CN103305076A - Water-based anticorrosive coating with rust and preparation method thereof - Google Patents
Water-based anticorrosive coating with rust and preparation method thereof Download PDFInfo
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- CN103305076A CN103305076A CN 201310208030 CN201310208030A CN103305076A CN 103305076 A CN103305076 A CN 103305076A CN 201310208030 CN201310208030 CN 201310208030 CN 201310208030 A CN201310208030 A CN 201310208030A CN 103305076 A CN103305076 A CN 103305076A
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Abstract
The invention relates to a water-based anticorrosive coating with rust and a preparation method thereof. The water-based anticorrosive coating with the rust comprises the raw materials: 22-35 parts of de-ionized water, 35-45 parts of a fluorine-containing emulsion with the rust, 1-3 parts of an additive, 8-13 parts of an antirust pigment, 1-3 parts of color paste, 5-10 parts of filler, 2-8 parts of a transforming agent or a rust stabilizing agent, and 1.5-3.5 parts of an anti-settling agent, wherein the fluorine-containing emulsion with the rust is a coreshell emulsion prepared from a monomer, an emulsifying agent and an initiating agent; the emulsifying agent comprises the components of a phosphate emulsifying agent and a sodium sulfonate emulsifying agent; a shell part comprises the transforming agent or the rust stabilizing agent. The preparation method comprises the following steps of: stirring part of the de-ionized water, the additive, the transforming agent or the rust stabilizing agent, the anti-settling agent, the antirust pigment and the filler, and grinding the mixture into slurry; adding the fluorine-containing emulsion with the rust and the like while stirring to prepare the anticorrosive coating with the rust. The coating is nontoxic, odorless, non-combustible, non-explosive, non-volatile and low in VOC (volatile organic compounds), can be used for replacing a derusting and descaling process; a protective primer with a high adhesion force is formed; a conventional derusting process can be replaced; the coating can be directly applied to a steel structure or maintenance engineering of mechanical equipment.
Description
Technical field
The present invention relates to the coating in the chemical industry field, particularly relate to a kind of aqueous rusty anti-corrosion paint and preparation method thereof.
Background technology
Metallic substance has become indispensable important materials, especially iron and steel in all fields of national economy, occupy larger proportion.Because chemistry or electrochemical corrosion failure easily occur in metallic substance surrounding medium of living in it under natural condition or working condition, be unfavorable for economic Sustainable development, also affect to environment.Corrosion and protection is an important science, by technology and the method for suitable control corrosion, can prevent or slowing down corrosion destruction, farthest alleviates the financial loss and the social danger that cause because of corrosion.
Method of inhibiting corrosion has a variety of, and wherein, coating antiseptic is because the advantages such as selectivity is wide, scope is wide, easy construction, the saving energy are still method the most effective, most economical and that application is the most general up to now.The method of anticorrosive metal finally is erosion shield (film), has protection, corrosion proof function but will anticorrosive coating is transformed into by application techniques and coating process, even has coating (film) structure of decoration functions concurrently.For anticorrosive coating is coated on the coated article surface equably, make it to form continuous, fine and close protective coating (or coating), most importantly metallic substance is carried out loaded down with trivial details thoroughly surface treatment.
This surface-treated mode comprises: (1) hand cleaning, but its production efficiency is low, and labour intensity is large, and labour protection is poor, and derusting is also good not; (2) chemical rust removing, its acid mist that produces in acid cleaning process can produce infringement to workmen's respiratory system, and volatilization gas and sewage can be to environments; (3) powertool cleaning, its quality is unstable, can't obtain the degree of cleaning of steel structure uniform surface, can not remove and steel surface attachment firmly oxide skin and iron rust; (4) compressed-air blast cleaning, dry blasting wherein can produce Health hazard to operator, and causes the pollution of environment, so the dry blast-cleaning method of open type has been subjected to forbidding of country at present; (5) wet abrasive blasting can make the metallic surface produce and dodge rust.
On rust paint is a kind of coating that can directly construct at the certain thickness rusty scale, it can make rust transform or be stable, stop the development of corrosion, play and not only eliminate rust but also the rot-resistant purpose, therefore the research and development of on rust paint are subject to the attention of domestic and international department as far back as the 1970s and 1980s, successively have many products to come out.Waterborne rusted paint is to wetting, the good penetrability of rust, the conversion that is conducive to become rusty and stable, the organic solvent-free volatilization, free from environmental pollution, do not burn, be well suited in the environment that draws badly, constructing, can directly in the maintenance engineering of multiple steel construction structures and other mechanical means, apply, play preferably protection effect.
But the filmogen major part of these aqueous rusties, rust proof paint all is to adopt the acrylics emulsion, the main outstanding problem that exists is that the physical and mechanical properties of filming is slightly poor, film fine and close not, the saturating property of water proof anti-seepage is bad, so resistance to salt water, humidity resistance, salt fog resistance is undesirable, affects it and applies.
The present invention has studied the basic of on rust paint, and its key is studied the high performance on rust paint of preparation to the conversion of filmogen, rust, stable and chemosmotic Analysis on Mechanism.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of aqueous rusty anti-corrosion paint.
