CN102876196A - Conductive polyaniline solvent-free anticorrosive coating not containing anti-rust pigments - Google Patents
Conductive polyaniline solvent-free anticorrosive coating not containing anti-rust pigments Download PDFInfo
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- CN102876196A CN102876196A CN2011101996124A CN201110199612A CN102876196A CN 102876196 A CN102876196 A CN 102876196A CN 2011101996124 A CN2011101996124 A CN 2011101996124A CN 201110199612 A CN201110199612 A CN 201110199612A CN 102876196 A CN102876196 A CN 102876196A
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- solvent
- anticorrosive coating
- electrically conductive
- conductive polyaniline
- bisphenol
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Abstract
The invention relates to a conductive polyaniline solvent-free anticorrosive coating not containing any anti-rust pigments. The coating comprises the following components in part by weight: 30 to 40 parts of mixed curing agent, 10 to 20 parts of epoxy resin, 10 to 55 parts of diluent and 0.3 to 3 parts of defoaming agent. Compared with the prior art, the coating does not contain any anti-rust pigments, avoids environment polluting heavy metals, is wide in application range, can be used in acid environments, and does not contain environmentally harmful phthalate plasticizers.
Description
Technical field
The present invention relates to the electrically conductive polyaniline anticorrosive coating, especially relate to a kind of solvent-free anticorrosive coating of electrically conductive polyaniline that does not contain 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 output, 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 anti-protection against corrosion, most convenient, one of the most effective means, wherein rust-proofing primer commonly used adopts epoxy zinc-rich and inorganic zinc-rich in the most important heavy duty system, zinc is that heavy metal limits the use of zinc to the harmful European Union of hydrobiont rules, and therefore seeking novel pollution-free anticorrosive coating is inevitable development trend.
No matter epoxy zinc-rich or zinc-rich coating; its protection against corrosion mechanism is to rely on the conduction of zinc powder in paint film to be used as sacrificial anode the metallic surface is shielded; be exactly now adopt similar protection against corrosion mechanism by way of; seek such material; polyaniline is that structure diversity is learned in preparation technology's letter in many conductive polymerss; unique mechanism of doping effect is arranged; 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 the traditional diamond-making technique moulding, thereby affected it and apply.Now existing a kind of method be with utilize suitable substituting group because of and doping agent prepare high-conductivity polyaniline, can make like this polyaniline coating have good mechanical strength and sticking power.
The visible CN1869101 of Wuhan Inst. of Material Protection of manufacture method (publication number, or application number CN20061001948.1) of the electrically conductive polyaniline that the present invention adopts.Domestic electrically conductive polyaniline protective system can have been accomplished solvent-free at present, can be used for marine finish and make protection against corrosion priming paint, but its use range is not too wide, particularly in acid-resistant environment, though and be solvent-free, but also contain the harmful softening agent of Phthalates, the kind of employing mainly contains electrically conductive polyaniline+Resins, epoxy, and solidifying agent is the polyethylene polyamine class.Although it is very fast that this class coating solidifies, and exists toxicity, the paint film after the curing is more crisp, and snappiness and impact are relatively poor, and paint film such as easily highlights at the problem under moisture conditions, so the present invention adopts modified phenolic amine to replace.To overcome above-mentioned disadvantage, because curing agent modified phenolic aldehyde amine, then just do not need rust-stabilising pigment, because even this class solidifying agent also can reach the protection against corrosion requirement without rust-stabilising pigment, just need not to add softening agent with this, abandoned the harm of phthalate to environment, the Resins, epoxy that the present invention was suitable for is also than " preparation method of the solvent-free protective system of conducting polyaniline " (patent publication No. CN1243852A of Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences of existing patent applied for, application number CN981169783) wants extensively, this is not limited to double A type Resins, epoxy and also has double F type Resins, epoxy etc., so just can vast its Application Areas, in acidproof situation.
Summary of the invention
Purpose of the present invention be exactly provide in order to overcome the defective that above-mentioned prior art exists a kind of applied widely, can be used for sour environment, without the solvent-free anticorrosive coating of the electrically conductive polyaniline that does not contain rust-stabilising pigment of environmentally harmful phthalic ester plasticizer.
