CN103555137B - Doped polyaniline-epoxy-zinc powder composite coating and preparation method thereof - Google Patents
Doped polyaniline-epoxy-zinc powder composite coating and preparation method thereof Download PDFInfo
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- CN103555137B CN103555137B CN201310512448.7A CN201310512448A CN103555137B CN 103555137 B CN103555137 B CN 103555137B CN 201310512448 A CN201310512448 A CN 201310512448A CN 103555137 B CN103555137 B CN 103555137B
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Abstract
The present invention discloses a kind of doped polyaniline-epoxy-zinc powder composite coating, wherein, component and the mass percentage thereof of the host of described doped polyaniline-epoxy-zinc powder composite coating are as follows: doped polyaniline: 5% ~ 20%, epoxy resin: 5% ~ 25%, solvent: 10% ~ 40%, anti-settling agent: 0% ~ 4%, zinc powder: 30% ~ 75%; Described doped polyaniline-epoxy-zinc powder composite coating also comprises solidifying agent, and the mass ratio of described host and solidifying agent is 10:10 ~ 10:3.Doped polyaniline-epoxy-zinc powder composite coating of the present invention and preparation method thereof improves the erosion resistance of the coating that it is formed; for the steel construction in ocean environment provides better electro-chemical protection; and decrease the consumption of zinc powder in coating, improve the workability of coating.
Description
Technical field
The present invention relates to a kind of protective system technology, particularly relate to a kind of doped polyaniline-epoxy-zinc powder composite coating and preparation method thereof
Background technology
Iron and steel is most widely used metallic substance, is widely applied at harbour, boats and ships, bridge spanning the sea, and in the construction of the ocean such as drilling unit and Coastal Power Plant Infrastructure, applicating history is long.Through permanent research, for the corrosion zone that ocean environment five is different, formed a set of to the effective sfgd. of steel construction: coating protection is taked in atmospheric zone; The method that submerged zone takes coating protection and cathode protection technology to combine, novel cladding coating technology adopts in Lang Jian district and Tidal zone can reach best protected effect.This its floating coat the most easily lost efficacy, and the raising of its protective value is conducive to the protection period extending whole system.Epoxy zinc rich primer is important steel construction heavy-duty coating, is widely used in ocean environment, and current people are constantly devoted to improve its long-effective protection performance, avoid frequently overhauling, save anticorrosion cost.
Epoxy zinc rich primer is one of priming paint commonly used in current China heavy-duty coating system.Its corrosion-resisting function in corrosive environment, sacrifices zinc powder by corrosion reach protection steel substrate.Epoxy zinc rich primer anticorrosion mechanism can be summarized as 2 points:
One, epoxy zinc rich primer plays electro-chemical protection.Because zinc is more bold and vigorous than ironwork, easily lose electronics, in corrosion process in early stage; zinc powder and steel substrate composition galvanic cell, the electropotential of zinc is born than the electropotential of iron, and zinc is anode (usual sacrificial anode); iron is negative electrode, and electric current flows to iron by zinc, and steel substrate just obtains galvanic protection.Because its zinc powder is to the electro-chemical protection of iron and steel, also known as electrochemistry rust-inhibiting paint.
Its two, your zine corrosion settling shielding protection looked for by epoxy zinc rich primer.In corrosion late stage, zinc powder paint is constantly corroded in application process, zinc powder gap and steel surface deposited corrosion product, i.e. zinc subcarbonate, are commonly called as " white rust ", its compact structure, and non-conductive, be the stable compound of indissoluble, the erosion with mask erosion medium can be stopped, play corrosion protection result, be therefore also described as " selfreparing " property of zinc powder paint.
Polyaniline is another kind of conventional antiseptic coating ofiron and steel.Polyaniline has the many merits such as cheaper starting materials is easy to get, synthesis technique simple, excellent conductivity and is subject to extensive concern, because it has electroconductibility, and also have a wide range of applications in anticorrosive metal, antistatic, the field such as electromagnetic shielding, field-effect transistor, be considered to the conductive polymers having actual application prospect most.Existing polyaniline type protective system mainly contains two kinds:
(1) electrochemical polymerization forms polyaniline coating.But this protective system uses inconvenience, be not suitable for the anticorrosion of site operation and larger metal parts;
(2) polyaniline (the reduced form polyaniline of the polyaniline in eigenstate adopting existing chemical oxidative polymerization to obtain, protonic acid solution doping or ammonium hydroxide remove the oxidized form polyaniline adulterated) is mixed to form organic composite coating with conventional filmogen (as epoxy resin, urethane and polyacrylic resin etc.).
But above-mentioned protective system does not meet the preservative effect that people reach desired by actual production activity yet.
