CN102838913B - Organosilicone modified heat-resistant self-cleaning waterborne electrochemistry corrosion-resistant paint and preparation method thereof - Google Patents
Organosilicone modified heat-resistant self-cleaning waterborne electrochemistry corrosion-resistant paint and preparation method thereof Download PDFInfo
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Abstract
Provided is organosilicone modified heat-resistant self-cleaning waterborne electrochemistry corrosion-resistant paint. The raw material comprises a resin emulsion. The organosilicone modified heat-resistant self-cleaning waterborne electrochemistry corrosion-resistant paint is characterized in that the resin emulsion is an MPM modified acrylic acid resin microemulsion, the raw material further comprises a coupling agent gamma-methacrylonitrile acyloxy trimethoxy silane, and the adding proportion of the coupling agent gamma-methacrylonitrile acyloxy trimethoxy silane is 0.5-3% of the raw material by mass. The organosilicone modified heat-resistant self-cleaning waterborne electrochemistry corrosion-resistant paint has the advantages that the organosilicone modified heat-resistant self-cleaning waterborne electrochemistry corrosion-resistant paint has perfect waterborne rusted, rust conversion and antirust characteristics; high hiding rate is integrated with high glossiness; weather resistance is high, and for example the products are acid-resisting, alkali-resisting, radiation-resistant and high-low temperature resistant; water repellency and a self-cleaning function are superstrong; the paint film is good in hardness, and the hardness is more than 2H; and organic solvents do not exist, volatile organic compounds (VOC) are low, and environmental protection is benefited.
Description
Technical field
This invention relates to antifouling paste preparation field.
Technical background
Development along with human society; the utilization of metal is ubiquitous in people's productive life field; people also go together with exploitation mutually to the protection of metal for a long time; but the metal protection coating causing due to past resin technology and other material technology limitation is because of problems such as comprehensive weathering resistance are poor; make metal protection seriously lag behind the utilization to metal, a large amount of metals has been corroded in noiseless place.
The oxidizing reaction occurring between metal and water and oxygen and have the material of chemical corrosivity as acid, alkali, salt etc. makes the electronics of metal lose under electrochemical effect, becomes oxidizing substance or other salt of loose water suction, thereby metal is corroded rapidly.According to data, the whole world approximately has 1,000,000,000 tons of metals to be corroded every year, is equivalent to when 20% of annual production, and cannot recycles, and causes surprising waste and environmental pollution.Thereby to the protection meaning of metal as many as metal manufacture.Traditional antifouling paste has following shortcoming:
1. traditional antifouling paste mostly is solvent borne, and summer, construction easily caused damage to workman's health, also unfriendly to environment.
2. traditional antifouling paste is the end, face separately, secondary construction type, and efficiency is low.
3., according to we scientific research personnel's repeated authentication repeatedly, all there is following problem in emerging (comprising published water-based patent antifouling paste) aqueous anticorrosion paint in recent years:
1.
hiding rare and glossiness are attended to one thing and lose sight of another.
paint film dependency is not strong, easily comes off.
non-refractory.
summary of the invention
Object of the present invention is exactly for the above-mentioned deficiency of traditional antifouling paste, and a kind of acrylic resin microemulsion that can be used for preparing the modification of high-temperature self-cleaning antifouling paste is provided.
Advantage of the present invention is: feature of the present invention is not only that its perfection has broken through aqueous anticorrosion paint " parcel with bonding " conventional physical way, electrochemistry molecular bridge connection technology and double salt and chelating technology have been introduced, for the first time methylphenyl siloxane is incorporated into anti-corrosion of metal industry, its finished product have following features:
1, perfectly aqueous rusty, turn rust, antirust feature;
2, the unification of high hiding rare and high-luster;
3, high-weatherability (thering is acidproof, alkaline-resisting, radiation hardness, high-low temperature resistant);
4, there is superpower water repellency and self-cleaning function;
5, hardness of paint film is good, and its hardness surpasses 2H;
6, organic solvent-free, low VOC, environmental.