Purpose of the present invention can be achieved through the following technical solutions:
Do not contain the solvent-free anticorrosive coating of electrically conductive polyaniline of rust-stabilising pigment, it is characterized in that, this coating comprises following component and weight part content:
Mixed curing agent 30～40;
Resins, epoxy 10～20;
Thinner 10～55;
Defoamer 0.3～3.
Described mixed curing agent is that intrinsically conducting polyaniline and solidifying agent are (10～20) by weight: (80～90) are mixed to get.
The molecular formula of described intrinsically conducting polyaniline is:
Wherein y is that 0～1, R1 is C
mH
2m+2O, m are that 1～6, n is 50～100.
Described solidifying agent is modified phenolic amine, comprises cashew nut gloss varnish modified phenolic amine.
Described Resins, epoxy 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 Resins, epoxy; Described bisphenol f type epoxy resin is commercially available DER354 Resins, epoxy; The hybrid resin of described bisphenol type epoxy and Bisphenol F type epoxy is commercially available DER351 Resins, epoxy.
Described thinner is glycidyl ether or the aliphatic glycidyl ether of alcohols.
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 advantages of following:
(1) do not contain any rust-stabilising pigment, avoided having the heavy metal suspicion of contaminate environment;
(2) scope of application is wider, can be used for sour environment;
(3) without environmentally harmful phthalic ester plasticizer.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1～4
The eigenmode polyaniline that will go out to conduct electricity by the weight part of table 1 is dissolved in the cashew nut gloss varnish modified phenolic amine of weight part shown in the table 1, made it dissolving in 2 hours with the magnetic stirrer stirring, then filter with glass funnel and make mixed curing agent, stand-by, take by weighing the Resins, epoxy by the weight part of table 2, the thinner that adds weight part shown in the table 2, silicone oil, carried out induction stirring 2 hours, make it even mixing, the mixed curing agent that adds again weight part shown in the above-mentioned table two, stirred after (2 hours) static 1 hour with magnetic stirrer, with this coating made from painting brush or be sprayed on after treatment No. 45 steel plates, with the coating of this preparation, on the steel plate of having processed, make its thickness remain on the 15-250 micron with painting brush or spray gun in construction.With carry out under the normal temperature solidifying in 8-24 hour, obtain homogeneous transparent and tough and tensile faint blue coating.
Then this painted steel sheet is dipped in 5% the NaCl solution, placed at normal temperatures 3 months, with coating and steel sheet peeling off, the surface of steel plate situation detects by an unaided eye after the taking-up.Find that surface of steel plate adheres to the tough and tensile and fine and close black thin film layer of one deck, test it through XPS and be Fe
3O
4And Fe
2O
3, peel off with blade and can be observed its ground light behind this layer film and without the metallic surface of rusty scale, this provable its anticorrosion ability is excellent.
Table 1 mixed curing agent
Table 2 formulation for coating material
Embodiment 5
The solvent-free anticorrosive coating of electrically conductive polyaniline that does not contain rust-stabilising pigment, this coating comprises following component and weight part content: mixed curing agent 30kg, Resins, epoxy 10kg, thinner 10kg, defoamer 0.3kg, wherein, mixed curing agent is that intrinsically conducting polyaniline and solidifying agent are to be mixed to get at 10: 90 by weight.
The molecular formula of intrinsically conducting polyaniline is:
Wherein y is that 0, R1 is CH
6O, n are 50, and solidifying agent adopts cashew nut gloss varnish modified phenolic amine, and Resins, epoxy is bisphenol A type epoxy resin, and the glycidyl ether of thinner Virahol, defoamer are the fatty acid alkyl ester of C3.
When synthetic, get polyaniline in eigenstate and under magnetic stirrer stirs, be added in the modified phenolic amine and dissolve, make mixed curing agent after stirring filtration in 2-4 hour;
Take by weighing Resins, epoxy by prescription, add thinner and defoamer, carry out induction stirring, make it even mixing, add again above-mentioned mixed curing agent.Stirred 2-3.5 hour, then placed 10-20 minute, namely prepare product.With the coating of this preparation, on the steel plate of having processed, make its thickness remain on the 15-250 micron with painting brush or spray gun in construction.With carry out under the normal temperature solidifying in 8-24 hour, obtain homogeneous transparent and tough and tensile faint blue coating.