Summary of the invention
The object of the invention is, improve the deficiencies in the prior art, a kind of doped polyaniline-epoxy-zinc powder composite coating adapting to the steel construction protection of ocean environment and preparation method thereof is provided.
For reaching above technical purpose, the technical solution used in the present invention is as follows:
A kind of doped polyaniline-epoxy-zinc powder composite coating, wherein, component and the mass percentage thereof of the host of described doped polyaniline-epoxy-zinc powder composite coating are as follows:
Doped polyaniline: 5% ~ 20%,
Epoxy resin: 5% ~ 25%,
Solvent: 10% ~ 40%,
Anti-settling agent: 0% ~ 4%,
Zinc powder: 30% ~ 75%;
Described doped polyaniline-epoxy-zinc powder composite coating also comprises solidifying agent, and the mass ratio of described host and solidifying agent is 10:10 ~ 10:3;
Wherein, preparation method's step of described doped polyaniline is as follows:
It is in the acid solution of 1.0mol/L that aniline and ammonium persulphate are dissolved in 20mL concentration respectively, and wherein the molar mass of aniline and ammonium persulphate is than being 0.2:0.25; Then two parts of solution are mixed rapidly, after fully stirring at 20 DEG C standing and reacting 24 hours; By products therefrom deionized water and ethanol purge extremely neutrality, after separation, vacuum-drying, obtain cyan doped polyaniline.
Particularly, the described acid solution preparing doped polyaniline is mineral acid or organic acid, and described mineral acid is hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid, and described organic acid is acetic acid, oxalic acid or vinylformic acid.
More preferably, component and the mass percentage thereof of the host of described doped polyaniline-epoxy-zinc powder composite coating are as follows:
Doped polyaniline: 10% ~ 12%,
Epoxy resin: 12% ~ 14%,
Solvent: 20% ~ 30%,
Anti-settling agent: 2%,
Zinc powder: 45% ~ 50%;
Described doped polyaniline-epoxy-zinc powder composite coating also comprises solidifying agent, and the mass ratio of described host and solidifying agent is 10:6.
Further, described epoxy resin is middle-molecular-weihydroxyethyl bisphenol A type epoxy resin, is E-12, E-14, E-20 or E-51.
Described solvent is any one or its two or more arbitrarily combination of aromatic hydrocarbon, alcohols, ketone or ester class; Particularly, described solvent is the mixed solvent of dimethylbenzene and propyl carbinol, and blending ratio is 3:1.
Described anti-settling agent is any one or its two or more arbitrarily combination of aerosil, wilkinite or ether of cellulose; Particularly, described anti-settling agent comprises the aerosil of 1.5% and the wilkinite of 0.5%.
The fineness of described zinc powder is 400 ~ 1200 orders.
Described solidifying agent is any one or its two or more arbitrarily combination of aliphatic polyamine, aromatic polyamine, alicyclic polyamine, polymeric amide polyamine or modified multicomponent amine.
A preparation method for foregoing doped polyaniline-epoxy-zinc powder composite coating, it comprises the following steps:
(1) raw material is prepared according to the mass percent of each component;
(2) described doped polyaniline, part epoxy and partial solvent are mixed, soak the granulated glass sphere vibration mixing machine adding equivalent after placing to grind 2 ~ 3 times, each 20 minutes, often grind after once needing to wait mixture to be down to room temperature and grind again next time, use 80 orders and 120 object copper mesh, 240 orders and 400 object silk filtering mixts after having ground successively, obtain component A;
(3) remaining epoxy resin, remaining solvent and described anti-settling agent are added in described component A successively, under the state that rotating speed is 1000rmp pre-dispersed 2 ~ 3 minutes, then add described zinc powder, disperse 20 minutes under the state that rotating speed is 3000rmp, obtain the host of doped polyaniline-epoxy-zinc powder composite coating;
(4) described solidifying agent is diluted to 20%, the host of described composite coating mixes by described mass ratio with this solidifying agent, obtains doped polyaniline-epoxy-zinc powder composite coating finished product.
Particularly, in described step (2), the soak time of mixture is 8 ~ 24 hours.
