CN108148485A - A kind of heatproof shock resistance graphene epoxy anticorrosion composite coating - Google Patents

A kind of heatproof shock resistance graphene epoxy anticorrosion composite coating Download PDF

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Publication number
CN108148485A
CN108148485A CN201810038435.3A CN201810038435A CN108148485A CN 108148485 A CN108148485 A CN 108148485A CN 201810038435 A CN201810038435 A CN 201810038435A CN 108148485 A CN108148485 A CN 108148485A
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China
Prior art keywords
graphene
shock resistance
agent
composite coating
heatproof
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Pending
Application number
CN201810038435.3A
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Chinese (zh)
Inventor
王树立
才政
饶永超
赵书华
陈磊
陈锋
代淳
陈宏�
黄从明
刘业宇
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Changzhou University
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Changzhou University
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Priority to CN201810038435.3A priority Critical patent/CN108148485A/en
Publication of CN108148485A publication Critical patent/CN108148485A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/346Clay
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances

Abstract

The present invention relates to a kind of heatproof shock resistance graphene epoxy anticorrosion composite coatings.It is characterized in that, it is by following material composition in mass ratio:Component A, 30%~50% epoxy resin, 20%~40% diluent, 0.1%~5% graphene, 0.5%~3% dispersant, 0.1%~1% antifoaming agent, 0.1%~0.5% levelling agent, 0.5%~5% montmorillonite, 10%~20% nano-calcium carbonate, 0.2%~5% coupling agent, 1%~2% adhesion promoter.B component, 15%~25% curing agent.By the functionalization of graphene and the addition of self-control dispersant, improve dispersibility and zygosity of the graphene in epoxy systems, substantially increase heatproof, shock resistance and the antiseptic property of coating.

