CN103627286B - A kind of aqueous heavy anti-corrosion paint finish paint and preparation method thereof - Google Patents
A kind of aqueous heavy anti-corrosion paint finish paint and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to protective system technical field, disclose a kind of aqueous heavy anti-corrosion paint finish paint and preparation method thereof, aqueous heavy anti-corrosion paint finish paint comprises water-based fluorine organosilicon crylic acid latex, color stuffing, auxiliary agent, thickening material and water; Water-based fluorine organosilicon crylic acid latex accounts for 50 ~ 60% of priming paint gross weight, be obtained by reacting by vinylbenzene, methacrylate monomer, acrylate monomer, fluorinated acrylate monomer, organosilicon mix monomer and function monomer, organosilicon mix monomer is the mixture of octamethylcyclotetrasiloxane and vinyl alkoxy silane, in water-based fluorine organosilicon crylic acid latex, the content of organosilane monomer is 15-25%, function monomer comprises methylene-succinic acid, the second-order transition temperature of described water-based fluorine organosilicon crylic acid latex is 45 ~ 60 DEG C, and the present invention also provides the preparation method of above-mentioned finish paint.The present invention adopts organosilicon and organic fluorine modified acroleic acid to obtain water-based emulsion, prepares heavy-duty coating finish paint, has the feature of low VOC quantity discharged and excellent anti-corrosion performance, and preparation method is simple, wide 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 ofly adopt the heavy-duty coating priming paint of water-based organosilicon crylic acid latex as membrane-forming agent and the preparation method of this priming paint, and a kind ofly adopt the heavy-duty coating finish paint of water-based fluorine organosilicon crylic acid latex as membrane-forming agent and the preparation method of this finish paint.
Background technology
Heavy-duty coating (Heavy-duty Coating) refers to relatively conventional protective system; can use in relatively harsh corrosive environment; and there is a class protective system of protection period longer than conventional protective system, be the matched coating comprising priming paint, middle layer and finish paint.Heavy antisepsis has the implication of two aspects, and 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 under having the condition of certain temperature, usually also can use more than 5 years.The coating that thus can reach heavy antisepsis requirement has that film forming thickness is large usually, multi-layer paint films compound and the exsertile feature of paint film erosion resistance, comprises marine finish, coating container, wind-powered electricity generation coating, bridge coating, storage tin paint etc.
Heavy-duty coating is generally made up 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, many employings organic solvent dissolves the system that the obtains base-material as heavy-duty coating to membrane-forming agent, in use discharge a large amount of volatile organic gas (VOC), to environment.In order to the requirement of the protection that conforms, the Main way that environmental protection will be following heavy-duty coating, specifically comprises the modification of environment-friendly type coating resin, improves the solid content of heavy-duty coating, the development etc. of aqueous heavy anti-corrosion paint.
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 good mechanical performance, the advantages such as hardness is good, be used widely, but it is long to determine that it exists time of drying by the character of epoxy resin itself in practice, weathering resistance is not good enough, film-forming process requires the shortcomings such as high to construction environment, thus 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
In order to solve above-mentioned prior art Problems existing, the invention provides a kind of low VOC content, environmentally friendly, strong adhesion, salt spray corrosion resistance excellent, without the need to solidification, aqueous heavy anti-corrosion paint priming paint easy to use, and the preparation method of this priming paint.
The present invention also provides a kind of low VOC content, environmentally friendly, water-fast weather resistance is given prominence to, without the need to the aqueous heavy anti-corrosion paint finish paint of solidification, and the preparation method of this finish paint.
The technical solution used in the present invention is:
A kind of 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, be obtained by reacting by vinylbenzene, methacrylate monomer, acrylate monomer, organosilane monomer and function monomer, 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 DEG C.
Described water-based organosilicon crylic acid latex is obtained by reacting by vinylbenzene, methacrylate monomer, acrylate monomer, organosilane monomer and function monomer.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 comprises one or more in glycidyl methacrylate, N hydroxymethyl acrylamide, vinylformic acid, methacrylic acid further.
