CN104877517A - Preparation method of waterborne epoxy composite anticorrosive coating - Google Patents
Preparation method of waterborne epoxy composite anticorrosive coating Download PDFInfo
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- CN104877517A CN104877517A CN201510240769.5A CN201510240769A CN104877517A CN 104877517 A CN104877517 A CN 104877517A CN 201510240769 A CN201510240769 A CN 201510240769A CN 104877517 A CN104877517 A CN 104877517A
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Abstract
The invention provides a preparation method of a waterborne epoxy composite anticorrosive coating and relates to a preparation method of a composite coating material. The waterborne epoxy composite anticorrosive coating provided by the invention is prepared by adopting carbodiimide (EDC) mediated condensation reaction to integrate zeolite and graphene, and then filling the integrated zeolite and graphene into waterborne epoxy resin. By adopting the method, the characteristics of more pore passages and large specific surface area of zeolite are combined with high strength and electron mobility of graphene; corrosive particles can be blocked from passing through a coating layer to reach a metal matrix and the time for the corrosive particles to pass through the coating layer to reach the metal matrix can be prolonged in the process of anticorrosive application of the coating; and the cathode reaction during corrosion can be transferred to an interface between the coating layer and air by virtue of the electrical conductivity of graphene, thereby slowing down the happening of electrochemical corrosion reaction. By adopting the method, the defects that the current waterborne anticorrosive coating layer is generally poor in barrier property and short in anticorrosion cycle are overcome, and the anticorrosion performance of the waterborne coating layer is greatly improved.
Description
Technical field
The present invention relates to a kind of preparation method of organic composite coating material, particularly relate to a kind of preparation method of water-base epoxy composite anticorrosion coating.
Background technology
Metallic corrosion brings huge potential safety hazard and financial loss to the development of industry and society, and adopts corrosion protection coating to be the method suppressing metallic corrosion general, the most most economical.In traditional solvent-borne coating, solvent is about about 40%, and some coating such as the solvent of pyroxylin(e)finish when constructing can up to 80%, and therefore development environment friendly coating has become the study hotspot of paint field.Environmentally friendly coatings refers to low VOC, hypotoxic coating, and kind main at present has water-borne coatings, powder coating, high solid coating and radiation curable coating.From product form and using method, water-borne coatings and solvent based coating are identical.The application of water-borne coatings is not generally by the restriction of occasion, and also do not need special coating tool and equipment, therefore water-borne coatings will become the leading product of coating.
In recent years, in numerous water-borne coatingss, aqueous epoxide resin paint and nanometer modified epoxy cold coating develop rapidly.Because epoxy resin has excellent process based prediction model, as good sticking power, chemical proofing and solvent resistance, and its hardness is high, good heat stability.But aqueous epoxy resins also exists certain deficiency in actual applications, as the strength degradation that Water-borne modification causes, degradation under barrier, therefore need a kind of new aqueous composite paint of exploitation badly.
Graphene is a kind of novel carbon material, and it is the Two-dimensional Carbon atomic shell that one deck is formed by connecting with sp2 hydridization by carbon atom, and its thickness only has 0.34nm, is the thinnest two-dimension nano materials found at present.Find after deliberation, Graphene is the material that intensity is the highest in the world at present, and its strength ratio high-strength carbon fibre is high 20 times, also higher 100 times than best iron and steel.In addition Graphene also has the speciality of the multiple excellences such as great specific surface area, high thermal conductivity and carrier mobility.Make it at transistor, ultracapacitor, permselectivity membrane, the numerous areas such as strongthener are with a wide range of applications.