Description

A kind of heatproof shock resistance graphene epoxy anticorrosion composite coating
Technical field
The invention belongs to steel pipeline corrosion protection engineering fields, and in particular to a kind of heatproof shock resistance graphene epoxy anticorrosion is answered Close coating.
Background technology
Epoxy resin (EP) can show different performances because possessing different molecular architectures.And due to easily with Different curing agent, diluent, auxiliary agent etc. are used in mixed way, and are prepared in machinery, mechanics, calorifics, cohesiveness, insulation and anti-corrosive properties Excellent epoxide resin material on energy, and it is widely used in pipeline anti-corrosive paint.But oil-gas pipeline is using, in operational process Elastic deformation or plastic deformation can be generated, for example pipe laying with elastic bending, sideboom tractor are by ditch, clod wash under the good lifting pipeline of assembling beside ditch. And the impact resistance of epoxy resin coating is generally less than 50cmkg, and the impact strength data phase of board test is tested with tinplate It is more much greater than the data in steel pipe material.But for pipeline when transport, lifting, suffered external force is much larger than 50cmkg, Lead to the easily peelable layering of coating, crack and come off, reduce the antiseptic property of coating.Therefore, it is good to develop a kind of shock resistance Coating is for oil-gas pipeline important in inhibiting.
Graphene is by sp2The planar carbon atomic building of hydridization possesses high-modulus, high intensity, Lee etc. and uses atomic force nanometer Indentation has studied the fracture strength and elastic property of single-layer graphene, and the Young's modulus of graphene is calculated by analysis For 1TPa, fracture strength is up to 130GPa.Transfer membrane is formed since graphene is easily transferred to epoxy coating antithesis surface, with ring Oxygen can improve the shock resistance of coating after being used in combination, domestic and international many scholars by its application among coating, for improving The heat-resisting of coating, shock resistance and antiseptic property.Although the comprehensive performance of coating can be significantly improved when starting to add a small amount of, Since the large specific surface area of graphene, surface energy are high, when being added to a certain amount of, the easily reunion in epoxy coating is applying Crackle, stress concentration point and defect are caused in layer, so as to cause the decline of various aspects of performance.
Invention content
For a kind of insufficient existing for background technology, the present invention proposition compound painting of heatproof shock resistance graphene epoxy anticorrosion Material, heatproof ageing resistance is good, and impact resistance and antiseptic property are excellent.
The principle of the present invention is:On the one hand, graphene is by sp2The planar carbon atomic building of hydridization possesses high-modulus, high-strength Degree is easily transferred to that after epoxy coating antithesis surface forms transfer membrane, with epoxy composite use the impact resistance of coating can be improved Energy;On the other hand, graphene is the current known material with highest thermal conductivity, and the heat-resisting of epoxy can be improved as filler addition Property.By the enhancing of these two aspects performance, reduce the corrosive pipeline caused by the factors such as coating breakage, aging and accelerate.
The present invention proposes a kind of heatproof shock resistance graphene epoxy anticorrosion composite coating, material composition in mass ratio For:Component A, 30%~40% epoxy resin, 20%~35% diluent, 3%~10% graphene, 0.5%~3% dispersion Agent, 0.1%~1% antifoaming agent, 0.1%~0.5% levelling agent, 0.5%~5% montmorillonite, 10%~20% nano-calcium carbonate, 0.2%~5% coupling agent, 1%~2% adhesion promoter.B component, 15%~25% curing agent.
Further, the one kind of the epoxy resin in epoxy resin E-51, epoxy resin E-54.
Further, the diluent is one or more in ethyl acetate, dimethylbenzene, absolute ethyl alcohol.
Further, the graphene is homemade functionalization graphene, and surface is connected to zinc stearate molecule.
Further, the dispersant is homemade salicyl epoxy resin.
Further, the antifoaming agent is the antifoaming agent silicone oil of Hua Kai.
Further, the one kind of the levelling agent in RB503 and BYK333.
Further, the nano-calcium carbonate granularity is 0.01~0.1 μm.
Further, the coupling agent is KH560.
Further, the adhesion promoter is phosphoester acrylic ester.
Further, the curing agent is the aliphatic amine modified firming agent T31 of Hua Kai.
Heatproof shock resistance graphene epoxy anticorrosion composite coating of the present invention can be according to conventional Paint preparation technology system It is standby.
Functionalization graphene through the following steps that realize:
1wt% graphene oxides are put into 94wt%N, in dinethylformamide (DMF), after ultrasonic disperse 2h, then are added Enter 2wt% zinc stearates, 3wt% coupling agent KH560 are stirred to react for 24 hours, finally that products therefrom dichloromethane and DMF is anti- After backwashing is washed repeatedly, obtains zinc stearate functional graphene oxide.
Above-mentioned 1wt% functional graphene oxides are put into 89wt%DMF, and add in 10wt% hydrazine hydrates, heating 100 DEG C reaction 6h is washed products therefrom with DMF repeatedly repeatedly to get to zinc stearate functionalization graphene.
Salicyl epoxy resin through the following steps that realize:
11wt% salicylic acids, 33wt% epoxychloropropane and 6wt% tetrabutylammonium bromide are added to three-necked flask, then It is placed in 130 DEG C of oil baths and stirs 2h, be cooled to room temperature and add in 50wt% sodium hydroxide solutions (mass fraction 30%) and stir Mix 1h.Finally, decompression removes unreacted epoxychloropropane, and obtained material is washed repeatedly with deionized water repeatedly, with nothing Aqueous sodium persulfate drying is for 24 hours to get to salicyl epoxy resin.
Advantageous effect
The heatproof shock resistance graphene epoxy anticorrosion composite coating of the present invention uses graphene to be added in for heatproof toughening filler In epoxy-resin systems, pass through the functionalization of graphene surface so that have good compatibility and zygosity with epoxy matrix;It is logical Cross the addition of homemade salicyl epoxy resin so that graphene can be preferably dispersed in coating, reduce painting break Sunken harm.By the processing of these two aspects not only improve graphene caused by reunion paint cracks, stress concentration point and lack The problem is fallen into, enhances that coating is heat-resisting and shock resistance, also improves the antiseptic property of coating.
Specific embodiment
With reference to specific example, the present invention is further elaborated.
A kind of heatproof shock resistance graphene epoxy anticorrosion composite coating, material composition in mass ratio are:Component A, 33% epoxy resin, 23% diluent, 5% graphene, 1.5% dispersant, 0.5% antifoaming agent, 0.5% levelling agent, 3%, which cover, to be taken off Soil, 15% nano-calcium carbonate, 2.5% coupling agent, 1% adhesion promoter.B component, 15% curing agent.
Specific preparation method can be prepared according to conventional Paint preparation technology.
Above-mentioned coating is uniformly painted on the tinplate of 120*50mm, thickness is about 120 μm.Pass through impact elasticity test Machine, test impact strength are 250cmkg;Heat-proof aging experiment is carried out by baking oven, baking 360h does not occur always at 100 DEG C Change phenomenon;By salt-fog resistant test case, salt-fog resistant time is more than 500h.And adhesive force (cross-hatching) grade is 1, is not easy to peel off.
Examples detailed above is only to clearly illustrate the citing that the thought of the invention is done, and simultaneously non-present invention is specifically real Apply the restriction of mode.For the engineers and technicians of fields, other can also be made on the basis of the above description Various forms of variations and change.There is no need and unable to enumerate all embodiments.And it thus amplifies out aobvious and easy The variation seen is changed within still in the invention scope of the claims.