Embodiment
One, the preparation of the acrylic resin microemulsion of MPM modification
(1) preparation method of methacryloxypropyl methoxymethyl phenyl silicone oil (MPM) is: catalyzing and condensing method, and by HO (MephSiO)
nh and CH2=CMeCOOC3H6SiMe (OMe) 2 hydrolytic condensation and obtaining under granular sulfonic acid ion exchange resin catalysis.Reaction formula is:
HO(MephSiO)
n H+2CH2＝CMeCOOC3H6SiMe(OMe)2
H +
CH2＝CMeCOOC3H6（MeO）MeSiO(MephSiO)nSiMe(OMe)C3H6OCOCMe＝CH2 ,[MPM]
MPM prepares example: by the HO (MephSiO) of 4.4mol
nthe CH2=CMeCOOC3H6SiMe (OMe) 2 of H (n approximately 300) and 9.1mol reacts 1h at (mean pore size>=40 μ m) catalysis of granular sulfonic acid ion exchange resin and 60 ℃, and the MPM transformation efficiency that obtains 4mol reaches as high as 95%.
(2) pre-emulsification of monomer: get AEO-7 (fatty alcohol-polyoxyethylene ether-7) 0.05-0.5kg, SDS (sodium lauryl sulphate) 0.25-1 kg, AES (polyoxyethylenated alcohol sodium sulfate) 0.25-1kg and PEG-400 (poly(oxyethylene glycol) 400) 0.4-0.75kg, MAA(methyl methacrylate) 1.2-1.4kg, ST (vinylbenzene) 0.5-0.8 kg, AN (vinyl cyanide) 1.0-2.0kg, mix and blend is made newborn pre-emulsion I; Get again AEO-7 (fatty alcohol-polyoxyethylene ether-7) 0.05-0.5kg, SDS (sodium lauryl sulphate) 0.2.5-1 kg, AES (polyoxyethylenated alcohol sodium sulfate) 0.25-1kg add in MMA (methyl methacrylate) 1.2-1.4kg, BA (n-butyl acrylate) 5-12kg, 2-EHA (vinylformic acid one 2 one ethylhexyls) 5-12kg, MPM1.4-1.8kg with AEO-3 (fatty alcohol-polyoxyethylene ether-3) 0.1-1kg, PEG-400 (poly(oxyethylene glycol) 400) 0.4-0.75kg, under agitation slowly add water 2-4kg, by phase inversion dispersion method, make pre-emulsion II;
(3) micro-emulsion polymerization: thermometer is being housed, agitator, in the four-hole bottle of prolong, add water 2-4kg, stir, the pre-emulsion I that adds total amount 1/2, with ammoniacal liquor adjust pH to 7, start to heat up, while being warming up to 57-63 ℃, add initiator A PS (ammonium persulphate) 0.4-0.6kg, continue to heat up and add residue pre-emulsion I and initiator A PS (ammonium persulphate) 0.4-0.6kg, temperature is controlled at 87-93 ℃, continue to add pre-emulsion II and APS (ammonium persulphate) 0.4-0.6kg, and maintenance reaction 1.5h, naturally cooling, filter, obtain the acrylic resin microemulsion of MPM modification.
Two, organic-silicon-modified high-temperature-resistant self-cleaning water electrochemical antifouling paste
Powder stock pre-treatment:
Get the containing hydrogen silicone oil of powder stock total mass 1.5%,
Get Surfactant OP-10 of silicone oil total mass 3%,
Get the deionized water of 10 times of silicone oil total masses;
Quantitative containing hydrogen silicone oil is dropped in high-speed dispersing kettle, then drop into quantitative Surfactant OP-10, open low-speed mixer, raw material is mixed, then close low-speed mixer, open high speed dispersor, after high speed dispersion 5 minutes, start to drip deionized water, by phase conversion method, containing hydrogen silicone oil is emulsified into containing hydrogen silicone oil emulsion, after filtration, put into spray tank standby;
Powder is dropped into stirred pot, containing hydrogen silicone oil emulsion is sprayed onto to stirred pot with atomizer, stir on spray limit, limit, stirs evenly;
Powder stock is respectively titanium dioxide, mica powder, kaolin, barium sulfate, every kind of independent pre-treatment of powder stock, and pretreated powder, is the pre-treatment powder stock of organic-silicon-modified high-temperature-resistant self-cleaning water electrochemical antifouling paste.