Another technical problem to be solved by this invention is to provide the preparation method of above-mentioned aqueous rusty anti-corrosion paint.
The present invention solves the problems of the technologies described above the technical scheme of taking: a kind of aqueous rusty anti-corrosion paint, and take hud typed fluorinated acrylate water-based emulsion as filmogen, described coating comprises following component by weight at least:
Deionized water 22～35
Fluorine-containing band rust emulsion 35～45
Auxiliary agent 1～3
Rust-stabilising pigment 8～13
Mill base 1～3
Filler 5～10
Transforming agent or the agent 2～8 of surely becoming rusty
Anti-settling agent 1.5～3.5;
Wherein, described fluorine-containing band rust emulsion is the core-shell emulsion with monomer, emulsifying agent, initiator preparation, the nuclear part is 1:1～2:1 with the weight ratio of shell part material, and in the monomer of shell part, comprise at least the organic fluorine reactive monomer, wherein, described emulsifying agent comprises phosphoric acid esters wedding agents and sodium sulfonate class emulsifying agent at least, by 60 parts of nuclear part material total amounts, emulsifier is 1.0～1.4 parts in the nuclear part material, by 40 parts of shell part material total amounts, emulsifier is 0.6～1.0 part in the shell part material; Described shell part also comprises transforming agent or the agent of surely becoming rusty that makes emulsion band rust, comprises at least two or three in phosphoric acid, yellow prussiate of potash, the tannic acid, and by 40 parts of shell part material total amounts, the consumption of transforming agent or the agent of surely becoming rusty is 0.2～0.4 part.
It is filmogen that the present invention has adopted the aqueous fluorine-containing band rust emulsion of development, select extraordinary transforming agent or the agent of surely becoming rusty, the conversion that is conducive to become rusty and stable, can directly play the reaction sequestering action to metal, its compactness of filming, permeability resistance is good, and physicochemical property is good, moisture-resistant is hot, resistance to salt water, salt fog resistance and resistance to deterioration are particularly outstanding, is a kind of aqueous rusty anti-corrosion paint of good combination property.
Concrete, by weight, the consumption of deionized water can be 22,25,28,30,32 or 35 parts; The consumption of fluorine-containing band rust emulsion can be 35,38,40,42 or 45 parts; The consumption of auxiliary agent can be 1,1.2,1.5,1.8,2,2.2,2.5,2.8 or 3 part; The consumption of rust-stabilising pigment can be 8,9,10,11,12 or 13 parts; The consumption of mill base can be 1,1.2,1.5,1.8,2,2.2,2.5,2.8 or 3 part; The consumption of filler can be 5,6,7,8,9 or 10 parts; The consumption of transforming agent or the agent of surely becoming rusty can be 2,3,4,5,6,7 or 8 parts; The consumption of anti-settling agent can be 1.5,1.8,2,2.2,2.5,2.8,3,3.2 or 3.5 parts.
Concrete, in fluorine-containing band rust emulsion, by 60 parts of nuclear part material total amounts, emulsifier can be 1.0,1.05,1.1,1.15,1.2,1.25,1.3,1.35 or 1.4 parts in the nuclear part material;
By 40 parts of shell part material total amounts, emulsifier can be 0.6,0.65,0.7,0.75,0.8,0.85,0.9,0.95 or 1.0 part in the shell part material;
By 40 parts of shell part material total amounts, the consumption of transforming agent or the agent of surely becoming rusty can be 0.2,0.22,0.25,0.28,0.3,0.32,0.35,0.38 or 0.4 part;
The nuclear part can be 1:1,1.1:1,1.2:1,1.3:1,1.4:1,1.5:1,1.6:1,1.7:1,1.8:1,1.9:1 or 2:1 with the weight ratio of shell part material.
On the basis of such scheme, described auxiliary agent comprises defoamer, dispersion agent, wetting agent, sterilant and flow agent at least, wherein by weight, 0.3～0.6 part of defoamer, 0.1～0.5 part of dispersion agent, 0.1～0.5 part of wetting agent, 0.1～0.2 part in sterilant, 0.4～0.8 part of flow agent.
Concrete, the consumption of defoamer can can can be 0.4,0.5,0.6,0.7 or 0.8 part for 0.1,0.12,0.15,0.18 or 0.2 part, the consumption of flow agent for 0.1,0.2,0.3,0.4 or 0.5 part, the consumption of sterilant for 0.1,0.2,0.3,0.4 or 0.5 part, the consumption of wetting agent for 0.3,0.4,0.5 or 0.6 part, the consumption of dispersion agent.
On the basis of such scheme, described rust-stabilising pigment is commercially available (the different trades mark) rust-stabilising pigment and/or barium metaborate.
On the basis of such scheme, described filler is selected from one or more the combination in china clay, talcum powder, process white, the mica powder.
On the basis of such scheme, the transforming agent in the described coating or the agent of surely becoming rusty comprise two kinds or above combination in phosphoric acid, tannic acid, yellow prussiate of potash, the thio urea at least.
On the basis of such scheme, described anti-settling agent is water-based wilkinite and/or attapulgite.