Compared with prior art, the present invention has following advantage:
The polyaniline of conduction is considered to the spot corrosion that can effectively prevent Cl-from causing in the coating, and has self-repair function.The polyaniline being applicable to ratio adds in epoxy zinc rich primer; the conductivity of its uniqueness and fibrous texture are considered to the protection period that greatly can extend the coating that this priming paint is formed; for base material provides effective electro-chemical protection; simultaneously; suitably can reduce the consumption of zinc powder in epoxy zinc rich primer; thus improve the workability of epoxy zinc rich primer, improve the suitability of epoxy zinc rich primer in ocean environment.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Be below the preparation method of doped polyaniline-epoxy-zinc powder composite coating of the present invention:
60g doped polyaniline, 120g epoxy resin E-20 and 120g dimethylbenzene, n-butanol mixed solvent (3:1) is pre-dispersed, add after soaking placement 12h and vibrate mixing machine vibro-grinding 2 ~ 3 times with the granulated glass sphere of system equivalent, each 20 minutes, often grind (about 25 DEG C) after once noting being down to room temperature to grind again next time, grind and filtered successively with 80 orders and 120 object copper mesh respectively, then filter to obtain epoxy resin and polyaniline abrasive component with 240 orders and 400 order silks successively, be decided to be component A.Take 150g component A, a certain amount of epoxy resin, solvent and anti-settling agent are added in component A successively, under the state that rotating speed is 1000rmp, add a certain amount of 800 order zinc powders after pre-dispersed 2-3min, make the mass percent of each component in reaction system reach the numerical value preset.Control mixing speed 3000rmp, obtain composite coating with high speed dispersor dispersion 20min; Solidifying agent is diluted to 20%, and during use, host mixes by 3:1 with solidifying agent, sprays, obtain composite coating coating after stirring.
Embodiment 2
Reference table 1, changes the mass percent of each component in the reaction system of doped polyaniline-epoxy-zinc powder composite coating of the present invention, obtains following coating A ~ H, and carry out performance evaluation to described each coating.
The different reaction system of table 1 doped polyaniline-epoxy-zinc powder composite coating and performance evaluation thereof
From above table:
(1) component of anti-settling agent affects the important factor in order that hard-caked sediment or soft precipitation appear in this composite coating, from the performance evaluation of above-mentioned coating, the best anti-settling agent of composite coating of the present invention be combined as the aerosil of 1.5% and the wilkinite of 0.5%;
(2) consumption of doped polyaniline is the key factor affecting coating adhesion and salt-fog resistant time, when described composite coating containing 3% ~ 5% doped polyaniline, its sticking power of coating formed and salt-fog resistant time significantly lower than containing 8% ~ 12% the composite coating of doped polyaniline;
(3) when the mass percent suitably improving doped polyaniline in this composite coating, as table 1 floating coat G(10%) and coating H(12%) shown in, the time of the coating salt spray resistance not only making this composite coating be formed increases further, also the moderate reduction consumption of zinc powder, makes zinc powder account for 40% ~ 50% of total mass.
In sum; doped polyaniline-epoxy-zinc powder composite coating of the present invention and preparation method thereof improves the erosion resistance of the coating that it is formed; for the steel construction in ocean environment provides better electro-chemical protection, and decrease the consumption of zinc powder in coating, improve the workability of coating.
Above-described embodiment is the present invention's preferably embodiment; but be not merely restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be all included within protection scope of the present invention.
Claims (12)
1. doped polyaniline-epoxy-zinc powder composite coating, is characterized in that, component and the mass percentage thereof of the host of described doped polyaniline-epoxy-zinc powder composite coating are as follows:
Doped polyaniline: 8% ~ 12%,
Epoxy resin: 5% ~ 25%,
Solvent: 10% ~ 40%,
Anti-settling agent: 2%,
Zinc powder: 30% ~ 75%;
Above-mentioned each component mixes in a dispersed form;
Described doped polyaniline-epoxy-zinc powder composite coating also comprises solidifying agent, and the mass ratio of described host and solidifying agent is 10:10 ~ 10:3;
Wherein, preparation method's step of described doped polyaniline is as follows:
It is in the acid solution of 1.0mol/L that aniline and ammonium persulphate are dissolved in 20mL concentration respectively, and wherein the molar mass of aniline and ammonium persulphate is than being 0.2:0.25; Then two parts of solution are mixed rapidly, after fully stirring at 20 DEG C standing and reacting 24 hours; By products therefrom deionized water and ethanol purge extremely neutrality, after separation, vacuum-drying, obtain cyan doped polyaniline.
2. doped polyaniline-epoxy-zinc powder composite coating as claimed in claim 1, it is characterized in that: the described acid solution preparing doped polyaniline is mineral acid or organic acid, described mineral acid is hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid, and described organic acid is acetic acid, oxalic acid or vinylformic acid.
3. doped polyaniline-epoxy-zinc powder composite coating as claimed in claim 1, it is characterized in that, component and the mass percentage thereof of the host of described doped polyaniline-epoxy-zinc powder composite coating are as follows:
Doped polyaniline: 8% ~ 12%,
Epoxy resin: 12% ~ 16%,
Solvent: 22% ~ 38%,
Anti-settling agent: 2%,
Zinc powder: 40% ~ 50%;
Described doped polyaniline-epoxy-zinc powder composite coating also comprises solidifying agent, and the mass ratio of described host and solidifying agent is 10:6.
