy anti-corrosion paint finish paint, and the preparation method of this finish paint.
The technical solution used in the present invention is:
An aqueous heavy anti-corrosion paint priming paint, comprises water-based organosilicon crylic acid latex, color stuffing, auxiliary agent, thickening material and water;
Described water-based organosilicon crylic acid latex accounts for 45～55% of priming paint gross weight, by vinylbenzene, methacrylate monomer, acrylate monomer, organosilane monomer and function monomer reaction, obtained, described organosilane monomer content is 3～8%, described function monomer comprises methylene-succinic acid, (methyl) crylic acid hydroxy ester and vinyl cyanide, and the second-order transition temperature of described water-based organosilicon crylic acid latex is 35～50 ℃.
Described water-based organosilicon crylic acid latex is obtained by vinylbenzene, methacrylate monomer, acrylate monomer, organosilane monomer and function monomer reaction.Preferably, described methacrylate monomer is selected from methyl methacrylate.Preferably, described acrylate monomer is selected from one or more in butyl acrylate, Isooctyl acrylate monomer, ethyl propenoate, methyl acrylate.
Preferably, the mass ratio of described vinylbenzene and methacrylate monomer is 1:(2～6), the mass ratio of described vinylbenzene and methacrylate monomer quality sum and acrylate monomer is (1.5～4): 1.
Preferably, in described function monomer, methylene-succinic acid: (methyl) crylic acid hydroxy ester: the mol ratio of vinyl cyanide is (0.5～2): (1～2.5): (3～5).
Preferably, in described function monomer, (methyl) crylic acid hydroxy ester is selected from one or more in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410.
Preferably, described function monomer further comprises one or more in glycidyl methacrylate, N hydroxymethyl acrylamide, vinylformic acid, methacrylic acid.
Preferably, described function monomer accounts for the 7-12% of monomer total mass.
Preferably, described organosilane monomer is one or several in vinyltriethoxysilane, γ-aminopropyl triethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltrimethoxy silane, methacryloxypropyl trimethoxy silane, vinyl silane triisopropoxide.
The content of described organosilane monomer is 3-8%, refers to that organosilane monomer accounts for the per-cent of vinylbenzene, methacrylate monomer, acrylate monomer, organosilane monomer and function monomer total mass.
Preferably, described color stuffing accounts for 25～35% of priming paint gross weight.
More preferably, described color stuffing comprises the following component of meter by weight:
Described auxiliary agent comprises film forming accelerating, film coalescence aid and anticorrosive additive.Preferably, described film forming accelerating comprises dispersion agent, wetting agent, defoamer and flow agent.
Preferably, described film coalescence aid is water-soluble silicon oil, and its consumption is to account for 3.8～6% of priming paint total mass.
Preferably, described thickening material is polyurethane associative thickener RM-8W.
Described anticorrosive additive comprises the agent of anti-sudden strain of a muscle rust.
The preparation method of priming paint for aqueous heavy anti-corrosion paint of the present invention, comprises the following steps:
By vinylbenzene, methacrylate monomer, acrylate monomer and function monomer pre-emulsification, obtain pre-emulsion A; By organosilane monomer pre-emulsification, obtain pre-emulsion B;
Reactive emulsifier is mixed with water, be warming up to 78～82 ℃, add after initiator solution, drip part pre-emulsion A, drip again pre-emulsion B, remaining pre-emulsion A and initiator solution simultaneously, after being added dropwise to complete, be warming up to 78-82 ℃ of isothermal reaction 1～3h, be cooled to room temperature, obtain water-based organosilicon crylic acid latex;
After color stuffing, auxiliary agent and water blending dispersion is even, add water-based organosilicon crylic acid latex to stir, add thickening material adjusting viscosity to 80～100ku, regulate pH value to 7-9, stir, filter, obtain aqueous heavy anti-corrosion paint priming paint.
In the process of preparation water-based organosilicon crylic acid latex, during polyreaction, first drip part vinylbenzene, acrylate, functional monomer etc., drip again organosilane monomer and residue comonomer, form organosilicon core-shell emulsion particle outside, can give full play to organosilyl modification advantage.
Preferably, described reactive emulsifier is allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate.