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 counted 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 quality accounts 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 aqueous heavy anti-corrosion paint priming 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 DEG C, after adding initiator solution, drip part pre-emulsion A, drip pre-emulsion B, remaining pre-emulsion A and initiator solution more simultaneously, be warming up to 78-82 DEG C of isothermal reaction 1 ~ 3h after being added dropwise to complete, 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 and stir, add thickening material adjusting viscosity to 80 ~ 100ku, adjust ph, to 7-9, stirs, and filters, obtains aqueous heavy anti-corrosion paint priming paint.
In the process of preparation water-based organosilicon crylic acid latex, part styrene, acrylate, functional monomer etc. are first dripped during polyreaction, drip organosilane monomer and residue comonomer again, form organosilicon core-shell emulsion particle outside, organosilyl modification advantage can be given full play to.
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 finish paint gross weight, be obtained by reacting by vinylbenzene, methacrylate monomer, acrylate monomer, fluorinated acrylate monomer, organosilicon mix monomer and function monomer, 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 DEG C.
Described water-based fluorine organosilicon crylic acid latex is obtained by reacting by vinylbenzene, methacrylate monomer, acrylate monomer, organosilane monomer and function monomer.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 ester, 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 comprises one or more in glycidyl methacrylate, N hydroxymethyl acrylamide, vinylformic acid, methacrylic acid further.
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:
Zinc phosphate 25 ~ 31 parts
Superfine talcum powder 20 ~ 26 parts
Rutile type Titanium Dioxide 10 ~ 14 parts
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 quality accounts for 4 ~ 6.5% of finish paint total mass.
Preferably, described thickening material is polyurethane associative thickener RM-8W.
The preparation method of aqueous heavy anti-corrosion paint finish paint of the present invention, 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 DEG C, drip octamethylcyclotetrasiloxane and vinyl alkoxy silane successively, in 80-87 DEG C 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, 80-87 DEG C of isothermal reaction 1 ~ 3h is warming up to after being added dropwise to complete, 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 and stir, add thickening material adjusting viscosity to 80 ~ 100ku, then adjust ph is to 7-9, stirs, 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, react with vinyl alkoxy silane after utilizing octamethylcyclotetrasiloxane (D4) open loop, generate the silicone intermediate with vinyl, copolymerized grafting is carried out again with vinylbenzene, acrylate, fluorinated acrylate monomer etc., obtain high silicon content take organosilicon as core, the fluorinated silicone modified acrylate polymer emulsion that is shell with vinylformic acid organic fluorine multipolymer, significantly improve the weather-proof of finish paint and corrosion resistance nature.
The technique effect that the present invention is useful: aqueous heavy anti-corrosion paint priming paint of the present invention adopts water-based organosilicon crylic acid latex as film forming binder, priming paint is made to have excellent sticking power and corrosion resistance nature, and aqueous heavy anti-corrosion paint finish paint of the present invention adopts water-based fluorine organosilicon crylic acid latex to be film forming binder, finish paint weather resistance is given prominence to, when both combine the aqueous heavy anti-corrosion paint that obtains coat-thickness are 100 μm in actual applications, the acid resistance salt fog time is more than 1500h, well beyond heavy antisepsis performance requriements, and raw material is easy to get, preparation technology is simple, VOC free discharges, safety and environmental protection, be convenient to industrialization.
Embodiment
Below provide specific embodiment to be further detailed the present invention, wherein embodiment 1 ~ 3 is for preparing the specific embodiment of aqueous heavy anti-corrosion paint priming paint, and embodiment 4 ~ 6 is for preparing the specific embodiment of aqueous heavy anti-corrosion paint finish paint.
Embodiment 1
The preparation method of aqueous heavy anti-corrosion paint priming 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 emulsification in the 90g water containing 0.6g sodium lauryl sulphate, obtains pre-emulsion A;
Vinyltriethoxysilane 18g is added in the 15g water containing 0.2g Arlacel-80,0.1g sodium lauryl sulphate and carry 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 DEG C, add 25g ammonium persulfate aqueous solution (mass concentration is 2%), drip 140g pre-emulsion A, time for adding is 2h, drip 33g pre-emulsion B again after being added dropwise to complete 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 DEG C of reaction 2.5h, be cooled to room temperature, PH to 7 is adjusted with the ammoniacal liquor that mass percent concentration is 28%, obtain water-based organosilicon crylic acid latex.
