CN102876196B - Not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment - Google Patents
Not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment Download PDFInfo
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- CN102876196B CN102876196B CN201110199612.4A CN201110199612A CN102876196B CN 102876196 B CN102876196 B CN 102876196B CN 201110199612 A CN201110199612 A CN 201110199612A CN 102876196 B CN102876196 B CN 102876196B
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- epoxy resin
- rust
- electrically conductive
- bisphenol
- corrosion prevention
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Abstract
The present invention relates to not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment, this coating comprises following component and weight part content: mixed curing agent 30 ~ 40, epoxy resin 10 ~ 20, thinner 10 ~ 55, defoamer 0.3 ~ 3.Compared with prior art, the present invention containing any rust-stabilising pigment, does not avoid the heavy metal suspicion of contaminate environment, and the scope of application is wider, can be used for sour environment, in addition not containing environmentally harmful phthalic ester plasticizer.
Description
Technical field
The present invention relates to electrically conductive polyaniline anticorrosive coating, especially relate to a kind of not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment.
Background technology
Metallic corrosion is a difficult problem of the puzzled development of the national economy always, the annual metallic corrosion loss amount in the whole world is up to the 20-40% of annual metal production, it is earthquake, floods, the summations such as the natural calamity such as typhoon doubly, it is that to tackle metallic corrosion most economical that coating is produced in resistance to protection against corrosion, most convenient, one of the most effective means, wherein conventional in most important heavy duty system rust-proofing primer adopts epoxy zinc-rich and inorganic zinc-rich, zinc is that heavy metal is harmful to EC regulations to hydrobiont and limits the use of zinc, therefore finding Novel pollution-free anticorrosive coating is inevitable development trend.
No matter epoxy zinc-rich or zinc-rich coating, its anticorrosion mechanism relies on the conduction of zinc powder in paint film to be used as sacrificial anode to shield to metallic surface, be exactly now adopt similar protection against corrosion mechanism by way of, seek such material, polyaniline is that in many conductive polymerss, structure diversity is learned in preparation technology's letter, there is unique mechanism of doping effect, excellent physical and chemical performance and raw material material cheap and easy to get, but the comprehensive mechanical property of polyaniline is poor, be insoluble to common organic solvents and rheological property is bad, so be difficult to adopt traditional diamond-making technique shaping, thus have impact on it to apply.Now a kind of existing method be with utilize suitable substituting group because of and doping agent prepare high-conductivity polyaniline, polyaniline coating can be made like this to have good mechanical strength and sticking power.
The visible Wuhan Inst. of Material Protection CN1869101 of manufacture method (publication number, or application number CN20061001948.1) of the electrically conductive polyaniline that the present invention adopts.Electrically conductive polyaniline protective system domestic at present can have been accomplished solvent-free, may be used in marine finish, making protection against corrosion priming paint, but its use range is not too wide, particularly in acid-resistant environment, though and be solvent-free, but be also harmful to softening agent containing Phthalates, the kind of employing mainly contains electrically conductive polyaniline+epoxy resin, and solidifying agent is polyethylene polyamine class.Although the solidification of this kind of coating is very fast, there is toxicity, the paint film after solidification is more crisp, snappiness and impact poor, under moisture conditions, paint film such as easily to highlight at the problem, and therefore the present invention adopts modified phenolic amine to replace.To overcome above-mentioned disadvantage, due to curing agent modified phenolic aldehyde amine, then just do not need rust-stabilising pigment, even if because this kind of solidifying agent also can reach protection against corrosion requirement without rust-stabilising pigment, with this just without the need to adding softening agent, abandon the harm of phthalate to environment, the present invention the epoxy resin that is suitable for also than " preparation method of conducting polyaniline solvent free corrosion prevention coating " (Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences patent publication No. CN1243852A of existing patent applied for, application number CN981169783) want extensively, this is not limited to double A type epoxy resin and also has double F type epoxy resin etc., so just can its Application Areas vast, especially in acidproof situation.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and provide a kind of applied widely, can be used for sour environment, without environmentally harmful phthalic ester plasticizer not containing rust-stabilising pigment electrically conductive polyaniline solvent free corrosion prevention erosion coating.