The present invention also provides a kind of aqueous heavy anti-corrosion paint finish paint, comprises water-based fluorine organosilicon crylic acid latex, color stuffing, auxiliary agent, thickening material and water;
Described water-based fluorine organosilicon crylic acid latex accounts for 50～60% of priming paint gross weight, by vinylbenzene, methacrylate monomer, acrylate monomer, fluorinated acrylate monomer, organosilicon mix monomer and function monomer reaction, obtained, described organosilicon mix monomer is the mixture of octamethylcyclotetrasiloxane and vinyl alkoxy silane, in described water-based fluorine organosilicon crylic acid latex, the content of organosilane monomer is 15-25%, described function monomer comprises methylene-succinic acid, and the second-order transition temperature of described water-based fluorine organosilicon crylic acid latex is 45～60 ℃.
Described water-based fluorine organosilicon crylic acid latex is obtained by vinylbenzene, methacrylate monomer, acrylate monomer, organosilane monomer and function monomer reaction.Preferably, described methacrylate monomer is selected from methyl methacrylate.Preferably, described acrylate monomer is selected from one or more in butyl acrylate, Isooctyl acrylate monomer, ethyl propenoate, methyl acrylate.
Preferably, the mass ratio of described vinylbenzene and methacrylate monomer is 1:(3.5～8), the mass ratio of described vinylbenzene and methacrylate monomer quality sum and acrylate monomer is (2～5): 1.
Preferably, described fluorinated acrylate monomer is one or more in dodecafluoroheptyl methacrylate, Hexafluorobutyl mathacrylate, trifluoroethyl methacrylate, vinylformic acid 19 fluorine esters, perfluoro capryl ethyl propenoate.
Preferably, the content of described fluorinated acrylate monomer is 5～10%, is fluorinated acrylate monomer and the ratio of vinylbenzene, methacrylate monomer, acrylate monomer, fluorinated acrylate monomer, organosilane monomer and function monomer total mass.
Preferably, in described function monomer, the content of methylene-succinic acid is 1-3%.
Preferably, described function monomer further comprises one or more in glycidyl methacrylate, N hydroxymethyl acrylamide, vinylformic acid, methacrylic acid.
Preferably, described vinyl silanes is selected from one or more in vinyltriethoxysilane, γ-aminopropyl triethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltrimethoxy silane, methacryloxypropyl trimethoxy silane, vinyl silane triisopropoxide.
Preferably, in described organosilicon mix monomer, the mol ratio of octamethylcyclotetrasiloxane and vinyl alkoxy silane is (2-3): (0.8-1.2).
The content of described organosilane monomer is 15-25%, refers to that organosilane monomer accounts for the per-cent of vinylbenzene, methacrylate monomer, acrylate monomer, fluorinated acrylate monomer, organosilicon mix monomer and function monomer total mass.
Preferably, described color stuffing accounts for 20～30% of finish paint gross weight.
Preferably, described color stuffing comprises the component of the following meter of mark by weight:
25～31 parts of zinc phosphates
20～26 parts of superfine talcum powders
10～14 parts of Rutile type Titanium Dioxides
Described auxiliary agent comprises film forming accelerating and film coalescence aid.Preferably, film forming accelerating comprises dispersion agent, wetting agent, defoamer and flow agent.
Preferably, described film coalescence aid is water-soluble silicon oil, and its consumption is to account for 4～6.5% of finish paint total mass.
Preferably, described thickening material is polyurethane associative thickener RM-8W.
The preparation method of finish paint for aqueous heavy anti-corrosion paint of the present invention, comprises the following steps:
By vinylbenzene, methacrylate monomer, acrylate monomer, fluorinated acrylate monomer and function monomer emulsification, obtain pre-emulsion C;
Reactive emulsifier, catalyzer are mixed with water, be warming up to 80～87 ℃, drip successively octamethylcyclotetrasiloxane and vinyl alkoxy silane, in 80-87 ℃ of isothermal reaction 0.5～2h, add part initiator solution and part pre-emulsion C, then drip residue pre-emulsion C and residue initiator solution simultaneously, after being added dropwise to complete, be warming up to 80-87 ℃ of isothermal reaction 1～3h, be cooled to room temperature, regulate pH to neutral, obtain water-based fluorine organosilicon crylic acid latex;
After color stuffing, auxiliary agent and water blending dispersion is even, add water-based fluorine organosilicon crylic acid latex to stir, add thickening material adjusting viscosity to 80～100ku, then regulate pH value to 7-9, stir, filter, obtain aqueous heavy anti-corrosion paint finish paint.