This painted steel sheet is dipped in 5% the NaCL solution, placed at normal temperatures 3 months, with coating and steel sheet peeling off, the surface of steel plate situation detects by an unaided eye after the taking-up.Find that surface of steel plate adheres to the tough and tensile and fine and close black thin film layer of one deck, test it through XPS and be Fe304 and Fe203, peel off with blade and can be observed its ground light behind this layer film and without the metallic surface of rusty scale, this provable its anticorrosion ability is excellent.
Embodiment 6
The solvent-free anticorrosive coating of electrically conductive polyaniline that does not contain rust-stabilising pigment, this coating comprises following component and weight part content: mixed curing agent 35kg, Resins, epoxy 15kg, thinner 30kg, defoamer 1kg, wherein, mixed curing agent is that intrinsically conducting polyaniline and solidifying agent are to be mixed to get at 15: 85 by weight.
The molecular formula of intrinsically conducting polyaniline is:
Wherein y is that 0, R1 is C
3H
8O, n are 80.Solidifying agent adopts cashew nut gloss varnish modified phenolic amine, and Resins, epoxy is bisphenol f type epoxy resin, and thinner is the polypropylene glycol glycidyl ether, and defoamer is oligomeric polyoxyethylene.
When synthetic, get polyaniline in eigenstate and under magnetic stirrer stirs, be added in the modified phenolic amine and dissolve, make mixed curing agent after stirring filtration in 2-4 hour;
Take by weighing Resins, epoxy by prescription, add thinner and defoamer, carry out induction stirring, make it even mixing, add again above-mentioned mixed curing agent.Stirred 2-3.5 hour, then placed 10-20 minute, namely prepare product.With the coating of this preparation, on the steel plate of having processed, make its thickness remain on the 15-250 micron with painting brush or spray gun in construction.With carry out under the normal temperature solidifying in 8-24 hour, obtain homogeneous transparent and tough and tensile faint blue coating.
This painted steel sheet is dipped in 5% the NaCL solution, placed at normal temperatures 3 months, with coating and steel sheet peeling off, the surface of steel plate situation detects by an unaided eye after the taking-up.Find that surface of steel plate adheres to the tough and tensile and fine and close black thin film layer of one deck, test it through XPS and be Fe304 and Fe203, peel off with blade and can be observed its ground light behind this layer film and without the metallic surface of rusty scale, this provable its anticorrosion ability is excellent.
Embodiment 7
The solvent-free anticorrosive coating of electrically conductive polyaniline that does not contain rust-stabilising pigment, this coating comprises following component and weight part content: mixed curing agent 40kg, Resins, epoxy 20kg, thinner 55kg, defoamer 3kg, wherein, mixed curing agent is that intrinsically conducting polyaniline and solidifying agent are to be mixed to get at 20: 80 by weight.
The molecular formula of intrinsically conducting polyaniline is:
Wherein y is that 1, R1 is C
6H
14O, n are 100, and solidifying agent adopts cashew nut gloss varnish modified phenolic amine, and Resins, epoxy is the hybrid resin of bisphenol type epoxy and Bisphenol F type epoxy, and thinner is trihydroxymethylpropanyltri diglycidyl ether, and defoamer is silicone oil.
When synthetic, get polyaniline in eigenstate and under magnetic stirrer stirs, be added in the modified phenolic amine and dissolve, make mixed curing agent after stirring filtration in 2-4 hour;
Take by weighing Resins, epoxy by prescription, add thinner and defoamer, carry out induction stirring, make it even mixing, add again above-mentioned mixed curing agent.Stirred 2-3.5 hour, then placed 10-20 minute, namely prepare product.With the coating of this preparation, on the steel plate of having processed, make its thickness remain on the 15-250 micron with painting brush or spray gun in construction.With carry out under the normal temperature solidifying in 8-24 hour, obtain homogeneous transparent and tough and tensile faint blue coating.
This painted steel sheet is dipped in 5% the NaCL solution, placed at normal temperatures 3 months, with coating and steel sheet peeling off, the surface of steel plate situation detects by an unaided eye after the taking-up.Find that surface of steel plate adheres to the tough and tensile and fine and close black thin film layer of one deck, test it through XPS and be Fe304 and Fe203, peel off with blade and can be observed its ground light behind this layer film and without the metallic surface of rusty scale, this provable its anticorrosion ability is excellent.