4. doped polyaniline-epoxy-zinc powder composite coating as claimed in claim 3, it is characterized in that: described epoxy resin is middle-molecular-weihydroxyethyl bisphenol A type epoxy resin, is E-12, E-14, E-20 or E-51.
5. doped polyaniline-epoxy-zinc powder composite coating as claimed in claim 3, is characterized in that: described solvent is any one or its two or more arbitrarily combination of aromatic hydrocarbon, alcohols, ketone or ester class.
6. doped polyaniline-epoxy-zinc powder composite coating as claimed in claim 5, it is characterized in that: described solvent is the mixed solvent of dimethylbenzene and propyl carbinol, blending ratio is 3:1.
7. doped polyaniline-epoxy-zinc powder composite coating as claimed in claim 3, is characterized in that: described anti-settling agent is any one or its two or more arbitrarily combination of aerosil, wilkinite or ether of cellulose.
8. doped polyaniline-epoxy-zinc powder composite coating as claimed in claim 7, is characterized in that: described anti-settling agent comprises the aerosil of 1.5% and the wilkinite of 0.5%.
9. doped polyaniline-epoxy-zinc powder composite coating as claimed in claim 3, is characterized in that: the fineness of described zinc powder is 400 ~ 1200 orders.
10. doped polyaniline-epoxy-zinc powder composite coating as claimed in claim 3, is characterized in that: described solidifying agent is any one or its two or more arbitrarily combination of aliphatic polyamine, aromatic polyamine, alicyclic polyamine, polymeric amide polyamine or modified multicomponent amine.
The preparation method of 11. 1 kinds of doped polyaniline-epoxy-zinc powder composite coatings as described in claim 1-10 any one, it is characterized in that, it comprises the following steps:
(1) raw material is prepared according to the mass percent of each component;
(2) described doped polyaniline, part epoxy and partial solvent are mixed, soak the granulated glass sphere vibration mixing machine adding equivalent after placing to grind 2 ~ 3 times, each 20 minutes, often grind after once needing to wait mixture to be down to room temperature and grind again next time, use 80 orders and 120 object copper mesh, 240 orders and 400 object silk filtering mixts after having ground successively, obtain component A;
(3) remaining epoxy resin, remaining solvent and described anti-settling agent are added in described component A successively, under the state that rotating speed is 1000r/min pre-dispersed 2 ~ 3 minutes, then add described zinc powder, disperse 20 minutes under the state that rotating speed is 3000r/min, obtain the host of doped polyaniline-epoxy-zinc powder composite coating;
(4) described solidifying agent is diluted to 20%, the host of described composite coating mixes by described mass ratio with this solidifying agent, obtains doped polyaniline-epoxy-zinc powder composite coating finished product.
The preparation method of 12. doped polyaniline-epoxy-zinc powder composite coatings as claimed in claim 11, is characterized in that: in described step (2), the soak time of mixture is 8 ~ 24 hours.
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| CN107099219A (en) * | 2017-05-09 | 2017-08-29 | 中国科学院海洋研究所 | A kind of polyaniline-modified epoxy zinc powder composite coating and preparation method |
| CN107057544A (en) * | 2017-06-07 | 2017-08-18 | 南京科技职业学院 | A kind of carbamide paint and preparation method thereof |
| CN109233559A (en) * | 2018-08-06 | 2019-01-18 | 浩力森涂料（上海）有限公司 | A kind of high-performance water-based container zinc-rich paint and its manufacturing method |
| JP6898006B2 (en) * | 2019-12-23 | 2021-07-07 | テック大洋工業株式会社 | Laminated body and rust prevention method |
| CN111534136B (en) * | 2020-04-01 | 2021-11-16 | 广州集泰化工股份有限公司 | Water-based epoxy zinc-rich coating and preparation method thereof |
| US20220112336A1 (en) * | 2020-10-08 | 2022-04-14 | The Boeing Company | Polyaniline compositions, articles thereof, and methods thereof |
| CN113637393A (en) * | 2021-09-24 | 2021-11-12 | 肇庆市海特复合材料技术研究院 | Composite anticorrosive paint and preparation method thereof |
| CN115537100A (en) * | 2022-11-09 | 2022-12-30 | 郑州圣莱特空心微珠新材料有限公司 | Epoxy zinc-rich primer containing conductive polyaniline coated hollow glass beads and preparation method thereof |
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