Zeolite is the representational molecular sieve of most, and it has uniform microvoid structure, and its hole diameter is even, and these holes the inside of the molecular adsorption less than its diameter to vestibule, and can have Preferential adsorption ability to polar molecule and unsaturated molecule.Possess adsorptive power just because of zeolite high, thermostability waits the unexistent advantage of other sorbent material by force, makes it receive much concern in every field always.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of water-base epoxy composite anticorrosion coating, the method is integrated with Graphene by zeolite by gentle reaction, compared to simple mechanical blending, there is higher stability, avoid the stacking again of graphene sheet layer, gathering.The weather resistance of aqueous epoxy coating, preservative property and intensity are all significantly improved.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for water-base epoxy composite anticorrosion coating, be composited with aqueous epoxy resins after the condensation reaction that described method adopts carbodiimide (EDC) to mediate is integrated with Graphene by zeolite, concrete synthesis step is as follows again:
The amination of a zeolite: the organic solvent zeolite of 3 ~ 4g being put into 50ml, is warmed up to 80 DEG C under stirring, then adds the silane coupling agent of 5 ~ 6ml, continues backflow 8h, is cooled to room temperature washing and filters, dry in 60 DEG C of warm airs;
B zeolite is integrated with Graphene: by reduced graphene ultrasonic disperse in 50 ~ 100ml distilled water; Configure EDC/N-hydroxysuccinimide (NHS) aqueous solution of 10mmol/5mmol and join in the Graphene of dispersion, activate and add amidized zeolite stirring at normal temperature 4 ~ 6 hours after 0.5 hour, centrifugal drying obtains the Graphene being grafted with zeolite;
C gets the above-mentioned Graphene being grafted with zeolite of 10-40 part as filler, joins in the mixed solution of 100-200 part water and 100-200 part water-base resin, in ball mill, disperses 1-2h, obtain the mother liquor of water-base epoxy composite anticorrosion coating;
D gets after 25-50 part waterborne curing agent mixes with 50-100 part water and mixes in the ratio of 1:3-4 with the mother liquor of water-base epoxy composite anticorrosion coating.
The preparation method of described a kind of water-base epoxy composite anticorrosion coating, the silane coupling agent added in described step a is KH550 or KH-560 or KH-570 or KH-580 or KH-590.
The preparation method of described a kind of water-base epoxy composite anticorrosion coating, the aqueous epoxy resins in described step c is Ar555 epoxy resin or H228A epoxy resin or E44 epoxy emulsion or E51 epoxy emulsion or E20 epoxy emulsion.
The preparation method of described a kind of water-base epoxy composite anticorrosion coating, in steps d waterborne curing agent be Aq419 or H228B or W651 or W650.
Advantage of the present invention and effect are:
1. preparation method of the present invention is by the reaction of gentleness, zeolite is integrated with Graphene, has higher stability compared to simple mechanical blending, avoids the stacking again of graphene sheet layer, gathering.
2. the present invention prepares water-base epoxy composite anticorrosion coating and successfully the high absorbability of zeolite and the high electron mobility of Graphene is well combined, and the weather resistance of aqueous epoxy coating, preservative property and intensity are all significantly improved.
3. adopt the Graphene being grafted with zeolite as filler in the present invention, nano level and micro-size particles acting in conjunction, further obviate the drawback causing preservative effect to decline because of coating defects such as brushing technique formation pin holes, brushing technique is more simplified.
Accompanying drawing explanation
Fig. 1 is the method for zeolite graft grapheme;
Fig. 2 is the corrosion-resisting function mechanism of water-base epoxy composite anticorrosion coating.
Note: accompanying drawing of the present invention is state analysis schematic diagram or photo, in figure, word or the unintelligible not image of image are to the understanding of technical solution of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
The present invention proposes the preparation method of the water-base epoxy composite anticorrosion coating used, and filler used is by novel inorganic filler integrated with Graphene for zeolite, and it not only has high voidage, also has high strength and high conductivity.When corroding particle and entering coating, vesicular structure due to zeolite can be good at intercepting the migration of corrosion particle in layer and extends the time that it arrives metallic matrix, and due to Graphene existence can also by corrosion produce electric charge derive fast, the interface making cathodic reaction transfer to coating and air is carried out, delay the development (Fig. 2) of galvanic corrosion, and then the development process of corrosion of slowing down, the weather resistance of coating and preservative property are all significantly improved.