Preferably, described reactive emulsifier is allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate.
Preferably, described catalyzer is Witco 1298 Soft Acid.
In the preparation process of above-mentioned water-based fluorine organosilicon crylic acid latex, after utilizing octamethylcyclotetrasiloxane (D4) open loop, react with vinyl alkoxy silane, generation is with the silicone intermediate of vinyl, carry out copolymerized grafting with vinylbenzene, acrylate, fluorinated acrylate monomer etc. again, what obtain high silicon content take organosilicon as the fluorinated silicone modified acrylate polymer emulsion that core, the vinylformic acid organic fluorine multipolymer of take are shell, significantly improves the weather-proof and corrosion resistance nature of finish paint.
The technique effect that the present invention is useful: aqueous heavy anti-corrosion paint of the present invention adopts water-based organosilicon crylic acid latex as film forming base-material with priming paint, make priming paint there is excellent sticking power and corrosion resistance nature, and aqueous heavy anti-corrosion paint of the present invention is film forming base-material with finish paint employing water-based fluorine organosilicon crylic acid latex, make finish paint weather resistance outstanding, the aqueous heavy anti-corrosion paint that both combinations obtain is when application floating coat thickness is 100 μ m, the acid resistance salt fog time surpasses 1500h, well beyond heavy antiseptic property requirement, and raw material is easy to get, preparation technology is simple, VOC free discharge, safety and environmental protection, be convenient to industrialization.
Embodiment
Below provide specific embodiment the present invention is further detailed, wherein embodiment 1～3 is for preparing the specific embodiment of priming paint for aqueous heavy anti-corrosion paint, and embodiment 4～6 is for preparing the specific embodiment of finish paint for aqueous heavy anti-corrosion paint.
Embodiment 1
The preparation method of priming paint for aqueous heavy anti-corrosion paint, comprises following operation steps:
Preparation water-based organosilicon crylic acid latex:
Vinylbenzene 45g, methyl methacrylate 174g, butyl acrylate 81.3g, methylene-succinic acid 7.4g, hydroxyethyl methylacrylate 10g and vinyl cyanide 12.6g are carried out to emulsification in the 90g water that contains 0.6g sodium lauryl sulphate, obtain pre-emulsion A;
Vinyltriethoxysilane 18g is added in the 15g water that contains 0.2g Arlacel-80,0.1g sodium lauryl sulphate and carries out emulsification, obtain pre-emulsion B;
2.4g allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate is added in 240g water and is uniformly mixed, be warming up to 80 ℃, add 25g ammonium persulfate aqueous solution (mass concentration is 2%), drip 140g pre-emulsion A, time for adding is 2h, after being added dropwise to complete, drip again 33g pre-emulsion B simultaneously, remaining 280.6g pre-emulsion A and remaining 50g ammonium persulfate aqueous solution (mass concentration is 2%), time for adding is 3h, after being added dropwise to complete, in 80 ℃ of reaction 2.5h, be cooled to room temperature, the ammoniacal liquor that is 28% with mass percent concentration is adjusted PH to 7, obtain water-based organosilicon crylic acid latex.
Adopting dsc (DSC) is 45 ℃ according to the second-order transition temperature of GB19466-2 test gained water-based organosilicon crylic acid latex, and adopting the viscosity of rotational viscosimeter test water-based organosilicon crylic acid latex is 250cps.
Prepare aqueous heavy anti-corrosion paint priming paint:
By kaolin 69.8g, zinc powder 44.1g, Rutile type Titanium Dioxide 26.9g, process white 10g and dispersion agent (5040, the pure and beautiful chemical industry in Guangzhou) 0.5g, wetting agent X-4050.25g, defoamer A1102g adds in 83.5g distilled water, in high speed dispersor with 2500r/min rotating speed high-speed stirring 0.5h, the water-based organosilicon crylic acid latex 276g that slowly adds above preparation, rotating speed with 1200r/min stirs 30min, add anti-sudden strain of a muscle rust agent CK161g, defoamer A1102g and film coalescence aid water-soluble silicon oil 25g, add again 1.8g polyurethane associative thickener RM-8W, with stormer viscosity instrumentation, determine viscosity and reach 90ku, with ammoniacal liquor, regulate PH=9, under the rotating speed of 800r/min, stir 15min, through 200 mesh filter screens, filter, obtain aqueous heavy anti-corrosion paint priming paint.