This antifouling paste is prepared example (1)
Remove ionized water 230g, PH conditioning agent AMP-951g, ammonium salt dispersion agent 1.7g, sodium salt dispersion agent 5g, wetting agent PE-1001g, ethylene glycol 5g, film coalescence aid lauryl alcohol fat 18g, defoamer NXZ1g, pretreated titanium dioxide 130g, pretreated kaolin 80g, pretreated barium sulfate 30g, modified phosphate aluminium 47g, zinc phosphate 47g, pretreated mica powder 50g, flow agent RM-20203.3g, successively above-mentioned raw materials is dropped in high-speed dispersing kettle, high speed dispersion 1h, under expect paint mixing kettle, add MPM modified emulsion 500g, defoamer NXZ1g, deionized water 35g, under stirring at low speed, drop into X-405(and disperse wetting agent) 2g, anti-sudden strain of a muscle rust agent 5g, preferred silane coupling agent γ-methacryloxy Trimethoxy silane 3g, add anticorrosion and bactericidal agent 3g, add each appropriate adjusting viscosity of alkali swelling and polyurethane type thickening material to desired value, filter and package, obtain white water organic silicon modified, high temperature resistant automatically cleaning water electrochemical antifouling paste.
This antifouling paste is prepared example (2)
Remove ionized water 230g, PH conditioning agent AMP-951g, ammonium salt dispersion agent 1.7g, sodium salt dispersion agent 5g, wetting agent (PE-100) 1g, ethylene glycol 5g, film coalescence aid lauryl alcohol fat 18g, defoamer NXZ1g, pretreated titanium dioxide 150g, pretreated barium sulfate 80g, modified phosphate aluminium 50g, zinc phosphate 40g, pretreated mica powder 60g, middle yellow 10g, pretreated kaolin 50g, bright red 10g, flow agent (RM-2020) 3g, successively above-mentioned raw materials is dropped in high-speed dispersing kettle, high speed dispersion 1h, under expect paint mixing kettle, add MPM modified emulsion 550g, defoamer NXZ1g, deionized water 35g, under stirring at low speed, drop into X-405(and disperse wetting agent) 2g, anti-sudden strain of a muscle rust agent 5g, preferred silane coupling agent γ-methacryloxy Trimethoxy silane 3.3g, add anticorrosion and bactericidal agent 3g, add each appropriate adjusting viscosity of alkali swelling and polyurethane type thickening material to desired value, filter and package, obtain orange waterborne organic silicon modified, high temperature resistant automatically cleaning water electrochemical antifouling paste.
This antifouling paste is prepared example (3)
Remove ionized water 300g, PH conditioning agent (AMP-95) 1g, ammonium salt dispersion agent 2.2g, sodium salt dispersion agent 4.8g, wetting agent (PE-100) 1g, ethylene glycol 5g, film coalescence aid lauryl alcohol fat 19g, defoamer NXZ1g, pretreated titanium dioxide 110g, ferrophosphorus powder 130g, pretreated kaolin 60g, modified phosphate aluminium 50g, zinc phosphate 40g, carbon black 5g, flow agent (RM-2020) 3g, successively above-mentioned raw materials is dropped in high-speed dispersing kettle, high speed dispersion 1h, under expect paint mixing kettle, add MPM modified emulsion 530g, defoamer NXZ1g, deionized water 50g, under stirring at low speed, drop into X-405(and disperse wetting agent) 2g, anti-sudden strain of a muscle rust agent 4.7g, preferred silane coupling agent γ-methacryloxy Trimethoxy silane 2.9g, add anticorrosion and bactericidal agent 3g, add each appropriate adjusting viscosity of alkali swelling and polyurethane type thickening material to desired value, filter and package, obtain iron gray waterborne organic silicon modified, high temperature resistant automatically cleaning water electrochemical antifouling paste.