On the basis of such scheme, in the emulsifying agent of described fluorine-containing band rust emulsion:
Phosphoric acid esters wedding agents be in alkyl phenol ether phosphoric acid ester, alkyl ethoxylated phosphoric acid ester, alkyl ethoxylated phosphoric acid ester ammonium salt, the double bond containing polyether phosphate two kinds or more than, by 60 parts of nuclear part material total amounts, the consumption of phosphoric acid esters wedding agents is 0.4～1 part in the nuclear part material, by 40 parts of shell part material total amounts, the consumption of phosphoric acid esters wedding agents is 0.4～0.6 part in the shell part material;
Sodium sulfonate class emulsifying agent is one or more in acrylamido sodium isopropyl xanthate, 2-allyl ethers 3-hydroxy propane-1-sodium sulfonate, the dodecyl diphenyl oxide sodium sulfonate, by 60 parts of nuclear part material total amounts, the consumption of sodium sulfonate class emulsifying agent is 0.1～0.6 part in the nuclear part material, by 40 parts of shell part material total amounts, the consumption of phosphoric acid esters wedding agents is 0.1～0.4 part in the shell part material;
Perhaps, also comprise the ethers emulsifying agent in the described emulsifying agent, be in double bond containing polyethers, alkyl phenol polyether, the alkyl phend ether sulfate one or more, by 60 parts of nuclear part material total amounts, the consumption of ethers emulsifying agent is 0.1～0.5 part in the nuclear part material, by 40 parts of shell part material total amounts, the consumption of ethers emulsifying agent is 0.1～0.2 part in the shell part material.
Concrete, by 60 parts of nuclear part material total amounts, the consumption of phosphoric acid esters wedding agents can be 0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85,0.9,0.95 or 1 part in the nuclear part material, by 40 parts of shell part material total amounts, the consumption of phosphoric acid esters wedding agents can be 0.4,0.45,0.5,0.55 or 0.6 part in the shell part material;
By 60 parts of nuclear part material total amounts, the consumption of sodium sulfonate class emulsifying agent can be 0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55 or 0.6 part in the nuclear part material, by 40 parts of shell part material total amounts, the consumption of phosphoric acid esters wedding agents can be 0.1,0.15,0.2,0.25,0.3,0.35 or 0.4 part in the shell part material;
By 60 parts of nuclear part material total amounts, the consumption of ethers emulsifying agent can be 0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45 or 0.5 part in the nuclear part material, by 40 parts of shell part material total amounts, the consumption of ethers emulsifying agent is 0.1,0.12,0.14,0.16,0.18 or 0.2 part in the shell part material.
On the basis of such scheme, the monomer in the described fluorine-containing band rust emulsion is the combination of hard monomer, soft monomer and function monomer, wherein,
Hard monomer is selected from two kinds or above combination in methyl methacrylate, vinylbenzene, methyl acrylate, methacrylic acid, the vinylformic acid;
Soft monomer is selected from two kinds or above combination in butyl acrylate, vinylformic acid isooctyl, tert-butyl acrylate, the 2-EHA;
Function monomer is selected from two kinds or above combination in N hydroxymethyl acrylamide, hydroxypropyl acrylate, diacetone-acryloamide(DAA), vinylformic acid phosphoric acid ester, β-propyloic acrylic ester, the allyl methacrylate(AMA);
By 60 parts of nuclear part material total amounts, the consumption of hard monomer is 8～12 parts in the nuclear part material, and the consumption of soft monomer is 12～18 parts, and the consumption of function monomer is 0.3～1.2 part;
By 40 parts of shell part material total amounts, the consumption of hard monomer is 10～15 parts in the shell part material, and the consumption of soft monomer is 4～8 parts, and the consumption of function monomer is 0.4～1 part.
Concrete, by 60 parts of nuclear part material total amounts, the consumption of hard monomer can be 8,8.5,9,9.5,10,10.5,11,11.5 or 12 parts in the nuclear part material, the consumption of soft monomer can be 12,12.5,13,13.5,14,14.5,15,15.5,16,16.5,17,17.5 or 18 parts, and the consumption of function monomer is 0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1 or 1.2 part;
By 40 parts of shell part material total amounts, the consumption of hard monomer is 10,10.5,11,11.5,12,12.5,13,13.5,14,14.5 or 15 parts in the shell part material, the consumption of soft monomer is 4,4.5,5,5.5,6,6.5,7,7.5 or 8 parts, and the consumption of function monomer is 0.4,0.5,0.6,0.7,0.8,0.9 or 1 part.
On the basis of such scheme, organic fluorine reactive monomer in the described fluorine-containing band rust emulsion is selected from one or more the combination in Hexafluorobutyl mathacrylate, vinylformic acid hexafluoro butyl ester, (methyl) vinylformic acid perfluoroalkyl second fat, the methacrylic acid ten difluoro fat in heptan, by 40 parts of shell part material total amounts, the consumption of function monomer is 1.5～2.5 parts in the shell part material.
Concrete, by 40 parts of shell part material total amounts, the consumption of function monomer can be 1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4 or 2.5 parts in the shell part material.
