CN105440884B - A kind of preparation and application of aqueous epoxy resins selfreparing erosion shield - Google Patents
A kind of preparation and application of aqueous epoxy resins selfreparing erosion shield Download PDFInfo
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- C09D—COATING 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3063—Treatment with low-molecular organic compounds
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3072—Treatment with macro-molecular organic compounds
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention devises a kind of aqueous epoxy resins selfreparing erosion shield, belongs to anti-corrosive metal coating field.It is characterized in that:Using the method for layer assembly by polyelectrolyte and corrosion inhibiter alternating deposit in water-based nano silicon dioxide material surface, by the nanometer silicon dioxide material centrifugation for coating polyelectrolyte and corrosion inhibiter layer by layer, washing, dry, obtain loading the nanometer silicon dioxide material of corrosion inhibiter, the nanometer silicon dioxide material for loading corrosion inhibiter is mixed according to a certain percentage with aqueous epoxy resins, curing agent, dispersant, ultrasonic wave disperses, and forms finely dispersed aqueous epoxy resins corrosion-inhibiting coating.There is good corrosion protection to carbon steel using aqueous epoxy resins coating produced by the present invention; in coating damage microcell; the nano silicon of load corrosion inhibiter can discharge inhibitor molecular absorption and form diaphragm in metal surface, play certain self-repair function.
Description
Technical field
The invention belongs to anti-corrosive metal coating, and in particular to a kind of system of aqueous epoxy resins selfreparing erosion shield
It is standby.
Background technology
Metal erosion can reduce the intensity of metal material, shorten the service life of hardware, and research and development is effective
Corrosion protection steps have great importance.Anti-corrosive metal coating is a kind of most widely used process for corrosion control, and coating exists
Aging can occur during long-term use, coat inside forms micro-crack, as micro-crack further expands and extends, coating meeting
Generation bubbling and peeling, ultimately result in coating failure.In recent years, exploitation " coating with self-reparing capability " turns into anti-corrosion of metal
The study hotspot of coatings art.
At present, developing the main method of coatings has three kinds:(1)Consolidant or corrosion inhibiter are encapsulated in micro-nano meter ruler
The macromolecule of degree(Urea-formaldehyde, carbamide, polyurethane, polystyrene etc.)In spherical shell, painting is then dispersed in
In layer.During coating breaks down, the consolidant being encapsulated in micro-nano ball flows out, and the solidification again to coating plays crosslinked action;Inhibition
Agent is flowed out, and the exposed metallic matrix in corrosive medium is played a protective role.(2)Consolidant or corrosion inhibiter, which are encapsulated in, to be had
The material of micro-vascular structures(Cellulose, glass fibre)In, then micro-vascular structures material is evenly spread in coating, formed
Self-healing coating system with biomimetic features.During coating breaks down, consolidant or corrosion inhibiter are along micro-vascular structures passage to broken
Microcell movement is split, plays healing rupture coating, protects the effect of metallic matrix.(3)Using (layer by layer) layer by layer certainly
The method of assembling, polyelectrolyte is sequentially deposited at nano material(SiO2、ZnO、TiO2、CeO2、CaCO3Deng)Surface, then will
Small molecule corrosion inhibiter is encapsulated in polyelectrolyte interlayer, and finally the nano material for loading corrosion inhibiter is distributed in coating.Work as coating
During rupture, corrosion inhibiter slowly discharges from polyelectrolyte interlayer, adsorbs in metal surface, makes metal avoid connecing with corrosive medium
Touch, reach the effect of healing holiday.It is pointed out that the research for self-healing coating has focused largely on solvent at present
Type coating system, the self-healing performance study to aqueous epoxy resins coating are seldom.
Aqueous epoxy resins coating is free of organic solvent, and non-environmental-pollution, the proportion accounted in the more corrosion-inhibiting coatings of weight is increasingly
Rise, will finally substitute traditional solvent-borne epoxy coating.But the corrosion protection effect of aqueous epoxy resins coating is poor,
Main cause is the poor filming performance of aqueous coating, hydrophilic radical residual and easily flash rusting etc. occurs.Therefore, water-based ring is improved
The antiseptic property of oxygen resinous coat has great importance.The studies above majority is directed to solvent-based coating, and research has selfreparing
The aqueous epoxy resins coating of ability has great importance.
The content of the invention
The purpose of the present invention is to improve the antiseptic property of aqueous epoxy resins, there is provided a kind of aqueous epoxy resins selfreparing is prevented
The preparation method of corrosion resistant coating, aqueous epoxy resins coating prepared by this method have the characteristics that green, preparation technology is simple,
It can be widely applied to the metal anti-corrosive paint such as shipping industry and Nuclear Power Industry field.