Object of the present invention can be achieved through the following technical solutions:
Not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment, it is characterized in that, this coating comprises following component and weight part content:
Mixed curing agent 30 ~ 40;
Epoxy resin 10 ~ 20;
Thinner 10 ~ 55;
Defoamer 0.3 ~ 3.
Described mixed curing agent is intrinsically conducting polyaniline and solidifying agent is (10 ~ 20) by weight: (80 ~ 90) are mixed to get.
The molecular formula of described intrinsically conducting polyaniline is:
Wherein y is 0 ~ 1, R1 is C
mh
2m+2o, m are 1 ~ 6, n is 50 ~ 100.
Described solidifying agent is modified phenolic amine, comprises cashew nut oil modified phenolic aldehyde amine.
Described epoxy resin is the hybrid resin of bisphenol A type epoxy resin, bisphenol f type epoxy resin or bisphenol type epoxy and bisphenol F type epoxy.
Described bisphenol A type epoxy resin is commercially available E35, E42, E44 epoxy resin; Described bisphenol f type epoxy resin is commercially available DER354 epoxy resin; Described bisphenol type epoxy and the hybrid resin of bisphenol F type epoxy are commercially available DER351 epoxy resin.
Described thinner is the glycidyl ether of alcohols or aliphatic glycidyl ether.
The glycidyl ether of described alcohols is the glycidyl ether of butanols, Virahol, high alcohol; Described aliphatic glycidyl ether comprises polypropylene glycol glycidyl ether or trihydroxymethylpropanyltri diglycidyl ether.
Described defoamer is the alkyl ester of C3-C11 lipid acid, oligomeric polyoxyethylene or silicone oil.
Compared with prior art, the present invention has following advantage:
(1) not containing any rust-stabilising pigment, the heavy metal suspicion of contaminate environment is avoided;
(2) scope of application is wider, can be used for sour environment;
(3) without environmentally harmful phthalic ester plasticizer.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1 ~ 4
The eigenmode polyaniline that goes out to conduct electricity by the weight part by table 1 is dissolved in the cashew nut oil modified phenolic aldehyde amine of weight part shown in table 1, within 2 hours, make it to dissolve with magnetic stirrer, then carry out filtration with glass funnel and make mixed curing agent, stand-by, take the epoxy resin of the weight part by table 2, add the thinner of weight part shown in table 2, silicone oil, carry out induction stirring 2 hours, make it Homogeneous phase mixing, add the mixed curing agent of weight part shown in above-mentioned table two again, (2 hours) static 1 hour are afterwards stirred with magnetic stirrer, on the coating painting brush that this is made or No. 45 steel plates being sprayed at after treatment, by the coating that this prepares, by painting brush or spray gun in construction on processed steel plate, its thickness is made to remain on 15-250 micron.With carry out 8-24 hour under normal temperature and solidify, obtain homogeneous transparent and tough and tensile faint blue coating.
Then be dipped in the NaCl solution of 5% by this painted steel sheet, place 3 months at normal temperatures, by coating and steel sheet peeling off after taking-up, detect by an unaided eye surface of steel plate situation.Find that surface of steel plate adheres to the tough and tensile and black thin film layer of densification of one deck, test it for Fe through XPS
3o
4and Fe
2o
3, can be observed its ground light after peelling off this layer film with blade and without the metallic surface of rusty scale, this its anticorrosion ability provable is excellent.
Table 1 mixed curing agent
Table 2 formulation for coating material
Embodiment 5
Not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment, this coating comprises following component and weight part content: mixed curing agent 30kg, epoxy resin 10kg, thinner 10kg, defoamer 0.3kg, wherein, to be intrinsically conducting polyaniline and solidifying agent be mixed curing agent is by weight mixed to get at 10: 90.
The molecular formula of intrinsically conducting polyaniline is:
Wherein y is 0, R1 is CH
6o, n are 50, and solidifying agent adopts cashew nut oil modified phenolic aldehyde amine, and epoxy resin is the glycidyl ether of bisphenol A type epoxy resin, thinner Virahol, and defoamer is the fatty acid alkyl ester of C3.
