CN103555137A - 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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- CN103555137A CN103555137A CN201310512448.7A CN201310512448A CN103555137A CN 103555137 A CN103555137 A CN 103555137A CN 201310512448 A CN201310512448 A CN 201310512448A CN 103555137 A CN103555137 A CN 103555137A
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Abstract
The invention discloses a doped polyaniline-epoxy-zinc powder composite coating. The main agent of the doped polyaniline-epoxy-zinc powder composite coating contains the following components in percentages by weight: 5%-20% of doped polyaniline, 5%-25% of epoxy resin, 10%-40% of a solvent, 0%-4% of an anti-settling agent, and 30%-75% of zinc powder; the doped polyaniline-epoxy-zinc powder composite coating also contains a curing agent; the weight ratio of the main agent to the curing agent is (10:10)-(10:3). According to the doped polyaniline-epoxy-zinc powder composite coating and a preparation method thereof, the corrosion resistance of a coating layer formed by the composite coating is improved, so that good electrochemical protection is provided for steel structures in marine environment, the use amount of the zinc powder in the coating is reduced and the application performance of the coating is improved.
Description
Technical field
The present invention relates to a kind of protective system technology, relate in particular 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, and boats and ships, bridge spanning the sea, in the construction of the ocean Infrastructure such as drilling unit and Coastal Power Plant, applicating history is long.Research through permanent, for five different corrosion region bands of ocean environment, has 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 multiple floor coating technology Lang Jian district and Tidal zone adopt and can reach best protection effect.This its floating coat the most easily lost efficacy, and the raising of its protective value is conducive to extend the protection period of whole system.Epoxy zinc rich primer is important steel construction heavy-duty coating, is widely used in ocean environment, and people are constantly devoted to improve its long-effective protection performance at present, avoid frequently overhauling, and save anticorrosion cost.
Epoxy zinc rich primer is one of priming paint conventional in current China heavy-duty coating system.Its corrosion-resisting function is in corrosive environment, by corrosion, to sacrifice zinc powder to reach protection steel substrate.Epoxy zinc rich primer protection against corrosion 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 form galvanic cell, and the electropotential of zinc is more negative than the electropotential of iron, and zinc is anode (sacrificial anode conventionally); iron is negative electrode, and electric current flows to iron by zinc, and steel substrate has just obtained galvanic protection.Because of the electro-chemical protection of its zinc powder to iron and steel, claim again electrochemistry rust-inhibiting paint.
Its two, epoxy zinc rich primer is looked for your zinc corrosion deposits shielding protection.In corrosion later stage process, zinc powder paint is constantly corroded in application process, zinc powder gap and steel surface have deposited corrosion product, and zinc subcarbonate, is commonly called as " white rust ", its compact structure, and non-conductive, be the stable compound of indissoluble, can stop the erosion with mask erosion medium, 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 raw material is cheap and 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 fields such as anticorrosive metal, antistatic, electromagnetic shielding, field-effect transistors, be considered to have most the conductive polymers of actual application prospect.Existing polyaniline type protective system mainly contains two kinds:
(1) electrochemical polymerization forms polyaniline coating.But this protective system is used inconvenience, be not suitable for the anticorrosion of site operation and larger metal parts;
(2) polyaniline (adopting the polyaniline in eigenstate that existing chemical oxidative polymerization makes, reduced form polyaniline or the ammonium hydroxide of protonic acid solute doping to remove the oxidized form polyaniline of doping) is mixed to form organic composite coating with conventional filmogen (as epoxy resin, urethane and polyacrylic resin etc.).
Yet above-mentioned protective system does not meet the desired preservative effect that reach of people in actual production activity yet.
Summary of the invention
The object of the invention is, improve the deficiencies in the prior art, doped polyaniline-epoxy-zinc powder composite coating that a kind of steel construction protection that adapts to ocean environment uses and preparation method thereof is provided.