Be more than the optimized embodiment of the present invention, comprise synthesis technique, the formula of MPM (organosilicon) modified acrylic acid emulsion; The preparation technology of finished product paint, formula for a product; According to the published content of the present invention, the replacement scheme that those skilled in the art can consider, identical embodiment, is category of the present invention.In the present invention, MPM modified acrylic resin emulsion also can be used as the important source material in high-end leather production.
Feature of the present invention and principle are set forth:
Accomplish the coating protection of metal under harsh environment, must start with from the following aspects research:
1.
must form fine and close paint film to completely cut off steam, oxygen and acid, alkali, salt atmosphere gas intrusion, this just needs film-forming resin to have enough cross-link intensity closely, once and resin itself must be antiacid, alkali, brine corrosion. paint film resin is destroyed under harsh environment, metal will reveal and be corroded very soon by Naked, at present, traditional acrylic acid system (comprising comparatively popular epoxide modified series) formed paint film of emulsion, its corrosion-resistant degree all can not be satisfactory.The present invention has introduced organic-silicon-modified acrylic resin, has comparatively perfectly solved the erosion resistance ability problem of paint film self.And make paint film obtain the outstanding characteristic of silicone resin.
2.
paint film is the persistent key factor of preservative effect with the adherence that is coated metal, because paint film belongs to organism, being coated metal is inorganics, is difficult between the two form firmly chemical bonding force, only depends on faint Van der Waals force to connect, under harsh environment, the easy Fen Hua of paint film comes off.
the present inventionpreferably silane coupling agent at paint film with between by matel coated, formed firmly electrochemistry key bridge joint, to traditional " parcel is with bonding " principle and method given revolutionary upgrading, perfect solution
adherencethis
keyproblem.
its formula of traditional aqueous anticorrosion paint is also unreasonable when selecting filler.Such as adding calcium carbonate, under the erosion of empty G&W, can become Calcium hydrogen carbonate, because Calcium hydrogen carbonate is slightly soluble in water, under rainwash, will cause running off and cause paint film empty, form defect. the present invention's unreasonable fillers such as calcium carbonate of having forgone, on the basis of conventional packing, add preferred zinc phosphate and modified phosphate aluminium etc. and can form double salt and fine and close inner complex with iron rust and free iron, thereby stoped the further free of metal, the surfactivity that terminated free metal loses electronics and the process of oxidized corrosion, inner complex can make active metal atom lose activity, double salt can make already oxidised each loose state ferric oxide (metal) form dense structure, thereby realized band rust, turn rust, with antirust perfect function. be exactly that zinc phosphate is to form at metallic surface and Fe3+ the complex compound Fe[Zn3(P04 of adhere firmly specifically) 3] beds of precipitation and suppress anodic reaction, simultaneously can with hydroxyl in coating, carboxyl complexing, make to form Chemical bond between pigment-coating-ground and improve sticking power and the impermeability of coating.Aluminium triphosphate is white pigment, is slightly soluble in water, while dissolving under coating, ionizes out, at anode position and metal ion, is combined into insoluble inner complex passive film, and this film hardness is high, adhere firmly.