Embodiment 2
The preparation method of priming paint for aqueous heavy anti-corrosion paint, comprises following operation steps:
Preparation water-based organosilicon crylic acid latex:
Vinylbenzene 25.5g, methyl methacrylate 150.2g, ethyl propenoate 113.3g, methylene-succinic acid 4g, hydroxyethyl methylacrylate 19.8g and vinyl cyanide 16g are carried out to emulsification in the 90g water that contains 0.6g sodium lauryl sulphate, obtain pre-emulsion A;
Vinyltriethoxysilane 10.9g is added in the 9g water that contains 0.12g Arlacel-80,0.06g sodium lauryl sulphate and carries out emulsification, obtain pre-emulsion B;
2.3g allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate is added in 234g water and is uniformly mixed, be warming up to 82 ℃, add 24g ammonium persulfate aqueous solution (mass concentration is 2%), drip 140g pre-emulsion A, time for adding is 1.5h, after being added dropwise to complete, drip again 20g pre-emulsion B, remaining 280g pre-emulsion A and remaining 49g ammonium persulfate aqueous solution (mass concentration is 2%) simultaneously, time for adding is 4h, after being added dropwise to complete, in 78 ℃ of reaction 1.5h, be cooled to room temperature, with ammoniacal liquor, adjust PH to 7, obtain water-based organosilicon crylic acid latex.
Adopting dsc (DSC) is 50 ℃ according to the second-order transition temperature of GB19466-2 test gained water-based organosilicon crylic acid latex, and adopting the viscosity of rotational viscosimeter test water-based organosilicon crylic acid latex is 350cps.
Prepare aqueous heavy anti-corrosion paint priming paint:
By kaolin 85.5g, zinc powder 60.5g, Rutile type Titanium Dioxide 27.3g, process white 13g and dispersion agent (5040, the pure and beautiful chemical industry in Guangzhou) 0.6g, wetting agent X-4050.3g, defoamer A1102.5g adds in 80.5g distilled water, in high speed dispersor with 2000r/min rotating speed high-speed stirring 1h, the water-based organosilicon crylic acid latex 244.1g that slowly adds above preparation, rotating speed with 1500r/min stirs 30min, add anti-sudden strain of a muscle rust agent CK161.2g, defoamer A1102.4g and film coalescence aid water-soluble silicon oil 20.6g, add again 1.5g polyurethane associative thickener RM-8W, with stormer viscosity instrumentation, determine viscosity and reach 85ku, with ammoniacal liquor, regulate PH=9, under the rotating speed of 700r/min, stir 25min, through 200 mesh filter screens, filter, obtain aqueous heavy anti-corrosion paint priming paint.
Embodiment 3
The preparation method of priming paint for aqueous heavy anti-corrosion paint, comprises following operation steps:
Preparation water-based organosilicon crylic acid latex:
Vinylbenzene 76.6g, methyl methacrylate 160.8g, butyl acrylate 60.1g, methylene-succinic acid 11.4g, hydroxyethyl methylacrylate 6.1g and vinyl cyanide 7.3g are carried out to emulsification in the 88g water that contains 0.58g sodium lauryl sulphate, obtain pre-emulsion A;
Vinyl silane triisopropoxide 27.6g is added in the 23g water that contains 0.3g Arlacel-80,0.15g sodium lauryl sulphate and carries out emulsification, obtain pre-emulsion B;
2.4g allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate is added in 240g water and is uniformly mixed, be warming up to 78 ℃, add 25g ammonium persulfate aqueous solution (mass concentration is 2%), drip 137g pre-emulsion A, time for adding is 4h, after being added dropwise to complete, drip again 51g pre-emulsion B, remaining 273.5g pre-emulsion A and remaining 50g ammonium persulfate aqueous solution (mass concentration is 2%) simultaneously, time for adding is 2h, after being added dropwise to complete, in 82 ℃ of reaction 3h, be cooled to room temperature, with ammoniacal liquor, adjust PH to 7, obtain water-based organosilicon crylic acid latex.
Adopting dsc (DSC) is 35 ℃ according to the second-order transition temperature of GB19466-2 test gained water-based organosilicon crylic acid latex, and adopting the viscosity of rotational viscosimeter test water-based organosilicon crylic acid latex is 200cps.
