CN103450762B - A kind of aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust and preparation method thereof - Google Patents
A kind of aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust and preparation method thereof Download PDFInfo
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- CN103450762B CN103450762B CN201310439261.9A CN201310439261A CN103450762B CN 103450762 B CN103450762 B CN 103450762B CN 201310439261 A CN201310439261 A CN 201310439261A CN 103450762 B CN103450762 B CN 103450762B
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Abstract
The invention discloses a kind of aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust and preparation method thereof, belong to anti-corrosive metal coating technical field.This coating primarily of gallic acid, Weibull, cation acrylic emulsion, permeate agent, defoamer, ethanol composition transforming agent emulsion and form polyaniline epoxy composite emulsion by epoxy emulsion and Polyaniline emulsion and form.The coating adopting the inventive method to prepare has the features such as rust transformation is thorough, film dense uniform, anti-scratch performance and antiseptic property are excellent.Because the method adopting epoxy emulsion, Polyaniline emulsion and transforming agent and ACRYLIC EMULSION to separate prepares two component Corrosion resisting paint without need of cleaning rust, thoroughly solve the deficiencies in the prior art, significantly improve working life and the salt water resistance performance of coating, thus have broad application prospects.
Description
Technical field
The invention belongs to anti-corrosive metal coating technical field, be specifically related to a kind of aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust and preparation method.
Technical background
Ferrous materials, as the maximum metallic substance of consumption, has numerous irreplaceable superiority, but due to the susceptibility-to-corrosion of iron and steel, brings tremendous economic to lose all to every year country and society, so the anticorrosive work of iron and steel is the focus that researcher is studied always.Coating antiseptic is method the simplest, effective and economic in steel anti-corrosive method, in order to obtain good Corrosion Protection, iron rust on base material must be removed clean by general protective system before application, otherwise paint film can be caused to destroy due to the continuous expansion of iron rust, affects preservative effect.Eliminate rust a very heavy work, many large-scale steel and iron member, as bridge, boats and ships etc., due to the restriction by execution conditions in maintenance process, be difficult to adopt mechanized construction method, craft or power tool can only be adopted to eliminate rust, so not only labour intensity large, construct difficult, expense is huge, and dust can endanger the healthy of workmen.
About the report of waterborne rusted paint is a lot, but be prepare using the acidic substance such as phosphoric acid, Weibull as transforming agent mostly, because phosphoric acid is compatible with most water-based emulsion, poor stability, and the consumption of phosphoric acid is difficult to grasp, if phosphoric acid is excessive can promote corrosion on the contrary, this series products is not thorough to the conversion performance of iron and steel corrosion, and film forming ability poor-performing, which limits the development of waterborne rusted paint.In order to address these problems, Chinese patent CNIO2391732A discloses a kind of water and milk environment-friendly type steel-iron with rust anticorrosive coating bed material, take benzene emulsion as film forming matter, Weibull is transforming agent, be equipped with Graphite Powder 99 and polyvinyl alcohol etc. and prepare coating, solve aqueous, environmental protective and the problem without the need to rust cleaning, but there is the problems such as film adhesive is little, the poor stability of coating.Chinese patent CN102993846A discloses a kind of steel structure aqueous rust face protective system and preparation method, adopt converting agent of iron rust, epoxy emulsion, cationic styrene-acrylic emulsion, film coalescence aid and thickening dispersion agent, add Polyaniline emulsion to converting agent of iron rust, solve the homogeneity of waterborne rusted paint film forming, film easily whitens, the problem of rust transformation sexuality difference, improve the sticking power of waterborne rusted paint, but this coating is by transforming agent, phosphoric acid etc. and epoxy emulsion, it is shorter to there is the shelf lives in the single-component coating that the film forming matters such as cationic styrene-acrylic emulsion are directly mixed with, the bad easy deposition of Polyaniline emulsion dispersion effect, actual mechanical process phosphoric acid is the shortcoming such as easy gel in composite emulsion.
Summary of the invention
The object of the present invention is to provide the aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust that a kind of rust transformation is thorough, film forming is fine and close, anti-corrosion performance is excellent, working life is long.