On the basis of such scheme, initiator in the described fluorine-containing band rust emulsion is selected from Potassium Persulphate, Sodium Persulfate or ammonium persulphate, by 60 parts of nuclear part material total amounts, the consumption of initiator is 0.1～0.15 part in the nuclear part material, by 40 parts of shell part material total amounts, the consumption of phosphoric acid esters wedding agents is 0.05～0.1 part in the shell part material.
Concrete, by 60 parts of nuclear part material total amounts, the consumption of initiator is 0.1,0.11,0.12,0.13,0.14 or 0.15 part in the nuclear part material, by 40 parts of shell part material total amounts, the consumption of phosphoric acid esters wedding agents can be 0.05,0.06,0.07,0.08,0.09 or 0.1 part in the shell part material.
On the basis of such scheme, described fluorine-containing band rust emulsion also comprises reductive agent in the shell part, be selected from pyrosulfite, hyposulfite, the rongalite one or more, by 40 parts of shell part material total amounts, the consumption of reductive agent is 0.03～0.05 part in the shell part material.
Concrete, by 40 parts of shell part material total amounts, the consumption of reductive agent is 0.03,0.035,0.04,0.045 or 0.05 part in the shell part material.
On the basis of such scheme, described nuclear part partly adopts identical monomer, emulsifying agent and initiator with shell.
Described various raw material all can obtain by commercially available approach.
The present invention solves the problems of the technologies described above another technical scheme of taking and provides preparation method for above-mentioned aqueous rusty anti-corrosion paint, may further comprise the steps:
The first step: the preparation of slurry:
4/5～whole deionized water, 1/3～1/2 auxiliary agent and 1/10～3/5 transforming agent or the agent of surely becoming rusty are stirred, under agitation condition, add anti-settling agent dispersed with stirring 10～30min, add again rust-stabilising pigment and filler dispersed with stirring 20～60min, then be ground to particle fineness being not more than 30 m with runner milling, make slurry;
Second step: the preparation of coating:
Under the agitation condition fluorine-containing band rust emulsion is added in the first step gained slurry, add mill base, remaining part deionized water, auxiliary agent and transforming agent or the agent of surely becoming rusty after stirring, stir 20～60min discharging, filter, make band rust anticorrosive coating;
Wherein, described slurry accounts for 2/5～3/5 of coating total amount.
Concrete, in the process of preparation slurry, the deionized water that uses is whole as 4/5,9/10 or 1(of total amount); The auxiliary agent that uses is 1/3,2/5 or 1/2 of total amount; The transforming agent that uses or the agent of surely becoming rusty are 1/10,1/5,3/10,2/5,1/2 or 3/5 of total amount.
Described slurry can account for 2/5,1/2 or 3/5 of coating total amount.
On the basis of such scheme, the auxiliary agent that adds in the slurry preparation comprises dispersion agent, wetting agent and defoamer; Mix the rear auxiliary agent that adds at slurry with fluorine-containing band rust emulsion and comprise defoamer, sterilant and flow agent.
On the basis of such scheme, the preparation method of described fluorine-containing band rust emulsion may further comprise the steps:
The first step: the preparation of nuclear part emulsion:
1/2～2/3 deionized water, 1/4～1/2 emulsifying agent, 1/2～1 initiator, 1/10～1/7 soft monomer, 1/10～1/7 hard monomer, 1/4～1/2 function monomer in the nuclear part material are added reactor, be warming up to 80～85 ℃ under agitation condition, reaction 10～15 min make nuclear part pre-emulsification emulsion;
Again remaining nuclear part material is added drop-wise in 2～3 h in the pre-emulsification emulsion (seed emulsion), 80～85 ℃ of temperature of reaction, insulation 1～1.5 h initiated polymerization forms nuclear part emulsion;
Second step: the preparation of Structure of Core/shell Emulsion:
The shell part material is mixed and made into shell part pre-emulsification emulsion;
Shell part pre-emulsification emulsion is added drop-wise in 2～3 h in the nuclear part emulsion, 80～85 ℃ of temperature of reaction, insulation 2～3 h initiated polymerizations form Structure of Core/shell Emulsion;
The 3rd step: be cooled to room temperature, with transforming agent or the agent of surely becoming rusty in 30min, be added drop-wise in the Structure of Core/shell Emulsion, filter, make fluorine-containing band rust emulsion.
Concrete, in the process of preparation nuclear part pre-emulsification emulsion, the deionized water of use is 1/2,3/5 or 2/3 of the nuclear part material; The emulsifying agent that uses is 1/4,1/3 or 1/2 of the nuclear part material; The initiator that uses is whole for 1/2,3/5,2/3,4/5 or 1(of nuclear part material); The soft monomer that uses is 1/10,1/9,1/8 or 1/7 of the nuclear part material; The hard monomer that uses is 1/10,1/9,1/8 or 1/7 of the nuclear part material; The function monomer that uses is 1/4,1/3 or 1/2 of the nuclear part material.
The invention has the beneficial effects as follows:
The present invention adds the coating that rust-stabilising pigment and transforming agent or the agent of surely becoming rusty etc. are made take fluorine-containing band rust protection against corrosion emulsion as main film forming substance, nontoxic, tasteless, do not fire, not quick-fried, non-volatile, low VOC, belong to environment-friendly type band rust anticorrosive coating.Can replace heavy rust cleaning descaling technique, the formation high adhesive force is protected priming paint, can directly be coated on the certain thickness rusty scale to support the use with other anticorrosive coating, improves effective protective layer.Can be widely used in maintenance and the protection of the engineerings such as the bridge that become rusty, steel tower, equipment, facility, boats and ships, vehicle, pipeline, heavy-duty machinery, iron skill, construction steel structure.