Prepare aqueous heavy anti-corrosion paint priming paint:
By kaolin 78g, zinc powder 47g, Rutile type Titanium Dioxide 30.6g, process white 13.2g and dispersion agent (5040, the pure and beautiful chemical industry in Guangzhou) 0.6g, wetting agent X-4050.3g, defoamer A1102.2g adds in 39.5g distilled water, in high speed dispersor with 2300r/min rotating speed high-speed stirring 0.5h, the water-based organosilicon crylic acid latex 297.6g that slowly adds above preparation, rotating speed with 1200r/min stirs 40min, add anti-sudden strain of a muscle rust agent CK161.1g, defoamer A1102.2g and film coalescence aid water-soluble silicon oil 31.6g, add again 1.2g polyurethane associative thickener RM-8W, with stormer viscosity instrumentation, determine viscosity and reach 100ku, with ammoniacal liquor, regulate PH=9, under the rotating speed of 600r/min, stir 25min, through 200 mesh filter screens, filter, obtain aqueous heavy anti-corrosion paint priming paint.
Embodiment 4
The preparation method of finish paint for aqueous heavy anti-corrosion paint, comprises following operation steps:
Preparation water-based fluorine organosilicon crylic acid latex:
Vinylbenzene 13.1g, methyl methacrylate 57.4g, Isooctyl acrylate monomer 24g, methylene-succinic acid 2.4g, dodecafluoroheptyl methacrylate 10.8g are carried out to emulsification in the 30g water that contains 0.18g sodium lauryl sulphate, obtain pre-emulsion C;
Allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate 0.6g, Witco 1298 Soft Acid 0.4g are added in 100g water and be uniformly mixed, be warming up to 80 ℃, drip 22.4g octamethylcyclotetrasiloxane, time for adding is 2h, drip again 5.6g vinyltriethoxysilane, time for adding is 1.5h, after being added dropwise to complete in 82 ℃ of isothermal reaction 2h; Add 8.5g ammonium persulfate aqueous solution (mass concentration is 2%), drip 46g pre-emulsion C, time for adding is 2h, after being added dropwise to complete, drip again remaining 91g pre-emulsion C and 16.5g ammonium persulfate aqueous solution (mass concentration is 2%) simultaneously, time for adding is 3h, after being added dropwise to complete, in 80 ℃ of isothermal reaction 2h, after cooling, with ammoniacal liquor, regulate pH to neutral, obtain water-based fluorine organosilicon crylic acid latex.
Adopting dsc (DSC) is 50 ℃ according to the second-order transition temperature of GB19466-2 test gained water-based fluorine organosilicon crylic acid latex, and adopting the viscosity of rotational viscosimeter test water-based fluorine organosilicon crylic acid latex is 300cps.
Prepare aqueous heavy anti-corrosion paint finish paint:
By zinc phosphate 55g, superfine talcum powder 45g, Rutile type Titanium Dioxide 25g and dispersion agent (5040, the pure and beautiful chemical industry in Guangzhou) 0.5g, wetting agent X-4050.25g, defoamer A1102g mixes with distilled water 85g, in high speed dispersor with 2500r/min rotating speed high-speed stirring 1h, the water-based fluorine organosilicon crylic acid latex 275g that slowly adds above preparation, rotating speed with 1200r/min stirs 30min, add successively defoamer A1102g, film coalescence aid water-soluble silicon oil 25g, add again 1g polyurethane associative thickener RM-8W, with stormer viscosity instrumentation, determine viscosity and reach 85ku, with ammoniacal liquor, adjust PH=9, rotating speed with 800r/min stirs 15min, through 200 mesh filter screens, filter, obtain aqueous heavy anti-corrosion paint finish paint.
Embodiment 5
The preparation method of finish paint for aqueous heavy anti-corrosion paint, comprises following operation steps:
Preparation water-based fluorine organosilicon crylic acid latex:
Vinylbenzene 30g, methyl methacrylate 107.8g, butyl acrylate 28.7g, methylene-succinic acid 6.4g, vinylformic acid 19 fluorine ester 22.3g are carried out to emulsification in the 54g water that contains 0.33g sodium lauryl sulphate, obtain pre-emulsion C;
Allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate 1g, Witco 1298 Soft Acid 0.7g are added in 170g water and be uniformly mixed, be warming up to 85 ℃, drip 25.4g octamethylcyclotetrasiloxane, time for adding is 2h, drip again 9.6g vinyltriethoxysilane, time for adding is 1h, after being added dropwise to complete in 80 ℃ of isothermal reaction 0.5h; Add 14g ammonium persulfate aqueous solution (mass concentration is 2%), drip 83g pre-emulsion C, time for adding is 2h, after being added dropwise to complete, drip again remaining 165g pre-emulsion C and 28g ammonium persulfate aqueous solution (mass concentration is 2%) simultaneously, time for adding is 4h, after being added dropwise to complete, in 82 ℃ of isothermal reaction 1h, is cooled to room temperature, with ammoniacal liquor, regulate pH to neutral, obtain water-based fluorine organosilicon crylic acid latex.