During synthesis, get polyaniline in eigenstate and be added in modified phenolic amine under magnetic stirrer and dissolve, stir after within 2-4 hour, filtering and make mixed curing agent;
Take epoxy resin by formula, add thinner and defoamer, carry out induction stirring, make it Homogeneous phase mixing, then add above-mentioned mixed curing agent.Stir 2-3.5 hour, then place 10-20 minute, namely prepare product.By the coating that this prepares, by painting brush or spray gun in construction on processed steel plate, its thickness is made to remain on 15-250 micron.With carry out 8-24 hour under normal temperature and solidify, obtain homogeneous transparent and tough and tensile faint blue coating.
Be dipped in by this painted steel sheet in the NaCL solution of 5%, place 3 months at normal temperatures, by coating and steel sheet peeling off after taking-up, detect by an unaided eye surface of steel plate situation.Find that surface of steel plate adheres to the tough and tensile and black thin film layer of densification of one deck, test it for Fe304 and Fe203 through XPS, can be observed its ground light after peelling off this layer film with blade and without the metallic surface of rusty scale, this its anticorrosion ability provable is excellent.
Embodiment 6
Not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment, this coating comprises following component and weight part content: mixed curing agent 35kg, epoxy resin 15kg, thinner 30kg, defoamer 1kg, wherein, to be intrinsically conducting polyaniline and solidifying agent be mixed curing agent is by weight mixed to get at 15: 85.
The molecular formula of intrinsically conducting polyaniline is:
Wherein y is 0, R1 is C
3h
8o, n are 80.Solidifying agent adopts cashew nut oil modified phenolic aldehyde amine, and epoxy resin is bisphenol f type epoxy resin, and thinner is polypropylene glycol glycidyl ether, and defoamer is oligomeric polyoxyethylene.
During synthesis, get polyaniline in eigenstate and be added in modified phenolic amine under magnetic stirrer and dissolve, stir after within 2-4 hour, filtering and make mixed curing agent;
Take epoxy resin by formula, add thinner and defoamer, carry out induction stirring, make it Homogeneous phase mixing, then add above-mentioned mixed curing agent.Stir 2-3.5 hour, then place 10-20 minute, namely prepare product.By the coating that this prepares, by painting brush or spray gun in construction on processed steel plate, its thickness is made to remain on 15-250 micron.With carry out 8-24 hour under normal temperature and solidify, obtain homogeneous transparent and tough and tensile faint blue coating.
Be dipped in by this painted steel sheet in the NaCL solution of 5%, place 3 months at normal temperatures, by coating and steel sheet peeling off after taking-up, detect by an unaided eye surface of steel plate situation.Find that surface of steel plate adheres to the tough and tensile and black thin film layer of densification of one deck, test it for Fe304 and Fe203 through XPS, can be observed its ground light after peelling off this layer film with blade and without the metallic surface of rusty scale, this its anticorrosion ability provable is excellent.
Embodiment 7
Not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment, this coating comprises following component and weight part content: mixed curing agent 40kg, epoxy resin 20kg, thinner 55kg, defoamer 3kg, wherein, to be intrinsically conducting polyaniline and solidifying agent be mixed curing agent is by weight mixed to get at 20: 80.
The molecular formula of intrinsically conducting polyaniline is:
Wherein y is 1, R1 is C
6h
14o, n are 100, and solidifying agent adopts cashew nut oil modified phenolic aldehyde amine, and epoxy resin is the hybrid resin of bisphenol type epoxy and bisphenol F type epoxy, and thinner is trihydroxymethylpropanyltri diglycidyl ether, and defoamer is silicone oil.
During synthesis, get polyaniline in eigenstate and be added in modified phenolic amine under magnetic stirrer and dissolve, stir after within 2-4 hour, filtering and make mixed curing agent;
Take epoxy resin by formula, add thinner and defoamer, carry out induction stirring, make it Homogeneous phase mixing, then add above-mentioned mixed curing agent.Stir 2-3.5 hour, then place 10-20 minute, namely prepare product.By the coating that this prepares, by painting brush or spray gun in construction on processed steel plate, its thickness is made to remain on 15-250 micron.With carry out 8-24 hour under normal temperature and solidify, obtain homogeneous transparent and tough and tensile faint blue coating.