The second-order transition temperature adopting dsc (DSC) to test gained water-based organosilicon crylic acid latex according to GB 19466-2 is 45 DEG C, and the viscosity adopting 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, with 2500r/min rotating speed high-speed stirring 0.5h in high speed dispersor, slowly add the water-based organosilicon crylic acid latex 276g of above preparation, 30min is stirred with the rotating speed of 1200r/min, add anti-sudden strain of a muscle rust agent CK161g, defoamer A1102g and film coalescence aid water-soluble silicon oil 25g, add 1.8g polyurethane associative thickener RM-8W again, determine viscosity with stormer viscosity measurement and reach 90ku, PH=9 is regulated with ammoniacal liquor, 15min is stirred under the rotating speed of 800r/min, filter through 200 mesh filter screens, obtain aqueous heavy anti-corrosion paint priming paint.
Embodiment 2
The preparation method of aqueous heavy anti-corrosion paint priming 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 emulsification in the 90g water containing 0.6g sodium lauryl sulphate, obtains pre-emulsion A;
Vinyltriethoxysilane 10.9g is added in the 9g water containing 0.12g Arlacel-80,0.06g sodium lauryl sulphate and carry 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 DEG C, add 24g ammonium persulfate aqueous solution (mass concentration is 2%), drip 140g pre-emulsion A, time for adding is 1.5h, drip 20g pre-emulsion B, remaining 280g pre-emulsion A and remaining 49g ammonium persulfate aqueous solution (mass concentration is 2%) again after being added dropwise to complete simultaneously, time for adding is 4h, after being added dropwise to complete, in 78 DEG C of reaction 1.5h, be cooled to room temperature, adjust PH to 7 with ammoniacal liquor, obtain water-based organosilicon crylic acid latex.
The second-order transition temperature adopting dsc (DSC) to test gained water-based organosilicon crylic acid latex according to GB 19466-2 is 50 DEG C, and the viscosity adopting 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, with 2000r/min rotating speed high-speed stirring 1h in high speed dispersor, slowly add the water-based organosilicon crylic acid latex 244.1g of above preparation, 30min is stirred with the rotating speed of 1500r/min, 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 1.5g polyurethane associative thickener RM-8W again, determine viscosity with stormer viscosity measurement and reach 85ku, PH=9 is regulated with ammoniacal liquor, 25min is stirred under the rotating speed of 700r/min, filter through 200 mesh filter screens, obtain aqueous heavy anti-corrosion paint priming paint.
Embodiment 3
The preparation method of aqueous heavy anti-corrosion paint priming 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 emulsification in the 88g water containing 0.58g sodium lauryl sulphate, obtains pre-emulsion A;
Vinyl silane triisopropoxide 27.6g is added in the 23g water containing 0.3g Arlacel-80,0.15g sodium lauryl sulphate and carry 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 DEG C, add 25g ammonium persulfate aqueous solution (mass concentration is 2%), drip 137g pre-emulsion A, time for adding is 4h, drip 51g pre-emulsion B, remaining 273.5g pre-emulsion A and remaining 50g ammonium persulfate aqueous solution (mass concentration is 2%) again after being added dropwise to complete simultaneously, time for adding is 2h, after being added dropwise to complete, in 82 DEG C of reaction 3h, be cooled to room temperature, adjust PH to 7 with ammoniacal liquor, obtain water-based organosilicon crylic acid latex.
The second-order transition temperature adopting dsc (DSC) to test gained water-based organosilicon crylic acid latex according to GB 19466-2 is 35 DEG C, and the viscosity adopting 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, with 2300r/min rotating speed high-speed stirring 0.5h in high speed dispersor, slowly add the water-based organosilicon crylic acid latex 297.6g of above preparation, 40min is stirred with the rotating speed of 1200r/min, 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 1.2g polyurethane associative thickener RM-8W again, determine viscosity with stormer viscosity measurement and reach 100ku, PH=9 is regulated with ammoniacal liquor, 25min is stirred under the rotating speed of 600r/min, filter through 200 mesh filter screens, obtain aqueous heavy anti-corrosion paint priming paint.