Aqueous rusty anti-corrosion paint has comprehensive property, can replace craft or mechanical grinding, sandblast or Acid Rust Removalling Technics belong to a kind of energy saving environmental protection product, can directly be coated on the various steel construction structures or be used for the maintenance engineering of other mechanical means, play good protection effect.
Embodiment
Below by specific specific examples explanation embodiments of the present invention, advantage of the present invention and effect can be understood easily by the described content of specification sheets in this area.The present invention can be implemented or used by different embodiments, and the every details in this specification sheets also can be based on different viewpoints and application, carries out various modifications or change under the spirit of the present invention not deviating from.
Notice, the not concrete processing unit that indicates all adopts the conventional equipment in this area in the following example.In addition, should understand the method steps that is mentioned to one or more mixing among the present invention and repel to exist between additive method step and the step before and after the institute combination step and can also insert the additive method step, unless otherwise indicated.
Embodiment 1
The preparation method:
The first step: the preparation of slurry:
Deionized water, dispersion agent, wetting agent, defoamer and HZJ-601-4 rust-preventive agent are stirred, under agitation condition, add anti-settling agent dispersed with stirring 15min, add again rust-stabilising pigment, barium metaborate and filler high-speed stirring and disperse 30min, then grind with runner milling, sampling detects, the product particle fineness should reach about 25 m, makes slurry;
Second step: the preparation of coating:
Under the agitation condition fluorine-containing band rust emulsion is added in the first step gained slurry, add mill base, sterilant, flow agent after stirring, with defoamer, transforming agent or the agent of surely becoming rusty of remaining part deionized water mediation, stir the 30min discharging, filter, make band rust anticorrosive coating.
The prescription of fluorine-containing band rust emulsion
The preparation method:
The first step: the preparation of nuclear part emulsion:
Deionized water, the emulsifying agent of 0.5g, the initiator of 0.1g, 1.7g soft monomer, 1g hard monomer, the 0.5g function monomer of 19g in the nuclear part material are added reactor, be warming up to 80～85 ℃ under agitation condition, reaction 10～15 min make nuclear part pre-emulsification emulsion;
Again remaining nuclear part material is added drop-wise in 2～3 h in the pre-emulsification emulsion (seed emulsion), 80～85 ℃ of temperature of reaction, insulation 1～1.5 h initiated polymerization forms nuclear part emulsion;
Second step: the preparation of Structure of Core/shell Emulsion:
The shell part material is mixed and made into shell part pre-emulsification emulsion;
Shell part pre-emulsification emulsion is added drop-wise in 2～3 h in the nuclear part emulsion, 80～85 ℃ of temperature of reaction, insulation 2～3 h initiated polymerizations form Structure of Core/shell Emulsion;
The 3rd step: be cooled to room temperature, with transforming agent or the agent of surely becoming rusty in 30min, be added drop-wise in the Structure of Core/shell Emulsion, filter, make fluorine-containing band rust emulsion.
Performance Detection is as shown in table 1.
Embodiment 2
The preparation method:
The first step: the preparation of slurry:
Deionized water, dispersion agent, wetting agent, defoamer and HZJ-601-4 rust-preventive agent are stirred, under agitation condition, add anti-settling agent dispersed with stirring 15min, add again rust-stabilising pigment, barium metaborate and filler high-speed stirring and disperse 30min, then grind with runner milling, sampling detects, the product particle fineness should reach about 25 m, makes slurry;
Second step: the preparation of coating:
Under the agitation condition fluorine-containing band rust emulsion is added in the first step gained slurry, add mill base, sterilant, flow agent, defoamer, transforming agent or the agent of surely becoming rusty after stirring, stir the 30min discharging, filter, make band rust anticorrosive coating.
The prescription of fluorine-containing band rust emulsion
The preparation method:
The first step: the preparation of nuclear part emulsion:
Deionized water, the emulsifying agent of 0.55g, the initiator of 0.1g, 1.8g soft monomer, 1.1g hard monomer, the 0.21g function monomer of 20g in the nuclear part material are added reactor, be warming up to 80～85 ℃ under agitation condition, reaction 10～15 min make nuclear part pre-emulsification emulsion;
Again remaining nuclear part material is added drop-wise in 2～3 h in the pre-emulsification emulsion (seed emulsion), 80～85 ℃ of temperature of reaction, insulation 1～1.5 h initiated polymerization forms nuclear part emulsion;
Second step: the preparation of Structure of Core/shell Emulsion:
The shell part material is mixed and made into shell part pre-emulsification emulsion;
Shell part pre-emulsification emulsion is added drop-wise in 2～3 h in the nuclear part emulsion, 80～85 ℃ of temperature of reaction, insulation 2～3 h initiated polymerizations form Structure of Core/shell Emulsion;
The 3rd step: be cooled to room temperature, with transforming agent or the agent of surely becoming rusty in 30min, be added drop-wise in the Structure of Core/shell Emulsion, filter, make fluorine-containing band rust emulsion.