Claims (9)

1. a kind of heatproof shock resistance graphene epoxy anticorrosion composite coating, which is characterized in that by following raw material in mass ratio into It is divided into:
Component A, 30%~40% epoxy resin, 20%~35% diluent, 3%~10% graphene, 0.5%~3% dispersion Agent, 0.1%~1% antifoaming agent, 0.1%~0.5% levelling agent, 0.5%~5% montmorillonite, 10%~20% nano-calcium carbonate, 0.2%~5% coupling agent, 1%~2% adhesion promoter.B component, 15%~25% curing agent.
2. a kind of heatproof shock resistance graphene epoxy anticorrosion composite coating as described in claim 1, it is characterised in that:The ring The one kind of oxygen resin in epoxy resin E-51, epoxy resin E-54.
3. a kind of heatproof shock resistance graphene epoxy anticorrosion composite coating as described in claim 1, it is characterised in that:It is described dilute It is one or more in ethyl acetate, dimethylbenzene, absolute ethyl alcohol to release agent.
4. a kind of heatproof shock resistance graphene epoxy anticorrosion composite coating as described in claim 1, it is characterised in that:The stone Black alkene is homemade functionalization graphene, and surface is connected to zinc stearate molecule.
5. a kind of heatproof shock resistance graphene epoxy anticorrosion composite coating as described in claim 1, it is characterised in that:Dispersant For homemade salicyl epoxy resin.
6. a kind of heatproof shock resistance graphene epoxy anticorrosion composite coating as described in claim 1, it is characterised in that:It is described to disappear Infusion is antifoaming agent silicone oil.
7. a kind of heatproof shock resistance graphene epoxy anticorrosion composite coating as described in claim 1, it is characterised in that:The stream The one kind of flat agent in RB503 and BYK333, the coupling agent are KH560, and the curing agent is modified solidified for aliphatic amine Agent T31, the adhesion promoter are phosphoester acrylic ester.
8. a kind of heatproof shock resistance graphene epoxy anticorrosion composite coating as described in claim 1, it is characterised in that:It is described to receive Rice Carbonate Particle Size is 0.01~0.1 μm.
9. a kind of heatproof shock resistance graphene epoxy anticorrosion composite coating as described in claim 1, it is characterised in that:Functionalization Graphene through the following steps that realize:
1wt% graphene oxides are put into 94wt%N, in dinethylformamide (DMF), after ultrasonic disperse 2h, are added 2wt% zinc stearates, 3wt% coupling agent KH560, are stirred to react for 24 hours, finally by products therefrom dichloromethane and DMF repeatedly Washing is multiple, obtains zinc stearate functional graphene oxide.
Above-mentioned 1wt% functional graphene oxides are put into 89wt%DMF, and add in 10wt% hydrazine hydrates, heat up 100 DEG C instead 6h is answered, products therefrom is washed with DMF repeatedly repeatedly to get to zinc stearate functionalization graphene.
CN201810038435.3A 2018-01-13 2018-01-13 A kind of heatproof shock resistance graphene epoxy anticorrosion composite coating Pending CN108148485A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109306226A (en) * 2018-08-29 2019-02-05 华月圆 A kind of metal base long-effective corrosion priming paint and preparation method thereof
CN111876005A (en) * 2019-08-06 2020-11-03 江苏大地电缆有限公司 Anti-corrosion photovoltaic cable coating and preparation method thereof
CN113025162A (en) * 2021-03-16 2021-06-25 青岛爱尔家佳新材料股份有限公司 Zinc stearate graphene composite anticorrosive paint and preparation method thereof

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CN105295327A (en) * 2014-06-24 2016-02-03 安炬科技股份有限公司 Graphene Polymer Composite Material
CN105733405A (en) * 2016-03-18 2016-07-06 信和新材料股份有限公司 Graphene-based enhanced high-solid epoxy anticorrosive coating and method for preparing same
CN105906854A (en) * 2016-02-02 2016-08-31 重庆墨希科技有限公司 Graphene-modified natural latex polymer and modification method thereof
CN106750545A (en) * 2017-01-11 2017-05-31 山东欧铂新材料有限公司 A kind of zinc stearate/graphene oxide composite material and preparation method thereof
CN106833285A (en) * 2017-03-06 2017-06-13 重庆中领环保产业技术研究院有限公司 A kind of watersoluble plumbago alkene anti-corrosive powder paint and preparation method thereof

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CN102276788A (en) * 2011-05-09 2011-12-14 中国科学院宁波材料技术与工程研究所 Epoxy resin based on gallic acids as well as preparation method and application thereof
CN103450024A (en) * 2013-09-09 2013-12-18 辽宁石油化工大学 Preparation method of glycerol monostearate p-hydroxybenzoate
CN103500597A (en) * 2013-09-30 2014-01-08 广州市尤特新材料有限公司 Functionalized graphene-based solar back aluminum slurry and preparation method thereof
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109306226A (en) * 2018-08-29 2019-02-05 华月圆 A kind of metal base long-effective corrosion priming paint and preparation method thereof
CN109306226B (en) * 2018-08-29 2020-12-29 华月圆 Long-acting anticorrosion primer for metal substrate and preparation method thereof
CN111876005A (en) * 2019-08-06 2020-11-03 江苏大地电缆有限公司 Anti-corrosion photovoltaic cable coating and preparation method thereof
CN113025162A (en) * 2021-03-16 2021-06-25 青岛爱尔家佳新材料股份有限公司 Zinc stearate graphene composite anticorrosive paint and preparation method thereof

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