Adopting dsc (DSC) is 45 ℃ according to the second-order transition temperature of GB19466-2 test gained water-based fluorine organosilicon crylic acid latex, and adopting the viscosity of rotational viscosimeter test water-based fluorine organosilicon crylic acid latex is 350cps.
Prepare aqueous heavy anti-corrosion paint finish paint:
By zinc phosphate 47.5g, superfine talcum powder 35g, Rutile type Titanium Dioxide 21.5g and dispersion agent (5040, the pure and beautiful chemical industry in Guangzhou) 0.4g, wetting agent X-4050.2g, defoamer A1101.7g mixes with distilled water 82g, in high speed dispersor with 2200r/min rotating speed high-speed stirring 1.5h, slowly add water-based fluorine organosilicon crylic acid latex 306.8g, rotating speed with 1500r/min stirs 25min, add successively defoamer A1101.7g, film coalescence aid water-soluble silicon oil 21.3g, add again 1.5g polyurethane associative thickener RM-8W, with stormer viscosity instrumentation, determine viscosity and reach 90ku, with ammoniacal liquor, adjust PH=9, rotating speed with 700r/min stirs 20min, through 200 mesh filter screens, filter, obtain aqueous heavy anti-corrosion paint finish paint.
Embodiment 6
The preparation method of finish paint for aqueous heavy anti-corrosion paint, comprises following operation steps:
Preparation water-based fluorine organosilicon crylic acid latex:
Vinylbenzene 5.4g, methyl methacrylate 41.7g, butyl acrylate 22.4g, methylene-succinic acid 1.1g, dodecafluoroheptyl methacrylate 5.2g are carried out to emulsification in the 21g water that contains 0.13g sodium lauryl sulphate, obtain pre-emulsion C;
Allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate 0.5g, Witco 1298 Soft Acid 0.3g are added in 75g water and be uniformly mixed, be warming up to 80 ℃, drip 20.4g octamethylcyclotetrasiloxane, time for adding is 2h, drip again 4.6g methacryloxypropyl trimethoxy silane, time for adding is 0.5h, after being added dropwise to complete in 80 ℃ of isothermal reaction 0.5h; Add 6.3g ammonium persulfate aqueous solution (mass concentration is 2%), drip 32g pre-emulsion C, time for adding is 2h, after being added dropwise to complete, drip again remaining 64g pre-emulsion C and 12.2g ammonium persulfate aqueous solution (mass concentration is 2%) simultaneously, time for adding is 3h, after being added dropwise to complete, in 87 ℃ of isothermal reaction 3h, is cooled to room temperature, with ammoniacal liquor, regulate pH to neutral, obtain water-based fluorine organosilicon crylic acid latex.
Adopting dsc (DSC) is 60 ℃ according to the second-order transition temperature of GB19466-2 test gained water-based fluorine organosilicon crylic acid latex, and adopting the viscosity of rotational viscosimeter test water-based fluorine organosilicon crylic acid latex is 400cps.
Prepare aqueous heavy anti-corrosion paint finish paint:
By zinc phosphate 48.9g, superfine talcum powder 44.5g, Rutile type Titanium Dioxide 22.7g and dispersion agent (5040, the pure and beautiful chemical industry in Guangzhou) 0.5g, wetting agent X-4050.25g, defoamer A1101.9g mixes with distilled water 53g, in high speed dispersor with 1500r/min rotating speed high-speed stirring 1h, the water-based fluorine organosilicon crylic acid latex 200g that slowly adds above preparation, rotating speed with 1500r/min stirs 20min, add successively defoamer A1101.9g, film coalescence aid water-soluble silicon oil 25g, add again 0.8g polyurethane associative thickener RM-8W, with stormer viscosity instrumentation, determine viscosity and reach 100ku, with ammoniacal liquor, adjust PH=9, rotating speed with 700r/min stirs 20min, through 200 mesh filter screens, filter, obtain aqueous heavy anti-corrosion paint finish paint.