In order to solve the problems of the technologies described above, the present invention is achieved by following technical proposal.
The invention provides a kind of aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust, this coating is made up of according to mass ratio 6 ~ 8:1 transforming agent emulsion and polyaniline epoxy composite emulsion, wherein:
Described transforming agent emulsion, by percentage to the quality, its formula consists of:
Described polyaniline epoxy composite emulsion, by percentage to the quality, its formula consists of:
Epoxy emulsion 92 ~ 96
Polyaniline emulsion 4 ~ 8.
Further, described Polyaniline emulsion be with Witco 1298 Soft Acid, citric acid be Tree-tea interplantation, ammonium persulphate for oxygenant, adopt positive micro emulsion oxidation style synthesis; Described cation acrylic emulsion is JH ~ 3030 type that Ma'an Mountain nine and Chemical Industry Science Co., Ltd produce.
Further, described permeate agent is glycerol; Described defoamer is tributyl phosphate.
Invention also provides a kind of method preparing above-mentioned aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust, this preparation method comprises the following steps:
(1) preparation of transforming agent emulsion:
Get 1 ~ 2 part of gallic acid respectively and 8 ~ 12 parts of ethanol is mixed with gallic acid ethanolic soln, gets 1 ~ 2 part of Weibull and 8 ~ 10 parts of water are mixed with the Weibull aqueous solution, then by two kinds of solution mixing and stirring, this mixing solutions is joined in the cation acrylic emulsion container being equipped with 70 ~ 80 parts again and stir, finally add the transforming agent emulsion just obtaining this coating after the permeate agent of 0.2 ~ 0.5 part and 0.2 ~ 0.3 part of defoamer stir successively;
(2) preparation of polyaniline epoxy composite emulsion:
Add 92 ~ 96 parts of epoxy emulsions and 4 ~ 8 parts of Polyaniline emulsions in a reservoir, rapid stirring 10 ~ 20min obtains the polyaniline epoxy composite emulsion of this coating when it's convenient after making it evenly;
(3) aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust preparation:
The polyaniline epoxy composite emulsion prepared of the transforming agent emulsion prepare step (1) and step (2) just obtains aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust after 6 ~ 8:1 mixing and stirring in mass ratio.
Adopt the aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust that aforesaid method is obtained, adopt the method for spraying or be directly coated in brush on the steel plate of yellow iron rust, the inherent surface of steel plate of 10min can form dense uniform black coating film, and the salient features of this film is as shown in table 1.
Table 1 aqueous polyanion composite epoxy of the present invention Corrosion resisting paint without need of cleaning rust salient features
Compared with prior art, the present invention has following technique effect:
1, owing to adopting Tree-tea interplantation, emulsifying dispersant prepares Polyaniline emulsion, select to make it possess good film forming curing performance and fine and close shielding effect with epoxy emulsion and cation acrylic emulsion etc., and can have with polyphenol transforming agent (gallic acid and Weibull) and act synergistically to promote iron rust thoroughly to transform and be fixed in steel substrate, formed have excellent anti-scratch, anti-spot corrosion long-effective corrosion band rust coating, solve waterborne rusted paint film-forming properties in prior art poor, rust transformation is not thorough, matrix and coating binding force weak, the problems such as salt water resistance poor performance.The effect that polyaniline is served as in film is formed " forming a connecting link ", polyaniline and polyphenol and the iron-based body of doping form interpenetrative inner complex, solve to a certain extent ubiquity in waterborne rusted paint " change rust and loses ", " film forming and conversion ", " Water-borne modification and water-repellancy ' etc. between a conflicting difficult problem.Because containing emulsifying agent and assistant for emulsifying agent and high molecular polymer protecting glue in Polyaniline emulsion, during a small amount of interpolation, these materials have dispersion, hydrotropy, wetting, osmosis, effective constituent rapid osmotic in coating can be helped and react with rusty scale, make, in its coating drying and forming-film process, chemically crosslinked occurs, polyaniline participates in the chemical sequestering action of transforming agent and iron-based body simultaneously and ironing surface corrosion is converted into hydrophobic passivation layer, the high molecular polymer molecule being coated on the metallic surface of having got rusty is formed when film forming align, thus create extraordinary derusting rust-proofing effect.