Be dipped in by this painted steel sheet in the NaCL solution of 5%, place 3 months at normal temperatures, by coating and steel sheet peeling off after taking-up, detect by an unaided eye surface of steel plate situation.Find that surface of steel plate adheres to the tough and tensile and black thin film layer of densification of one deck, test it for Fe304 and Fe203 through XPS, can be observed its ground light after peelling off this layer film with blade and without the metallic surface of rusty scale, this its anticorrosion ability provable is excellent.
Claims (6)
1., not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment, it is characterized in that, this coating adopts following component and weight part content:
Described mixed curing agent be intrinsically conducting polyaniline and solidifying agent by weight for (10 ~ 20) ︰ (80 ~ 90) are mixed to get,
The molecular formula of described intrinsically conducting polyaniline is:
Wherein y is 0 ~ 1, R1 is C
mh
2m+2o, m are 1 ~ 6, n is 50 ~ 100,
Described solidifying agent is cashew nut oil modified phenolic aldehyde amine.
2. according to claim 1 not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment, it is characterized in that, described epoxy resin is the hybrid resin of bisphenol A type epoxy resin, bisphenol f type epoxy resin or bisphenol A type epoxy resin and bisphenol f type epoxy resin.
3. according to claim 2 not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment, it is characterized in that, described bisphenol A type epoxy resin is commercially available E35, E42, E44 epoxy resin; Described bisphenol f type epoxy resin is commercially available DER354 epoxy resin; Described bisphenol A type epoxy resin and the hybrid resin of bisphenol f type epoxy resin are commercially available DER351 epoxy resin.
4. according to claim 1 not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment, it is characterized in that, described thinner is the glycidyl ether of alcohols.
5. according to claim 4 not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment, it is characterized in that, the glycidyl ether of described alcohols is the glycidyl ether of butanols, Virahol, high alcohol.
6. according to claim 1 not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment, it is characterized in that, described defoamer is the alkyl ester of C3-C11 lipid acid, oligomeric polyoxyethylene or silicone oil.
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| CN201110199612.4A CN102876196B (en) | 2011-07-15 | 2011-07-15 | Not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment |
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| CN201110199612.4A CN102876196B (en) | 2011-07-15 | 2011-07-15 | Not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7278334B2 (en) | 2021-02-24 | 2023-05-19 | 南亞塑膠工業股▲分▼有限公司 | Anticorrosive paint and its manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103865361B (en) * | 2014-04-04 | 2016-04-20 | 山东旭锐新材有限公司 | A kind of under water or the polyaniline anti-corrosive paint of wet structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1243852A (en) * | 1998-07-30 | 2000-02-09 | 中国科学院长春应用化学研究所 | Non-solvent anticorrosion conducting paint of polyphenylamine and its preparing process |
| CN101643608A (en) * | 2008-08-06 | 2010-02-10 | 中国科学院金属研究所 | Polyaniline modified metal carbon nanotube coating and preparation method thereof |
| CN101643615A (en) * | 2008-08-06 | 2010-02-10 | 中国科学院金属研究所 | Polyaniline modified glass flake heavy-duty anti-corrosive coating and preparation method thereof |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1243852A (en) * | 1998-07-30 | 2000-02-09 | 中国科学院长春应用化学研究所 | Non-solvent anticorrosion conducting paint of polyphenylamine and its preparing process |
| CN101643608A (en) * | 2008-08-06 | 2010-02-10 | 中国科学院金属研究所 | Polyaniline modified metal carbon nanotube coating and preparation method thereof |
| CN101643615A (en) * | 2008-08-06 | 2010-02-10 | 中国科学院金属研究所 | Polyaniline modified glass flake heavy-duty anti-corrosive coating and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7278334B2 (en) | 2021-02-24 | 2023-05-19 | 南亞塑膠工業股▲分▼有限公司 | Anticorrosive paint and its manufacturing method |
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Effective date of registration: 20180503 Address after: 201512 738 Jinhuan Road, Jinshan Town, Jinshan District, Shanghai Patentee after: Shanghai chase exhibition curtain new energy-saving materials Limited by Share Ltd Address before: 201208 Jindu Road, Minhang District, Shanghai, No. 4289 Patentee before: Shanghai Datong High-tech Material Co., Ltd. |
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Granted publication date: 20160217 Termination date: 20200715 |