For reaching above technical purpose, the technical solution used in the present invention is as follows:
-epoxy-zinc powder composite coating, wherein, component and the quality percentage composition 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:
Aniline and ammonium persulphate are dissolved in respectively in the acid solution that 20mL concentration is 1.0mol/L, 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 ℃ standing and reacting 24 hours; Products therefrom is cleaned to neutral with deionized water and ethanol, after separation, vacuum-drying, obtain cyan doped polyaniline.
Particularly, the described acid solution of 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, the component of the host of described doped polyaniline-epoxy-zinc powder composite coating and quality percentage composition thereof 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 weight bisphenol A type epoxy resin, is E-12, E-14, E-20 or E-51.
Described solvent is any one or its arbitrarily two or more 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 arbitrarily two or more combination of aerosil, wilkinite or ether of cellulose; Particularly, described anti-settling agent comprises 1.5% aerosil and 0.5% wilkinite.
The fineness of described zinc powder is 400～1200 orders.
Described solidifying agent is any one or its arbitrarily two or more 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) according to the mass percent of each component, prepare raw material;
(2) described doped polyaniline, part epoxy and partial solvent are mixed, soak and after placing, add the granulated glass sphere of equivalent to grind 2～3 times with vibration mixing machine, each 20 minutes, every grinding is ground after once needing to wait mixture to be down to room temperature more next time, after grinding completes, use successively 80 orders and 120 object copper mesh, 240 orders and 400 object silk filtering mixts, 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 is 1000rmp at rotating speed pre-dispersed 2～3 minutes, then add described zinc powder, under the state that is 3000rmp at rotating speed, disperse 20 minutes, 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 is mixed 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 can effectively prevent the spot corrosion that Cl-causes in coating, and has self-repair function.The polyaniline that is applicable to ratio adds in epoxy zinc rich primer; the conductivity that it is unique and fibrous texture are considered to greatly to extend the protection period of the coating that this priming paint forms; for base material provides effective electro-chemical protection; simultaneously; can suitably reduce the consumption of zinc powder in epoxy zinc rich primer; thereby 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 of the present invention-zinc powder composite coating:
By 60g doped polyaniline, 120g epoxy resin E-20 and 120g dimethylbenzene, n-butanol mixed solvent, (3:1) is pre-dispersed, soak to place and to add after 12h and vibration mixing machine vibro-grinding 2～3 times for the granulated glass sphere of system equivalent, each 20 minutes, every grinding is once noted being down to (25 ℃ of left and right) after room temperature and is ground next time again, grinding completes respectively and filters successively with 80 orders and 120 object copper mesh, then with 240 orders and 400 order silks, filter to obtain epoxy resin and polyaniline abrasive component 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 is 1000rmp at rotating speed, after pre-dispersed 2-3min, add a certain amount of 800 order zinc powders, make the mass percent of each component in reaction system reach predefined numerical value.Control mixing speed 3000rmp, with high speed dispersor, disperse 20min to obtain composite coating; Solidifying agent is diluted to 20%, and during use, host is mixed by 3:1 with solidifying agent, and after stirring, spraying, obtains composite coating coating.
Embodiment 2
Reference table 1, changes the mass percent of each component in the reaction system of doped polyaniline-epoxy of the present invention-zinc powder composite coating, obtains following coating A～H, and described each coating is carried out to performance evaluation.
Different reaction systems and the performance evaluation thereof of table 1 doped polyaniline-epoxy-zinc powder composite coating
From above table:
(1) component of anti-settling agent is to affect 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 1.5% aerosil and 0.5% wilkinite;
(2) consumption of doped polyaniline is the key factor that affects coating adhesion and salt-fog resistant time, when described composite coating is containing 3%～5% doped polyaniline, the sticking power of the coating of its formation and salt-fog resistant time are significantly lower than the composite coating of the doped polyaniline containing 8%～12%;
(3) mass percent of doped polyaniline in this composite coating of suitable raising, as table 1 floating coat G(10%) and coating H(12%) as shown in, not only make the time of the coating salt spray resistance of this composite coating formation further increase, also moderate reduction the consumption of zinc powder, make zinc powder account for 40%～50% of total mass.