2, owing to adopting Polyaniline emulsion to mix packing separately with epoxy emulsion, can avoid with vinylformic acid in there is carboxyl, ester group and potential active hydrogen and epoxy group(ing) when liquid state and deferred reaction occur and affects stability in storage, can promote that again film in drying process, chemically crosslinked occurs and improves the waterproof of coating, antiseptic property.Particularly salt water resistance Performance Ratio prior art improves 40 ~ 50h.Because Polyaniline emulsion and epoxy emulsion have the dispersion stabilization that good dispersiveness and consistency, polyphenol transforming agent (gallic acid and Weibull) have height in cation acrylic emulsion system, therefore adopt this method can overcome the deficiencies in the prior art completely.In addition, the present invention adopts and has grown its working life compared with common bicomponent epoxy resin coating a lot, and the working life of coating of the present invention is 72h, and the working life of general two component epoxy coating is within 5h.
Do not need heating in the preparation process of 3, this coating, all raw materials are all water-soluble or water-dispersions, therefore aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust of the present invention belongs to energy-saving and cost-reducing, environmentally friendly product.
Embodiment
Be further described below in conjunction with the preparation process of embodiment to target product of the present invention:
Embodiment 1
(1) preparation of transforming agent emulsion:
Get 1g gallic acid respectively and 10g alcohol is mixed with gallic acid ethanolic soln, gets 1g part Weibull and 9g water is mixed with the Weibull aqueous solution, then by two kinds of solution mixing and stirring, this mixing solutions is joined in the cation acrylic emulsion container that 75g is housed again and stir, finally add the transforming agent emulsion just obtaining this coating after the glycerol of 0.3g and 0.3 tributyl phosphate stir successively;
(2) preparation of polyaniline epoxy composite emulsion:
Add 93g epoxy emulsion and 7g Polyaniline emulsion in a reservoir, rapid stirring 10 ~ 20min obtains the polyaniline epoxy composite emulsion of this coating when it's convenient after making it evenly
(3) aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust preparation:
By the quality of the quality of transforming agent emulsion and polyaniline epoxy composite emulsion by 7:1 than just obtaining aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust after mixing and stirring.
The aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust that aforesaid method is obtained, adopts the method for spraying to be coated on the steel plate of yellow iron rust, and the inherent surface of steel plate of 10min can form dense uniform black coating film, and surface drying time is the salient features of 20min, film:
Hardness (pencil method): 3H
Sticking power (frame method): 0 grade
The rust transformation time (estimating complete blackening): 12min
Rust transformation degree (film observes metal matrix body colour after peeling off): 99%
Resistance to salt water (saline soak): 192 hours non-foaming, do not peel off, non-corrosive
Salt-fog resistant time (in salt fog cut non-corrosive): 77h
Embodiment 2
(1) preparation of transforming agent emulsion:
Get 2g gallic acid respectively and 12g alcohol is mixed with gallic acid ethanolic soln, gets 2g part Weibull and 10g water is mixed with the Weibull aqueous solution, then by two kinds of solution mixing and stirring, this mixing solutions is joined in the cation acrylic emulsion container that 80g is housed again and stir, finally add the transforming agent emulsion just obtaining this coating after 0.2g glycerol and 0.2 tributyl phosphate stir successively;
(2) preparation of polyaniline epoxy composite emulsion:
Add 92g epoxy emulsion and 8g Polyaniline emulsion in a reservoir, rapid stirring 10 ~ 20min obtains the polyaniline epoxy composite emulsion of this coating when it's convenient after making it evenly
(3) aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust preparation:
By the quality of the quality of transforming agent emulsion and polyaniline epoxy composite emulsion by 8:1 than just obtaining aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust after mixing and stirring.
The aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust that aforesaid method is obtained, adopts brushing method to be coated on the steel plate of yellow iron rust, and the inherent surface of steel plate of 8min can form dense uniform black coating film, and surface drying time is the salient features of 25min, film:
Hardness (pencil method): 3H
Sticking power (frame method): 1 grade
The rust transformation time (estimating complete blackening): 10min
Rust transformation degree (film observes metal matrix body colour after peeling off): 99%
Resistance to salt water (saline soak): 196 hours non-foaming, do not peel off, non-corrosive
Salt-fog resistant time (in salt fog cut non-corrosive): 78h
Embodiment 3
(1) preparation of transforming agent emulsion:
Get 2g gallic acid respectively and 12g alcohol is mixed with gallic acid ethanolic soln, gets 1g part Weibull and 8g water is mixed with the Weibull aqueous solution, then by two kinds of solution mixing and stirring, this mixing solutions is joined in the cation acrylic emulsion container that 80g is housed again and stir, finally add the transforming agent emulsion just obtaining this coating after 0.5g glycerol and 0.2 tributyl phosphate stir successively.
(2) preparation of polyaniline epoxy composite emulsion:
Add 94g epoxy emulsion and 6g Polyaniline emulsion in a reservoir, rapid stirring 10 ~ 20min obtains the polyaniline epoxy composite emulsion of this coating when it's convenient after making it evenly.
(3) aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust preparation:
By the quality of the quality of transforming agent emulsion and polyaniline epoxy composite emulsion by 6:1 than just obtaining aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust after mixing and stirring.
The aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust that aforesaid method is obtained, adopts brushing method to be coated on the steel plate of yellow iron rust, and the inherent surface of steel plate of 9min can form dense uniform black coating film, and surface drying time is the salient features of 25min, film:
Hardness (pencil method): 3H
Sticking power (frame method): 0 grade
The rust transformation time (estimating complete blackening): 13min
Rust transformation degree (film observes metal matrix body colour after peeling off): 98%
Resistance to salt water (saline soak): 198 hours non-foaming, do not peel off, non-corrosive
Salt-fog resistant time (in salt fog cut non-corrosive): 74h
Embodiment 4 ~ 8
Preparation method is identical with embodiment 1, only changes the consumption of each component of step (1) transforming agent emulsion, and fixing step (2) and (3) form and method is pressed following constant, and its performance test is in table 2
(2) preparation of polyaniline epoxy composite emulsion:
Add 95g epoxy emulsion and 5g Polyaniline emulsion in a reservoir, rapid stirring 10 ~ 20min obtains the polyaniline epoxy composite emulsion of this coating when it's convenient after making it evenly
(3) aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust preparation:
By the quality of the quality of transforming agent emulsion and polyaniline epoxy composite emulsion by 7:1 than just obtaining aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust after mixing and stirring.
Table 2 embodiment 4 ~ 8 transforming agent emulsion composition and aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust performance
Note: resistance to salt water refers to, the salt solution that sample is 3% in concentration soaks, 25 DEG C, non-foaming, does not peel off, non-corrosive.
Claims (2)
1. an aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust, is characterized in that: this coating is made up of according to mass ratio 6 ~ 8:1 transforming agent emulsion and polyaniline epoxy composite emulsion, wherein:
Described transforming agent emulsion, by percentage to the quality, its formula consists of:
Described polyaniline epoxy composite emulsion, by percentage to the quality, its formula consists of:
Epoxy emulsion 92 ~ 96
Polyaniline emulsion 4 ~ 8
Described Polyaniline emulsion be with Witco 1298 Soft Acid, citric acid be Tree-tea interplantation, ammonium persulphate for oxygenant, adopt positive micro emulsion oxidation style synthesis;
Described cation acrylic emulsion is JH ~ 3030 that Ma'an Mountain nine and Chemical Industry Science Co., Ltd produce;
Described permeate agent is glycerol, and described defoamer is tributyl phosphate.