Test implementation example
The performance of preparing the emulsion of using in aqueous heavy anti-corrosion paint process has crucial impact to the antiseptic property of coating, thereby provides respectively below the performance test embodiment that emulsion, priming paint and finish paint and priming paint and finish paint apply the coating of formation simultaneously:
One, respectively the water-based fluorine organosilicon crylic acid latex of preparation in the water-based organosilicon crylic acid latex of preparation in embodiment 1～3 and embodiment 4～6 is mixed with water-soluble silicon oil, obtain test filming emulsion, wherein, the mass ratio of emulsion and film coalescence aid is 11:1, filming emulsion is carried out respectively to performance test, and method is as follows:
According to GB1728-79 paint film, putty membrane assay method time of drying, measure the surface drying of the paint film that filming emulsion forms and do solid work the time;
According to mechanical stability and the Calcium ion stability of GB/T20623-2006 test filming emulsion;
According to GB9286-98 hundred lattice testing standards, measure the sticking power after filming emulsion film forming;
Water resistance test: preparing device is evenly coated on glass by filming emulsion with filming, standing one day of room temperature, then puts into 50 ℃ of loft drier inner dryings 6 hours, after taking-up is cooled to room temperature, is dipped in water, 2/3 latex film is dipped in water, observes the time of filming and turning white and coming off.
Test result is in Table 1.
Table 1
From table 1, water-based organosilicon crylic acid latex prepared by the present invention and water-based fluorine organosilicon crylic acid latex have excellent sticking power, water tolerance and stability.
Two, respectively the finish paint for aqueous heavy anti-corrosion paint (abbreviation finish paint) of preparation in the priming paint for aqueous heavy anti-corrosion paint (abbreviation priming paint) of preparation in embodiment 1～3 and embodiment 4～6 is tested, investigated the application performance of priming paint and finish paint, method is as follows:
According to GB1728-79 paint film, putty membrane assay method time of drying, measure the surface drying of the paint film that priming paint and finish paint form and do solid work the time;
According to GB9286-98 hundred lattice testing standards, measure the sticking power after priming paint and finish paint film forming;
According to the resistance to salt water of GB/T1763-1979 test priming paint and finish paint;
Test result is in Table 2.
Table 2
From table 2, priming paint and the finish paint by water-based organosilicon crylic acid latex of the present invention and water-based fluorine organosilicon crylic acid latex, prepared all have excellent sticking power and salt water resistance performance.
The priming paint of further being prepared by embodiment and finish paint carry out corrosion resistance nature test, priming paint prepared by the embodiment 1 of take and the finish paint of embodiment 4 preparations are example, the corrosion resistance nature of the water-based anticorrosion coat that test priming paint and finish paint combination obtain, testing method is with reference to GB/T1771-91, specific as follows:
Sandblasting is carried out on the tinplate surface that is 0.3mm by 150mm * 50mm, thickness, make it to reach St2 level, under 0.5MPa air pressure, with seven apertures in the human head high atomization varnish spray gun, the priming paint of embodiment 1 preparation is sprayed on the tinplate of treated mistake, after surface drying, spray again, spray altogether 3 times, obtain primer coating, then by the finish paint spraying of embodiment 4 preparations 2 times, after surface drying, obtain the sample with water-based anticorrosion coat, testing coating thickness is 100 μ m;
Sample is put into after 90 ℃ of oven drying 4h, on the water-based anticorrosion coat of sample, draw after " * " dark and base material, put into salt-spray cabinet and carry out acid salt mist experiment, acid salt fog experimental technique is with reference to GB/T1771-91, it is the acid test solution after 3 that neutralisation test solution is wherein replaced with vinegar acid for adjusting pH, and in testing liquid, salt concn is constant.By corrosion degree and the coating adhesion of sample after the acid salt mist experiment of investigation 2000h, investigate the Corrosion Protection of anticorrosion coat, as not good in Corrosion Protection, drawing " * " locates just corrosion to occur, cause coating to expand and bubble, and spreading under coating, causing drawing " * " and locate to produce more large-area corrosion, also tested the sticking power through anticorrosion coat before and after acid salt-fog test, sticking power test is carried out according to GB9286-98 hundred lattice testing standards simultaneously.In order to contrast the coating of ，Dui U.S. Wei Shibai epoxy resin-matrix heavy-duty coating, carry out above-mentioned corrosion resistance nature test, test result is in Table 3.