Embodiment 4
The preparation method of aqueous heavy anti-corrosion paint finish 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 emulsification in the 30g water containing 0.18g sodium lauryl sulphate, obtains 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 is uniformly mixed, be warming up to 80 DEG C, drip 22.4g octamethylcyclotetrasiloxane, time for adding is 2h, drip 5.6g vinyltriethoxysilane again, time for adding is 1.5h, in 82 DEG C of isothermal reaction 2h after being added dropwise to complete; Add 8.5g ammonium persulfate aqueous solution (mass concentration is 2%), drip 46g pre-emulsion C, time for adding is 2h, drip remaining 91g pre-emulsion C and 16.5g ammonium persulfate aqueous solution (mass concentration is 2%) again after being added dropwise to complete simultaneously, time for adding is 3h, in 80 DEG C of isothermal reaction 2h after being added dropwise to complete, regulating pH to neutral with ammoniacal liquor after cooling, obtain water-based fluorine organosilicon crylic acid latex.
The second-order transition temperature adopting dsc (DSC) to test gained water-based fluorine organosilicon crylic acid latex according to GB 19466-2 is 50 DEG C, and the viscosity adopting 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, with 2500r/min rotating speed high-speed stirring 1h in high speed dispersor, slowly add the water-based fluorine organosilicon crylic acid latex 275g of above preparation, 30min is stirred with the rotating speed of 1200r/min, add defoamer A1102g successively, film coalescence aid water-soluble silicon oil 25g, add 1g polyurethane associative thickener RM-8W again, determine viscosity with stormer viscosity measurement and reach 85ku, PH=9 is adjusted with ammoniacal liquor, 15min is stirred with the rotating speed of 800r/min, filter through 200 mesh filter screens, obtain aqueous heavy anti-corrosion paint finish paint.
Embodiment 5
The preparation method of aqueous heavy anti-corrosion paint finish 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 emulsification in the 54g water containing 0.33g sodium lauryl sulphate, obtains 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 is uniformly mixed, be warming up to 85 DEG C, drip 25.4g octamethylcyclotetrasiloxane, time for adding is 2h, drip 9.6g vinyltriethoxysilane again, time for adding is 1h, in 80 DEG C of isothermal reaction 0.5h after being added dropwise to complete; Add 14g ammonium persulfate aqueous solution (mass concentration is 2%), drip 83g pre-emulsion C, time for adding is 2h, drip remaining 165g pre-emulsion C and 28g ammonium persulfate aqueous solution (mass concentration is 2%) again after being added dropwise to complete simultaneously, time for adding is 4h, in 82 DEG C of isothermal reaction 1h after being added dropwise to complete, is cooled to room temperature, regulate pH to neutral with ammoniacal liquor, obtain water-based fluorine organosilicon crylic acid latex.
The second-order transition temperature adopting dsc (DSC) to test gained water-based fluorine organosilicon crylic acid latex according to GB 19466-2 is 45 DEG C, and the viscosity adopting 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, with 2200r/min rotating speed high-speed stirring 1.5h in high speed dispersor, slowly add water-based fluorine organosilicon crylic acid latex 306.8g, 25min is stirred with the rotating speed of 1500r/min, add defoamer A1101.7g successively, film coalescence aid water-soluble silicon oil 21.3g, add 1.5g polyurethane associative thickener RM-8W again, determine viscosity with stormer viscosity measurement and reach 90ku, PH=9 is adjusted with ammoniacal liquor, 20min is stirred with the rotating speed of 700r/min, filter through 200 mesh filter screens, obtain aqueous heavy anti-corrosion paint finish paint.
Embodiment 6
The preparation method of aqueous heavy anti-corrosion paint finish 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 emulsification in the 21g water containing 0.13g sodium lauryl sulphate, obtains 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 is uniformly mixed, be warming up to 80 DEG C, drip 20.4g octamethylcyclotetrasiloxane, time for adding is 2h, drip 4.6g methacryloxypropyl trimethoxy silane again, time for adding is 0.5h, in 80 DEG C of isothermal reaction 0.5h after being added dropwise to complete; Add 6.3g ammonium persulfate aqueous solution (mass concentration is 2%), drip 32g pre-emulsion C, time for adding is 2h, drip remaining 64g pre-emulsion C and 12.2g ammonium persulfate aqueous solution (mass concentration is 2%) again after being added dropwise to complete simultaneously, time for adding is 3h, in 87 DEG C of isothermal reaction 3h after being added dropwise to complete, is cooled to room temperature, regulate pH to neutral with ammoniacal liquor, obtain water-based fluorine organosilicon crylic acid latex.