Performance Detection is as shown in table 1.
Embodiment 3
The preparation method:
The first step: the preparation of slurry:
Deionized water, dispersion agent, wetting agent, defoamer and HZJ-601-4 rust-preventive agent are stirred, under agitation condition, add anti-settling agent dispersed with stirring 15min, add again rust-stabilising pigment, barium metaborate and filler high-speed stirring and disperse 30min, then grind with runner milling, sampling detects, the product particle fineness should reach about 25 m, makes slurry;
Second step: the preparation of coating:
Under the agitation condition fluorine-containing band rust emulsion is added in the first step gained slurry, add mill base, sterilant, flow agent after stirring, with defoamer, transforming agent or the agent of surely becoming rusty of remaining part deionized water mediation, stir the 30min discharging, filter, make band rust anticorrosive coating.
The prescription of fluorine-containing band rust emulsion
The preparation method:
The first step: the preparation of nuclear part emulsion:
Deionized water, the emulsifying agent of 0.45g, the initiator of 0.1g, 1.8g soft monomer, 1.15g hard monomer, the 0.2g function monomer of 21g in the nuclear part material are added reactor, be warming up to 80～85 ℃ under agitation condition, reaction 10～15 min make nuclear part pre-emulsification emulsion;
Again remaining nuclear part material is added drop-wise in 2～3 h in the pre-emulsification emulsion (seed emulsion), 80～85 ℃ of temperature of reaction, insulation 1～1.5 h initiated polymerization forms nuclear part emulsion;
Second step: the preparation of Structure of Core/shell Emulsion:
The shell part material is mixed and made into shell part pre-emulsification emulsion;
Shell part pre-emulsification emulsion is added drop-wise in 2～3 h in the nuclear part emulsion, 80～85 ℃ of temperature of reaction, insulation 2～3 h initiated polymerizations form Structure of Core/shell Emulsion;
The 3rd step: be cooled to room temperature, with transforming agent or the agent of surely becoming rusty in 30min, be added drop-wise in the Structure of Core/shell Emulsion, filter, make fluorine-containing band rust emulsion.
Performance Detection is as shown in table 1.
Embodiment 4
The preparation method:
The first step: the preparation of slurry:
Deionized water, dispersion agent, wetting agent, defoamer and HZJ-601-4 rust-preventive agent are stirred, under agitation condition, add anti-settling agent dispersed with stirring 15min, add again rust-stabilising pigment, barium metaborate and filler high-speed stirring and disperse 30min, then grind with runner milling, sampling detects, the product particle fineness should reach about 25 m, makes slurry;
Second step: the preparation of coating:
Under the agitation condition fluorine-containing band rust emulsion is added in the first step gained slurry, add mill base, sterilant, flow agent, defoamer, transforming agent or the agent of surely becoming rusty after stirring, stir the 30min discharging, filter, make band rust anticorrosive coating.
The prescription of fluorine-containing band rust emulsion
The preparation method:
The first step: the preparation of nuclear part emulsion:
Deionized water, the emulsifying agent of 0.4g, the initiator of 0.1g, 1.7g soft monomer, 1.1g hard monomer, the 0.3g function monomer of 17g in the nuclear part material are added reactor, be warming up to 80～85 ℃ under agitation condition, reaction 10～15 min make nuclear part pre-emulsification emulsion;
Again remaining nuclear part material is added drop-wise in the seed emulsion in 2～3 h, 80～85 ℃ of temperature of reaction, insulation 1～1.5 h initiated polymerization forms nuclear part emulsion;
Second step: the preparation of Structure of Core/shell Emulsion:
The shell part material is mixed and made into shell part pre-emulsification emulsion;
Shell part pre-emulsification emulsion is added drop-wise in 2～3 h in the nuclear part emulsion, 80～85 ℃ of temperature of reaction, insulation 2～3 h initiated polymerizations form Structure of Core/shell Emulsion;
The 3rd step: be cooled to room temperature, with transforming agent or the agent of surely becoming rusty in 30min, be added drop-wise in the Structure of Core/shell Emulsion, filter, make fluorine-containing band rust emulsion.
Performance Detection is as shown in table 1.
It is main film forming substance that the present invention adopts the protection against corrosion emulsion of fluorine-containing band rust, add transforming agent or surely become rusty agent and rust-stabilising pigment prepare aqueous rusty anti-corrosion paint, have tasteless, nontoxic, do not fire, not quick-fried, low VOC, can directly be coated in the steel surface of certain rusty scale thickness, outstanding protection effect is arranged.
In sum, defective in the prior art field that the present invention is effectively perfect demonstrates high industrial utilization.
Above-described embodiment has illustrated principle of the present invention and effect thereof, but not is used for restriction the present invention.