Embodiment 1
(1) zeolite graft grapheme:
1) amination of zeolite: the organic solvent zeolite of 4g being put into 50ml, is warmed up to 80 DEG C under stirring, then add the silane coupling agent of 6ml, continues backflow 8h, is cooled to room temperature washing and filters, dry in 60 DEG C of warm airs;
2) zeolite is integrated with Graphene: by reduced graphene ultrasonic disperse in 100ml distilled water.Configure the EDC/NHS aqueous solution of 10mmol/5mmol and join in the Graphene of dispersion, activate and add amidized zeolite stirring at normal temperature 6 hours after 0.5 hour, centrifugal drying obtains the Graphene being grafted with zeolite.
(2) preparation of protective system:
1) 100 parts of aqueous epoxy resins and 100 parts of water are got,
2) get 35 parts of zeolite graft grapheme fillers, add in above resin system, in ball mill, disperse 1h.3) get 50 parts of waterborne curing agents to mix with 100 parts of water; The mother liquor of water-base epoxy composite anticorrosion coating and the waterborne curing agent diluted being mixed in the ratio of 4:1 is coated on treated good metal substrate, controls thickness at 30-200um, self-vulcanizing.
Claims (4)
1. a preparation method for water-base epoxy composite anticorrosion coating, is characterized in that, be composited with aqueous epoxy resins after the condensation reaction that described method adopts carbodiimide (EDC) to mediate is integrated with Graphene by zeolite, concrete synthesis step is as follows again:
The amination of a zeolite: the organic solvent zeolite of 3 ~ 4g being put into 50ml, is warmed up to 80 DEG C under stirring, then adds the silane coupling agent of 5 ~ 6ml, continues backflow 8h, is cooled to room temperature washing and filters, dry in 60 DEG C of warm airs;
B zeolite is integrated with Graphene: by reduced graphene ultrasonic disperse in 50 ~ 100ml distilled water; Configure EDC/N-hydroxysuccinimide (NHS) aqueous solution of 10mmol/5mmol and join in the Graphene of dispersion, activate and add amidized zeolite stirring at normal temperature 4 ~ 6 hours after 0.5 hour, centrifugal drying obtains the Graphene being grafted with zeolite;
C gets the above-mentioned Graphene being grafted with zeolite of 10-40 part as filler, joins in the mixed solution of 100-200 part water and 100-200 part water-base resin, in ball mill, disperses 1-2h, obtain the mother liquor of water-base epoxy composite anticorrosion coating;
D gets after 25-50 part waterborne curing agent mixes with 50-100 part water and mixes in the ratio of 1:3-4 with the mother liquor of water-base epoxy composite anticorrosion coating.
2. the preparation method of a kind of water-base epoxy composite anticorrosion coating according to claim 1, is characterized in that, the silane coupling agent added in described step a is KH550 or KH-560 or KH-570 or KH-580 or KH-590.
3. the preparation method of a kind of water-base epoxy composite anticorrosion coating according to claim 1, it is characterized in that, the aqueous epoxy resins in described step c is Ar555 epoxy resin or H228A epoxy resin or E44 epoxy emulsion or E51 epoxy emulsion or E20 epoxy emulsion.