The second-order transition temperature adopting dsc (DSC) to test gained water-based fluorine organosilicon crylic acid latex according to GB 19466-2 is 60 DEG C, and the viscosity adopting 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, with 1500r/min rotating speed high-speed stirring 1h in high speed dispersor, slowly add the water-based fluorine organosilicon crylic acid latex 200g of above preparation, 20min is stirred with the rotating speed of 1500r/min, add defoamer A1101.9g successively, film coalescence aid water-soluble silicon oil 25g, add 0.8g polyurethane associative thickener RM-8W again, determine viscosity with stormer viscosity measurement and reach 100ku, PH=9 is adjusted with ammoniacal liquor, 20min is stirred with the rotating speed of 700r/min, filter through 200 mesh filter screens, obtain aqueous heavy anti-corrosion paint finish paint.
Testing example
The antiseptic property of performance to coating preparing the emulsion used in aqueous heavy anti-corrosion paint process has crucial effect, provides the performance test embodiment that emulsion, priming paint and finish paint and priming paint and finish paint apply the coating of formation simultaneously respectively thus:
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, carry out performance test respectively to filming emulsion, method is as follows:
Measure the surface drying of the paint film that filming emulsion is formed according to GB 1728-79 paint film, putty membrane assay method time of drying and do solid work the time;
Mechanical stability and the Calcium ion stability of filming emulsion is tested according to GB/T 20623-2006;
The sticking power after filming emulsion film forming is measured according to GB9286-98 hundred lattice testing standard;
Water resistance test: filming emulsion is spread evenly across on glass with film preparing device, room temperature leaves standstill one day, then puts into 50 DEG C of loft drier inner dryings 6 hours, takes out and is dipped in water after being cooled to room temperature, the latex film of 2/3 is dipped in water, observes the time that film turns white and comes 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 aqueous heavy anti-corrosion paint finish paint (abbreviation finish paint) of preparation in the aqueous heavy anti-corrosion paint priming paint (abbreviation priming paint) prepared in embodiment 1 ~ 3 and embodiment 4 ~ 6 is tested, investigate the application performance of priming paint and finish paint, method is as follows:
Measure the surface drying of the paint film of priming paint and finish paint formation according to GB 1728-79 paint film, putty membrane assay method time of drying and do solid work the time;
The sticking power after priming paint and finish paint film forming is measured according to GB9286-98 hundred lattice testing standard;
The resistance to salt water of priming paint and finish paint is tested according to GB/T 1763-1979;
Test result is in table 2.
Table 2
From table 2, the priming paint prepared by water-based organosilicon crylic acid latex of the present invention and water-based fluorine organosilicon crylic acid latex and finish paint all have excellent sticking power and salt water resistance performance.
The priming paint prepared embodiment further and finish paint carry out corrosion resistance nature test, finish paint prepared by the priming paint prepared for embodiment 1 and embodiment 4, the corrosion resistance nature of the water-based anticorrosion coat that test priming paint and topcoat composition obtain, testing method is with reference to GB/T 1771-91, specific as follows:
Be that sandblasting is carried out on the tinplate surface of 0.3mm by 150mm × 50mm, thickness, make it to reach St2 level, basecoat paint embodiment 1 prepared with seven apertures in the human head high atomization varnish spray gun under 0.5MPa air pressure is on processed tinplate, spray again after surface drying, spray 3 times altogether, obtain primer coating, then finish paint prepared by embodiment 4 is sprayed 2 times, obtain the sample with water-based anticorrosion coat after surface drying, testing coating thickness is 100 μm;
After sample being put into 90 DEG C of oven drying 4h, the water-based anticorrosion coat of sample draws "×" and 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, being replaced with by neutralisation test solution wherein with vinegar acid for adjusting pH is acid test solution after 3, 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 Corrosion Protection is not good, draw "×" place and just corrosion can occur, cause coating expansion and bubble, and spreading under coating, causing drawing "×" place and produce more large-area corrosion, be also tested for the sticking power of anticorrosion coat before and after acid salt-fog test, sticking power test is carried out according to GB9286-98 hundred lattice testing standard simultaneously.In order to contrast, carry out above-mentioned corrosion resistance nature test to the coating of U.S. Wei Shibai epoxy resin-matrix heavy-duty coating, test result is in table 3.