Organic-silicon-modified high-temperature-resistant self-cleaning water electrochemical antifouling paste
performance test table
Claims (1)
1. an organic-silicon-modified high-temperature-resistant self-cleaning water electrochemical antifouling paste, its raw material comprises resin emulsion and coupling agent γ-methacryloxy Trimethoxy silane, described resin emulsion is organosilicon modified crylic acid resin microemulsion, and the adding proportion of described coupling agent γ-methacryloxy Trimethoxy silane is the 0.5-3% of raw material total amount; Wherein the parts by weight of raw materials proportioning of organosilicon modified crylic acid resin microemulsion is:
Methacrylic acid 1.5-2.0
Methacryloxypropyl methoxymethyl phenyl silicone oil 1.4-1.8
Methyl methacrylate 1.2-1.4
Ammonium persulphate 0.1-1.0
Vinylbenzene 0.5-0.8
Concentration is 30% ammoniacal liquor 1.0-3.0
Vinyl cyanide 1.0-2.0
Fatty alcohol-polyoxyethylene ether-3 0.1-1
Fatty alcohol-polyoxyethylene ether-7 0.1-1
N-butyl acrylate 5-12
Poly(oxyethylene glycol) 400 0.8-1.5
Polyoxyethylenated alcohol sodium sulfate 0.5-2.0
Ethyl acrylate 5-12
Sodium lauryl sulphate 0.5-2
Water 4-8;
The preparation method of described organosilicon modified crylic acid resin microemulsion is:
(1) pre-emulsification of monomer: by a part of fatty alcohol-polyoxyethylene ether-7, sodium lauryl sulphate, polyoxyethylenated alcohol sodium sulfate, poly(oxyethylene glycol) 400, with methacrylic acid, vinylbenzene, vinyl cyanide, mix and blend is made pre-emulsion I; Again remaining fatty alcohol-polyoxyethylene ether-7 are added in fatty alcohol-polyoxyethylene ether-3, methyl methacrylate, n-butyl acrylate, ethyl acrylate, methacryloxypropyl methoxymethyl phenyl silicone oil, under agitation slowly add a part of water, by phase inversion dispersion method, make pre-emulsion II;
(2) micro-emulsion polymerization: add another part water in the four-hole bottle that thermometer, agitator, prolong are housed, stir, add part pre-emulsion I, with ammoniacal liquor adjust pH to 7, start to heat up, while being warming up to 57-63 ℃, add initiator ammonium persulfate, continue heat up and add another part pre-emulsion I and initiator ammonium persulfate, temperature is controlled at 87-93 ℃, continue to add pre-emulsion II and ammonium persulphate, and keep reaction 1.2-1.8h, naturally cooling, filter, obtain organic-silicon-modified acrylic resin microemulsion.
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| CN201210293904.9A CN102838913B (en) | 2012-08-17 | 2012-08-17 | Organosilicone modified heat-resistant self-cleaning waterborne electrochemistry corrosion-resistant paint and preparation method thereof |
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| CN201210293904.9A CN102838913B (en) | 2012-08-17 | 2012-08-17 | Organosilicone modified heat-resistant self-cleaning waterborne electrochemistry corrosion-resistant paint and preparation method thereof |
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| CN102838913B true CN102838913B (en) | 2014-08-13 |
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| CN105063624B (en) * | 2015-08-21 | 2017-08-25 | 海门市瑞泰纺织科技有限公司 | A kind of wheel hub antirust agent |
| CN107892856A (en) * | 2017-11-23 | 2018-04-10 | 江门市水星涂料科技有限公司 | A kind of water-based all-round conversion and prevention paint of rust and preparation method thereof |
| CN111019465B (en) * | 2019-12-27 | 2021-06-22 | 海安常州大学高新技术研发中心 | Preparation process of organic-inorganic composite water-based acrylic acid anticorrosive paint |
| CN117468268B (en) * | 2023-12-27 | 2024-03-22 | 湖南大道新材料有限公司 | Water-blocking paper bag and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5094889A (en) * | 1989-05-10 | 1992-03-10 | Ashland Oil, Inc. | Water based coating for roughened metal surfaces |
| CN101857753A (en) * | 2010-06-22 | 2010-10-13 | 深圳大学 | Anticorrosive coating as well as coating method and application thereof |
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2012
- 2012-08-17 CN CN201210293904.9A patent/CN102838913B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5094889A (en) * | 1989-05-10 | 1992-03-10 | Ashland Oil, Inc. | Water based coating for roughened metal surfaces |
| CN101857753A (en) * | 2010-06-22 | 2010-10-13 | 深圳大学 | Anticorrosive coating as well as coating method and application thereof |
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