4. the preparation method of a kind of water-base epoxy composite anticorrosion coating according to claim 1, is characterized in that, in steps d waterborne curing agent be Aq419 or H228B or W651 or W650.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105199159A (en) * | 2015-10-27 | 2015-12-30 | 沈阳化工大学 | Grafted graphene flame-retardation rubber and preparation method |
| CN105905887A (en) * | 2016-04-22 | 2016-08-31 | 上海晶顿科技有限公司 | Preparation method of aminated graphene applied to anticorrosive coatings |
| CN106893447A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院金属研究所 | A kind of epoxy resin-Graphene surface chemistry bonding anticorrosive paint and preparation method |
| CN106987165A (en) * | 2017-05-26 | 2017-07-28 | 成都新柯力化工科技有限公司 | A kind of graphene polymer water-repellent paint masterbatch and preparation method |
| CN107418256A (en) * | 2017-07-10 | 2017-12-01 | 上海理工大学 | A kind of graphene slurry of anion-type water-thinned polyurethane coating and its preparation method and application |
| CN107573817A (en) * | 2017-10-16 | 2018-01-12 | 沈阳顺风实业集团有限公司 | A kind of preparation method of composite water soluble anticorrosive paint |
| CN107619636A (en) * | 2017-11-07 | 2018-01-23 | 成都新柯力化工科技有限公司 | A kind of high dispersive, impact-resistant graphene anticorrosive paint and preparation method |
| CN107722830A (en) * | 2017-10-24 | 2018-02-23 | 长春顺风新材料有限公司 | A kind of preparation method of weatherability Environment-friendlyanti-corrosive anti-corrosive paint |
| CN108624195A (en) * | 2018-06-07 | 2018-10-09 | 西南石油大学 | A kind of g-C3N4The preparation method of-G/ water-base epoxy composite coatings |
| CN109486361A (en) * | 2018-12-14 | 2019-03-19 | 沈阳顺风实业集团有限公司 | A kind of preparation method of water-repellent preservation fire prevention integrative paint |
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| CN102643592A (en) * | 2012-04-16 | 2012-08-22 | 沈阳化工大学 | Preparation method of anticorrosive paint of polyaniline modified mesoporous molecular sieve |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105199159A (en) * | 2015-10-27 | 2015-12-30 | 沈阳化工大学 | Grafted graphene flame-retardation rubber and preparation method |
| CN106893447A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院金属研究所 | A kind of epoxy resin-Graphene surface chemistry bonding anticorrosive paint and preparation method |
| CN106893447B (en) * | 2015-12-17 | 2019-08-16 | 中国科学院金属研究所 | A kind of epoxy resin-graphene surface chemistry bonding anticorrosive paint and preparation method |
| CN105905887A (en) * | 2016-04-22 | 2016-08-31 | 上海晶顿科技有限公司 | Preparation method of aminated graphene applied to anticorrosive coatings |
| CN106987165B (en) * | 2017-05-26 | 2019-05-31 | 河北晨阳工贸集团有限公司 | A kind of graphene polymer water-repellent paint masterbatch and preparation method |
| CN106987165A (en) * | 2017-05-26 | 2017-07-28 | 成都新柯力化工科技有限公司 | A kind of graphene polymer water-repellent paint masterbatch and preparation method |
| CN107418256A (en) * | 2017-07-10 | 2017-12-01 | 上海理工大学 | A kind of graphene slurry of anion-type water-thinned polyurethane coating and its preparation method and application |
| CN107418256B (en) * | 2017-07-10 | 2019-04-19 | 上海理工大学 | A kind of graphene slurry of anion-type water-thinned polyurethane coating and its preparation method and application |
| CN107573817A (en) * | 2017-10-16 | 2018-01-12 | 沈阳顺风实业集团有限公司 | A kind of preparation method of composite water soluble anticorrosive paint |
| CN107722830A (en) * | 2017-10-24 | 2018-02-23 | 长春顺风新材料有限公司 | A kind of preparation method of weatherability Environment-friendlyanti-corrosive anti-corrosive paint |
| CN107722830B (en) * | 2017-10-24 | 2019-09-17 | 长春顺风新材料有限公司 | A kind of preparation method of weatherability Environment-friendlyanti-corrosive anti-corrosive paint |
| CN107619636B (en) * | 2017-11-07 | 2018-10-09 | 福建科华中盈新材料有限公司 | A kind of high dispersive, impact-resistant graphene anticorrosive paint and preparation method |
| CN107619636A (en) * | 2017-11-07 | 2018-01-23 | 成都新柯力化工科技有限公司 | A kind of high dispersive, impact-resistant graphene anticorrosive paint and preparation method |
| CN108624195A (en) * | 2018-06-07 | 2018-10-09 | 西南石油大学 | A kind of g-C3N4The preparation method of-G/ water-base epoxy composite coatings |
| CN108624195B (en) * | 2018-06-07 | 2020-11-06 | 西南石油大学 | g-C3N4Preparation method of (E) -G/waterborne epoxy composite coating |
| CN109486361A (en) * | 2018-12-14 | 2019-03-19 | 沈阳顺风实业集团有限公司 | A kind of preparation method of water-repellent preservation fire prevention integrative paint |
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