In sum; doped polyaniline-epoxy of the present invention-zinc powder composite coating and preparation method thereof has improved the erosion resistance of the coating of its formation; for the steel construction in ocean environment provides better electro-chemical protection, and reduce the consumption of zinc powder in coating, improved the workability of coating.
Above-described embodiment is preferably embodiment of the present invention; but be not merely restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being all included in protection scope of the present invention.
Claims (12)
1. doped polyaniline-epoxy-zinc powder composite coating, is characterized in that, component and the quality percentage composition 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%;
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:
Aniline and ammonium persulphate are dissolved in respectively in the acid solution that 20mL concentration is 1.0mol/L, 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 ℃ standing and reacting 24 hours; Products therefrom is cleaned to neutral with deionized water and ethanol, after separation, vacuum-drying, obtain cyan doped polyaniline.
2. doped polyaniline-epoxy as claimed in claim 1-zinc powder composite coating, it is characterized in that: the described acid solution of 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 as claimed in claim 1-zinc powder composite coating, is characterized in that, component and the quality percentage composition 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 as claimed in claim 3-zinc powder composite coating, is characterized in that: described epoxy resin is middle molecular weight bisphenol A type epoxy resin, is E-12, E-14, E-20 or E-51.
5. doped polyaniline-epoxy as claimed in claim 3-zinc powder composite coating, is characterized in that: described solvent is any one or its two or more combination arbitrarily of aromatic hydrocarbon, alcohols, ketone or ester class.
6. doped polyaniline-epoxy as claimed in claim 5-zinc powder composite coating, is characterized in that: described solvent is the mixed solvent of dimethylbenzene and propyl carbinol, and blending ratio is 3:1.
7. doped polyaniline-epoxy as claimed in claim 3-zinc powder composite coating, is characterized in that: described anti-settling agent is any one or its two or more combination arbitrarily of aerosil, wilkinite or ether of cellulose.
8. doped polyaniline-epoxy as claimed in claim 7-zinc powder composite coating, is characterized in that: described anti-settling agent comprises 1.5% aerosil and 0.5% wilkinite.
9. doped polyaniline-epoxy as claimed in claim 3-zinc powder composite coating, is characterized in that: the fineness of described zinc powder is 400～1200 orders.
10. doped polyaniline-epoxy as claimed in claim 3-zinc powder composite coating, is characterized in that: described solidifying agent is any one or its two or more combination arbitrarily 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, is characterized in that, it comprises the following steps:
(1) according to the mass percent of each component, prepare raw material;
(2) described doped polyaniline, part epoxy and partial solvent are mixed, soak and after placing, add the granulated glass sphere of equivalent to grind 2～3 times with vibration mixing machine, each 20 minutes, every grinding is ground after once needing to wait mixture to be down to room temperature more next time, after grinding completes, use successively 80 orders and 120 object copper mesh, 240 orders and 400 object silk filtering mixts, 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 is 1000rmp at rotating speed pre-dispersed 2～3 minutes, then add described zinc powder, under the state that is 3000rmp at rotating speed, disperse 20 minutes, 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 is mixed 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 as claimed in claim 11-zinc powder composite coatings, 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 |
| 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 |
| CN111534136A (en) * | 2020-04-01 | 2020-08-14 | 广州集泰化工股份有限公司 | Water-based epoxy zinc-rich coating and preparation method 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 |
| US20220112336A1 (en) * | 2020-10-08 | 2022-04-14 | The Boeing Company | Polyaniline compositions, articles thereof, and methods thereof |
| US11396707B2 (en) * | 2019-12-23 | 2022-07-26 | Tech-Taiyo Kogyo Co., Ltd. | Laminate and rust prevention method |
| 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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| 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 |
| US11396707B2 (en) * | 2019-12-23 | 2022-07-26 | Tech-Taiyo Kogyo Co., Ltd. | Laminate and rust prevention method |
| CN111534136A (en) * | 2020-04-01 | 2020-08-14 | 广州集泰化工股份有限公司 | Water-based epoxy zinc-rich coating and preparation method thereof |
| 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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