Claims (10)
1. aqueous rusty anti-corrosion paint, take hud typed fluorinated acrylate water-based emulsion as filmogen, it is characterized in that: described coating comprises following component by weight at least:
Deionized water 22～35
Fluorine-containing band rust emulsion 35～45
Auxiliary agent 1～3
Rust-stabilising pigment 8～13
Mill base 1～3
Filler 5～10
Transforming agent or the agent 2～8 of surely becoming rusty
Anti-settling agent 1.5～3.5;
Wherein, described fluorine-containing band rust emulsion is the core-shell emulsion with monomer, emulsifying agent, initiator preparation, the nuclear part is 1:1～2:1 with the weight ratio of shell part material, and in the monomer of shell part, comprise at least the organic fluorine reactive monomer, wherein, described emulsifying agent comprises phosphoric acid esters wedding agents and sodium sulfonate class emulsifying agent at least, by 60 parts of nuclear part material total amounts, emulsifier is 1.0～1.4 parts in the nuclear part material, by 40 parts of shell part material total amounts, emulsifier is 0.6～1.0 part in the shell part material; Described shell part also comprises transforming agent or the agent of surely becoming rusty that makes emulsion band rust, comprises at least two or three in phosphoric acid, yellow prussiate of potash, the tannic acid, and by 40 parts of shell part material total amounts, the consumption of transforming agent or the agent of surely becoming rusty is 0.2～0.4 part.
2. aqueous rusty anti-corrosion paint according to claim 1, it is characterized in that: described auxiliary agent comprises defoamer, dispersion agent, wetting agent, sterilant and flow agent at least, wherein by weight, 0.3～0.6 part of defoamer, 0.1～0.5 part of dispersion agent, 0.1～0.5 part of wetting agent, 0.1～0.2 part in sterilant, 0.4～0.8 part of flow agent.
3. aqueous rusty anti-corrosion paint according to claim 1 is characterized in that: described filler is selected from one or more the combination in china clay, talcum powder, process white, the mica powder.
4. aqueous rusty anti-corrosion paint according to claim 1, it is characterized in that: the transforming agent in the described coating or the agent of surely becoming rusty comprise two kinds or above combination in phosphoric acid, tannic acid, yellow prussiate of potash, the thio urea at least.
5. aqueous rusty anti-corrosion paint according to claim 1, it is characterized in that: described anti-settling agent is water-based wilkinite and/or attapulgite.
6. aqueous rusty anti-corrosion paint according to claim 1 is characterized in that: in the emulsifying agent of described fluorine-containing band rust emulsion:
Phosphoric acid esters wedding agents be in alkyl phenol ether phosphoric acid ester, alkyl ethoxylated phosphoric acid ester, alkyl ethoxylated phosphoric acid ester ammonium salt, the double bond containing polyether phosphate two kinds or more than, by 60 parts of nuclear part material total amounts, the consumption of phosphoric acid esters wedding agents is 0.4～1 part in the nuclear part material, by 40 parts of shell part material total amounts, the consumption of phosphoric acid esters wedding agents is 0.4～0.6 part in the shell part material;
Sodium sulfonate class emulsifying agent is one or more in acrylamido sodium isopropyl xanthate, 2-allyl ethers 3-hydroxy propane-1-sodium sulfonate, the dodecyl diphenyl oxide sodium sulfonate, by 60 parts of nuclear part material total amounts, the consumption of sodium sulfonate class emulsifying agent is 0.1～0.6 part in the nuclear part material, by 40 parts of shell part material total amounts, the consumption of phosphoric acid esters wedding agents is 0.1～0.4 part in the shell part material;
Perhaps, also comprise the ethers emulsifying agent in the described emulsifying agent, be in double bond containing polyethers, alkyl phenol polyether, the alkyl phend ether sulfate one or more, by 60 parts of nuclear part material total amounts, the consumption of ethers emulsifying agent is 0.1～0.5 part in the nuclear part material, by 40 parts of shell part material total amounts, the consumption of ethers emulsifying agent is 0.1～0.2 part in the shell part material.
7. aqueous rusty anti-corrosion paint according to claim 1 is characterized in that: the monomer in the described fluorine-containing band rust emulsion is the combination of hard monomer, soft monomer and function monomer, wherein,
Hard monomer is selected from two kinds or above combination in methyl methacrylate, vinylbenzene, methyl acrylate, methacrylic acid, the vinylformic acid;
Soft monomer is selected from two kinds or above combination in butyl acrylate, vinylformic acid isooctyl, tert-butyl acrylate, the 2-EHA;
Function monomer is selected from two kinds or above combination in N hydroxymethyl acrylamide, hydroxypropyl acrylate, diacetone-acryloamide(DAA), vinylformic acid phosphoric acid ester, β-propyloic acrylic ester, the allyl methacrylate(AMA);
By 60 parts of nuclear part material total amounts, the consumption of hard monomer is 8～12 parts in the nuclear part material, and the consumption of soft monomer is 12～18 parts, and the consumption of function monomer is 0.3～1.2 part;
By 40 parts of shell part material total amounts, the consumption of hard monomer is 10～15 parts in the shell part material, and the consumption of soft monomer is 4～8 parts, and the consumption of function monomer is 0.4～1 part.