2. a preparation method for aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust as claimed in claim 1, it is characterized in that, this preparation method comprises the following steps:
(1) preparation of transforming agent emulsion:
Get 1 ~ 2 part of gallic acid respectively and 8 ~ 12 parts of ethanol is mixed with gallic acid ethanolic soln, gets 1 ~ 2 part of Weibull and 8 ~ 10 parts of deionized waters are mixed with the Weibull aqueous solution, then by two kinds of solution mixing and stirring, this mixing solutions is joined in the cation acrylic emulsion container being equipped with 75 ~ 80 parts again and stir, finally add successively after the permeate agent of 0.2 ~ 0.5 part and 0.2 ~ 0.3 part of defoamer stir and just obtain described transforming agent emulsion;
(2) preparation of polyaniline epoxy composite emulsion:
Add 92 ~ 96 parts of epoxy emulsions and 4 ~ 8 parts of Polyaniline emulsions in a reservoir, rapid stirring 10 ~ 20min obtains described polyaniline epoxy composite emulsion after making it evenly when it's convenient;
(3) aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust preparation:
The polyaniline epoxy composite emulsion prepared of the transforming agent emulsion prepare step (1) and step (2) just obtains aqueous polyanion composite epoxy Corrosion resisting paint without need of cleaning rust after 6 ~ 8:1 mixing and stirring in mass ratio.
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| CN103897559B (en) * | 2014-03-21 | 2016-08-17 | 哈尔滨工程大学 | A kind of epoxidation zone rust coating process |
| CN104311823B (en) * | 2014-10-09 | 2016-08-17 | 安徽工业大学 | A kind of Polyaniline emulsion with derusting rust-proofing function and preparation method |
| CN105315829B (en) * | 2015-12-02 | 2017-05-24 | 马鞍山市三江机械有限公司 | Room-temperature rust removal blackening agent and preparation method thereof |
| CN105925092A (en) * | 2016-06-24 | 2016-09-07 | 无锡伊佩克科技有限公司 | Waterborne over-rust coating for steel and preparation method thereof |
| CN107227104A (en) * | 2017-07-18 | 2017-10-03 | 大悟县新生农业科技有限公司 | A kind of citric acid secondary doping polyaniline and its application in anticorrosive paint |
| CN107868546A (en) * | 2017-12-13 | 2018-04-03 | 广州宣宁化工科技有限公司 | A kind of preparation method and applications of electrostatic powder spraying band rust transformation primer |
| CN109622332A (en) * | 2018-11-22 | 2019-04-16 | 淮北市菲美得环保科技有限公司 | A kind of anticorrosion process of steel construction |
| CN111270253A (en) * | 2020-03-19 | 2020-06-12 | 陈承 | Water-based anticorrosive rust-removing penetrant and preparation method and application thereof |
| CN112143337B (en) * | 2020-09-25 | 2021-12-10 | 吉林省陆柒肆伍贰科技有限公司 | Carboxyl-containing polyphenol compound secondary-doped polyaniline epoxy resin coating and preparation method thereof |
| CN113403623B (en) * | 2021-06-10 | 2022-08-23 | 上海佳船工程监理发展有限公司 | Secondary rust remover for ships and secondary rust removing process for ships |
| CN114316731A (en) * | 2021-11-29 | 2022-04-12 | 广西盛隆冶金有限公司 | Corrosion-resistant graphene modified material and steel dip-coating process thereof |
| CN116445046A (en) * | 2023-02-17 | 2023-07-18 | 中国科学院长春应用化学研究所 | Water-based rust polyaniline conversion type anti-corrosion primer and preparation method thereof |
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| US5441773A (en) * | 1992-01-21 | 1995-08-15 | Betz Laboratories, Inc. | Composition and method of forming a black no-rinse conversion coating on metal surfaces |
| CN102993846A (en) * | 2012-12-02 | 2013-03-27 | 安徽工业大学 | Aqueous anticorrosive paint of steel structure and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5441773A (en) * | 1992-01-21 | 1995-08-15 | Betz Laboratories, Inc. | Composition and method of forming a black no-rinse conversion coating on metal surfaces |
| CN102993846A (en) * | 2012-12-02 | 2013-03-27 | 安徽工业大学 | Aqueous anticorrosive paint of steel structure and preparation method thereof |
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