Table 3
From table 3, with currently available products comparison, the anticorrosion coat that the priming paint of being prepared by the present invention and finish paint prepare all has excellent sticking power, erosion resistance and weather resistance, the time that can tolerate harsh acid salt fog testing circumstance surpasses 1500h, and well beyond heavy antiseptic property requirement, and raw material is easy to get, preparation technology is simple, VOC free discharge, safety and environmental protection, has a extensive future at heavy corrosion-resistant field.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. an aqueous heavy anti-corrosion paint finish paint, is characterized in that, comprises water-based fluorine organosilicon crylic acid latex, color stuffing, auxiliary agent, thickening material and water;
Described water-based fluorine organosilicon crylic acid latex accounts for 50～60% of priming paint gross weight, by vinylbenzene, methacrylate monomer, acrylate monomer, fluorinated acrylate monomer, organosilicon mix monomer and function monomer reaction, obtained, described organosilicon mix monomer is the mixture of octamethylcyclotetrasiloxane and vinyl alkoxy silane, in described water-based fluorine organosilicon crylic acid latex, the content of organosilane monomer is 15-25%, described function monomer comprises methylene-succinic acid, and the second-order transition temperature of described water-based fluorine organosilicon crylic acid latex is 45～60 ℃.
2. aqueous heavy anti-corrosion paint finish paint as claimed in claim 1, it is characterized in that, the mass ratio of described vinylbenzene and methacrylate monomer is 1:(3.5～8), the mass ratio of described vinylbenzene and methacrylate monomer quality sum and acrylate monomer is (2～5): 1.
3. aqueous heavy anti-corrosion paint finish paint as claimed in claim 1, is characterized in that, the content of described fluorinated acrylate monomer is 5～10%.
4. aqueous heavy anti-corrosion paint finish paint as claimed in claim 1, is characterized in that, the content of described methylene-succinic acid is 1-3%.
5. aqueous heavy anti-corrosion paint finish paint as claimed in claim 1, is characterized in that, in described organosilicon mix monomer, the mol ratio of octamethylcyclotetrasiloxane and vinyl alkoxy silane is (2-3): (0.8-1.2).
6. the aqueous heavy anti-corrosion paint finish paint as described in claim 1 to 5 any one, is characterized in that, described color stuffing accounts for 20～30% of priming paint gross weight.
7. aqueous heavy anti-corrosion paint finish paint as claimed in claim 6, is characterized in that, described color stuffing comprises the component of the following meter of mark by weight:
25～31 parts of zinc phosphates
20～26 parts of superfine talcum powders
10～14 parts of Rutile type Titanium Dioxides.
8. the aqueous heavy anti-corrosion paint finish paint as described in claim 1 to 5 any one, is characterized in that, described auxiliary agent comprises water-soluble silicon oil, and its quality accounts for 4～6.5% of finish paint total mass.
9. the preparation method of finish paint for the aqueous heavy anti-corrosion paint as described in claim 1 to 5 any one, is characterized in that, comprises the following steps:
By vinylbenzene, methacrylate monomer, acrylate monomer, fluorinated acrylate monomer and function monomer pre-emulsification, obtain pre-emulsion C;
After reactive emulsifier, catalyzer are mixed with water, be warming up to 80～87 ℃, drip successively octamethylcyclotetrasiloxane and vinyl alkoxy silane, in 80-87 ℃ of isothermal reaction 0.5～2h, add part initiator solution and part pre-emulsion C, then drip residue pre-emulsion C and residue initiator solution simultaneously, after being added dropwise to complete, be warming up to 80-87 ℃ of isothermal reaction 1～3h, be cooled to room temperature, regulate pH to neutral, obtain water-based fluorine organosilicon crylic acid latex;
After color stuffing, auxiliary agent and water blending dispersion is even, add water-based fluorine organosilicon crylic acid latex to stir, add thickening material adjusting viscosity to 80～100ku, then regulate pH value to 7-9, stir, filter, obtain aqueous heavy anti-corrosion paint finish paint.
10. the preparation method of finish paint for aqueous heavy anti-corrosion paint as claimed in claim 9, is characterized in that, described catalyzer is Witco 1298 Soft Acid.
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