8. aqueous rusty anti-corrosion paint according to claim 1, it is characterized in that: the organic fluorine reactive monomer in the described fluorine-containing band rust emulsion is selected from one or more the combination in Hexafluorobutyl mathacrylate, vinylformic acid hexafluoro butyl ester, (methyl) vinylformic acid perfluoroalkyl second fat, the methacrylic acid ten difluoro fat in heptan, by 40 parts of shell part material total amounts, the consumption of function monomer is 1.5～2.5 parts in the shell part material.
9. the preparation method for the described aqueous rusty anti-corrosion paint of one of claim 1 to 8 is characterized in that, may further comprise the steps:
The first step: the preparation of slurry:
4/5～whole deionized water, 1/3～1/2 auxiliary agent and 1/10～3/5 transforming agent or the agent of surely becoming rusty are stirred, under agitation condition, add anti-settling agent dispersed with stirring 10～30min, add again rust-stabilising pigment and filler dispersed with stirring 20～60min, then be ground to particle fineness being not more than 30 m with runner milling, make slurry;
Second step: the preparation of coating:
Under the agitation condition fluorine-containing band rust emulsion is added in the first step gained slurry, add mill base, remaining part deionized water, auxiliary agent and transforming agent or the agent of surely becoming rusty after stirring, stir 20～60min discharging, filter, make band rust anticorrosive coating;
Wherein, described slurry accounts for 2/5～3/5 of coating total amount.
10. the preparation method of aqueous rusty anti-corrosion paint according to claim 9 is characterized in that: the preparation method of described fluorine-containing band rust emulsion may further comprise the steps:
The first step: the preparation of nuclear part emulsion:
1/2～2/3 deionized water, 1/4～1/2 emulsifying agent, 1/2～1 initiator, 1/10～1/7 soft monomer, 1/10～1/7 hard monomer, 1/4～1/2 function monomer in the nuclear part material are added reactor, be warming up to 80～85 ℃ under agitation condition, reaction 10～15 min make nuclear part pre-emulsification emulsion;
Again remaining nuclear part material is added drop-wise in 2～3 h in the pre-emulsification emulsion, 80～85 ℃ of temperature of reaction, insulation 1～1.5 h initiated polymerization forms nuclear part emulsion;
Second step: the preparation of Structure of Core/shell Emulsion:
The shell part material is mixed and made into shell part pre-emulsification emulsion;
Shell part pre-emulsification emulsion is added drop-wise in 2～3 h in the nuclear part emulsion, 80～85 ℃ of temperature of reaction, insulation 2～3 h initiated polymerizations form Structure of Core/shell Emulsion;
The 3rd step: be cooled to room temperature, with transforming agent or the agent of surely becoming rusty in 30min, be added drop-wise in the Structure of Core/shell Emulsion, filter, make fluorine-containing band rust emulsion.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105017884A (en) * | 2014-04-16 | 2015-11-04 | 镇江德马化工有限公司 | Aqueous rotating rust steel iron surface treatment liquid and preparation method thereof |
| CN105860811A (en) * | 2016-06-22 | 2016-08-17 | 安徽汇利涂料科技有限公司 | Waterborne polyurethane paint and method for preparing same |
| CN106047000A (en) * | 2016-08-20 | 2016-10-26 | 哈尔滨锅炉厂有限责任公司 | Hydraulic pressure anti-rust agent for boiler auxiliary machine container products, and preparation method thereof |
| CN106519763A (en) * | 2016-10-31 | 2017-03-22 | 邓集叶 | Preparation method for anti-corrosion mechanical coating |
| CN106634097A (en) * | 2016-12-16 | 2017-05-10 | 钦州市高新技术产业服务中心 | Protective paint and preparation method thereof |
| CN112094559A (en) * | 2020-09-25 | 2020-12-18 | 广东电网有限责任公司 | Damp-proof and corrosion-proof plugging material for equipment and preparation method thereof |
| CN113913058A (en) * | 2021-11-18 | 2022-01-11 | 广东科力德新材料有限公司 | Novel rust conversion emulsion and paint integrating rust coating and bottom surface |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105017884A (en) * | 2014-04-16 | 2015-11-04 | 镇江德马化工有限公司 | Aqueous rotating rust steel iron surface treatment liquid and preparation method thereof |
| CN105860811A (en) * | 2016-06-22 | 2016-08-17 | 安徽汇利涂料科技有限公司 | Waterborne polyurethane paint and method for preparing same |
| CN106047000A (en) * | 2016-08-20 | 2016-10-26 | 哈尔滨锅炉厂有限责任公司 | Hydraulic pressure anti-rust agent for boiler auxiliary machine container products, and preparation method thereof |
| CN106519763A (en) * | 2016-10-31 | 2017-03-22 | 邓集叶 | Preparation method for anti-corrosion mechanical coating |
| CN106634097A (en) * | 2016-12-16 | 2017-05-10 | 钦州市高新技术产业服务中心 | Protective paint and preparation method thereof |
| CN112094559A (en) * | 2020-09-25 | 2020-12-18 | 广东电网有限责任公司 | Damp-proof and corrosion-proof plugging material for equipment 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 |
| CN113913058A (en) * | 2021-11-18 | 2022-01-11 | 广东科力德新材料有限公司 | Novel rust conversion emulsion and paint integrating rust coating and bottom surface |
| 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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Application publication date: 20130918 |