Table 3
From table 3, compare with currently available products, the anticorrosion coat that the priming paint prepared by the present invention and finish paint prepare all has excellent sticking power, erosion resistance and weather resistance, can time of acid salt fog testing circumstance of withstand harsh more than 1500h, well beyond heavy antisepsis performance requriements, and raw material is easy to get, preparation technology is simple, VOC free discharges, and safety and environmental protection, has a extensive future in heavy antisepsis 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, some simple deduction or replace can also be made, 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 finish paint gross weight, be obtained by reacting by vinylbenzene, methacrylate monomer, acrylate monomer, fluorinated acrylate monomer, organosilicon mix monomer and function monomer, 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 organosilicon mix 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 DEG C.
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, it 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, it 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, it 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 any one of claim 1 to 5, is characterized in that, described color stuffing accounts for 20 ~ 30% of finish paint gross weight.
7. aqueous heavy anti-corrosion paint finish paint as claimed in claim 6, it is characterized in that, described color stuffing comprises the component of the following meter of mark by weight:
Zinc phosphate 25 ~ 31 parts
Superfine talcum powder 20 ~ 26 parts
Rutile type Titanium Dioxide 10 ~ 14 parts.
8. the aqueous heavy anti-corrosion paint finish paint as described in any one of claim 1 to 5, it is characterized in that, described auxiliary agent comprises water-soluble silicon oil, its quality accounts for 4 ~ 6.5% of finish paint total mass.
9. the preparation method of the aqueous heavy anti-corrosion paint finish paint as described in any one of claim 1 to 5, is characterized in that, comprise 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 DEG C, drip octamethylcyclotetrasiloxane and vinyl alkoxy silane successively, in 80-87 DEG C 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, 80-87 DEG C of isothermal reaction 1 ~ 3h is warming up to after being added dropwise to complete, 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 and stir, add thickening material adjusting viscosity to 80 ~ 100ku, then adjust ph is to 7-9, stirs, filter, obtain aqueous heavy anti-corrosion paint finish paint.
10. the preparation method of aqueous heavy anti-corrosion paint finish paint as claimed in claim 9, it is characterized in that, described catalyzer is Witco 1298 Soft Acid.
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| CN104277652B (en) * | 2014-10-20 | 2017-02-01 | 芜湖县双宝建材有限公司 | Water-based anticorrosive paint |
| CN105889504B (en) * | 2016-05-03 | 2018-11-02 | 江苏久维压力容器制造有限公司 | Pressure vessel for containing corrosive liquids |
| CN108384375A (en) * | 2018-03-27 | 2018-08-10 | 占军 | Environment-friendlyanti-corrosive anti-corrosive paint |
| CN108410303A (en) * | 2018-03-27 | 2018-08-17 | 占军 | The anticorrosive derusting construction technology of steel construction |
| CN110003482B (en) * | 2019-04-24 | 2021-04-30 | 常州大学 | Polyacrylate emulsion for plastic base material and preparation method thereof |
| CN112552442B (en) * | 2020-11-23 | 2023-04-07 | 浙江理工大学 | Organic silicon modified polymer/pigment composite latex and preparation method thereof |
| CN115386036B (en) * | 2021-09-30 | 2023-06-30 | 浙江金质丽新材料有限公司 | Fluorine-containing acrylic resin for woodware seal primer and preparation method thereof |
| CN113980524A (en) * | 2021-10-22 | 2022-01-28 | 青岛睿鸿鑫环保科技有限公司 | Anticorrosion and heat-insulation integrated material and preparation method thereof |
| CN116554772A (en) * | 2023-06-07 | 2023-08-08 | 南京中金润恒金属科技股份有限公司 | Salt-fog-resistant metal antirust paint and preparation method thereof |
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