Claims (9)
1. do not contain the solvent-free anticorrosive coating of electrically conductive polyaniline of rust-stabilising pigment, it is characterized in that, this coating comprises following component and weight part content:
Mixed curing agent 30～40;
Resins, epoxy 10～20;
Thinner 10～55;
Defoamer 0.3～3.
2. the solvent-free anticorrosive coating of electrically conductive polyaniline that does not contain rust-stabilising pigment according to claim 1, it is characterized in that, described mixed curing agent is that intrinsically conducting polyaniline and solidifying agent are (10～20) by weight: (80～90) are mixed to get.
3. the solvent-free anticorrosive coating of electrically conductive polyaniline that does not contain rust-stabilising pigment according to claim 2 is characterized in that, the molecular formula of described intrinsically conducting polyaniline is:
Wherein y is that 0～1, R1 is C
mH
2m+2O, m are that 1～6, n is 50～100.
4. the solvent-free anticorrosive coating of electrically conductive polyaniline that does not contain rust-stabilising pigment according to claim 2 is characterized in that, described solidifying agent is modified phenolic amine, comprises cashew nut gloss varnish modified phenolic amine.
5. the solvent-free anticorrosive coating of electrically conductive polyaniline that does not contain rust-stabilising pigment according to claim 1 is characterized in that, described Resins, epoxy is the hybrid resin of bisphenol A type epoxy resin, bisphenol f type epoxy resin or bisphenol type epoxy and Bisphenol F type epoxy.
6. the solvent-free anticorrosive coating of electrically conductive polyaniline that does not contain rust-stabilising pigment according to claim 5 is characterized in that, described bisphenol A type epoxy resin is commercially available E35, E42, E44 Resins, epoxy; Described bisphenol f type epoxy resin is commercially available DER354 Resins, epoxy; The hybrid resin of described bisphenol type epoxy and Bisphenol F type epoxy is commercially available DER351 Resins, epoxy.
7. the solvent-free anticorrosive coating of electrically conductive polyaniline that does not contain rust-stabilising pigment according to claim 1 is characterized in that, described thinner is glycidyl ether or the aliphatic glycidyl ether of alcohols.
8. the solvent-free anticorrosive coating of electrically conductive polyaniline that does not contain rust-stabilising pigment according to claim 7 is characterized in that, 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.
9. the solvent-free anticorrosive coating of electrically conductive polyaniline that does not contain rust-stabilising pigment according to claim 1 is characterized in that, described defoamer is the alkyl ester of C3-C11 lipid acid, oligomeric polyoxyethylene or silicone oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 | Publication Date |
|---|---|
| CN102876196A true CN102876196A (en) | 2013-01-16 |
| CN102876196B CN102876196B (en) | 2016-02-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110199612.4A Expired - Fee Related 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865361A (en) * | 2014-04-04 | 2014-06-18 | 山东旭锐新材有限公司 | Polyaniline anti-corrosion coating for underwater or wet surfaces and preparation method thereof |
| CN114958137A (en) * | 2021-02-24 | 2022-08-30 | 南亚塑胶工业股份有限公司 | Environment-friendly anticorrosive paint and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| 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 |
-
2011
- 2011-07-15 CN CN201110199612.4A patent/CN102876196B/en not_active Expired - Fee Related
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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865361A (en) * | 2014-04-04 | 2014-06-18 | 山东旭锐新材有限公司 | Polyaniline anti-corrosion coating for underwater or wet surfaces and preparation method thereof |
| 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 |
| CN114958137A (en) * | 2021-02-24 | 2022-08-30 | 南亚塑胶工业股份有限公司 | Environment-friendly anticorrosive paint and preparation method thereof |
| JP2022129345A (en) * | 2021-02-24 | 2022-09-05 | 南亞塑膠工業股▲分▼有限公司 | Anticorrosive coating and method for producing the same |
| US11739226B2 (en) | 2021-02-24 | 2023-08-29 | Nan Ya Plastics Corporation | Environmentally friendly anti-corrosion coating material and method for preparing the same |
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| CN102876196B (en) | 2016-02-17 |
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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 |