To achieve the above object, the technical solution adopted by the present invention is:
A kind of preparation method of aqueous epoxy resins selfreparing erosion shield, it includes:
The first step:By the water nano SiO that particle diameter is 20nm2With deionized water by weight 1:20~1:10 mixing,
10~30min of uniform stirring in magnetic stirring apparatus, 10~20min is then disperseed in ultrasonic disperser.
Second step:The water nano SiO for taking 20~50mL first steps to prepare2The chitosan of dispersion liquid and 1~5mg/mL
(CS)5~10mL of solution is mixed, 10~20min of uniform stirring in magnetic stirring apparatus, is then disperseed in ultrasonic disperser
10~20min, 10~20min finally is separated with centrifuge, upper solution is outwelled after centrifugation, lower floor is cleaned with deionized water
Grain thing, obtain coating CS SiO2Particle:SiO2/CS.Wherein water nano SiO2Particle carries elecrtonegativity, and CS is to carry positive electricity
Natural polycations electrolyte.
3rd step:SiO prepared by second step2/ CS and 2~5mg/mL polyaniline sodium sulfonate(PSS)Or alginate
(AG)5~10mL of the aqueous solution is mixed, 10~20min of uniform stirring in magnetic stirring apparatus, is then divided in ultrasonic disperser
10~20min is dissipated, finally 10~20min is separated with centrifuge, upper solution is outwelled after centrifugation, lower floor is cleaned with deionized water
Particulate matter, PSS or AG, CS SiO are coated layer by layer2Particle:SiO2/ CS/PSS or SiO2/CS/AG.Wherein PSS and AG are
Polyanion electrolyte.
4th step:SiO prepared by the 3rd step2/ CS/PSS or SiO2/ CS/AG and 1~5mg/mL octadecylamine(ODA)Water
20~40mL of solution mix, 10~20min of uniform stirring in magnetic stirring apparatus, then in ultrasonic disperser disperse 10~
20min, 10~20min finally is separated with centrifuge, upper solution is outwelled after centrifugation, lower floor's particle is cleaned with deionized water
Thing, ODA, PSS or AG and CS SiO are coated layer by layer2Particle:SiO2/ CS/PSS/ODA or SiO2/CS/AG/ODA.Wherein
ODA is corrosion inhibiter, has good metal surface filming function.
5th step:SiO prepared by the 4th step2/ CS/PSS/ODA or SiO2/ CS/AG/ODA and 2~5mg/mL PSS or
5~10mL of the AG aqueous solution is mixed, 10~20min of uniform stirring in magnetic stirring apparatus, is then disperseed in ultrasonic disperser
10~20min, 10~20min finally is separated with centrifuge, upper solution is outwelled after centrifugation, lower floor is cleaned with deionized water
Grain thing, ODA, PSS or AG, CS SiO are coated layer by layer2Particle:SiO2/ CS/PSS/ODA/PSS or SiO2/CS/AG/ODA/
AG。
6th step:SiO prepared by the 5th step2/ CS/PSS/ODA/PSS or SiO2/ CS/AG/ODA/AG's and 1mg/mL
Octadecylamine(ODA)20~40mL of the aqueous solution is mixed, 10~20min of uniform stirring in magnetic stirring apparatus, then in ultrasonic wavelength-division
Dissipate and disperse 10~20min in device, finally separate 10~20min with centrifuge, upper solution is outwelled after centrifugation, uses deionized water
Lower floor's particulate matter is cleaned, is coated ODA, PSS or AG, CS SiO layer by layer2Particle:SiO2/ CS/PSS/ODA/PSS/ODA or
SiO2/ CS/AG/ODA/AG/ODA, final particulate matter is put into baking oven 24h is dried at 50~60 DEG C with standby.
7th step:The SiO coated layer by layer prepared by the 6th step2Particle and aqueous epoxy resins coating(Water-base epoxy tree
Fat, curing agent, dispersant are with 10:10:1 mixing)According to weight ratio with 1:20~1:10 is well mixed, and aqueous epoxy resins are made
Corrosion-inhibiting coating.
The present invention is beneficial to be had technical effect that:
1. using the method for LBL self-assembly in water nano SiO2Surface encapsulation corrosion inhibiter octadecylamine, polyelectrolyte sun
Ion is using the chitosan of asepsis environment-protecting, and polyelectrolyte anion is using polyaniline sodium sulfonate.
2. the Nano-meter SiO_2 of LBL self-assembly prepared by the present invention2Particle chargeding performance is good, can avoid reuniting, can
The high degree of dispersion in aqueous epoxy resins coating, realize structural advantage of the nano material in coated filler.
3. the water nano SiO that the present invention uses2Particle directly can be disperseed using deionized water, reduce organic solvent
Usage amount.
4. in coating damage microcell, inhibitor molecular absorption can be discharged in gold by loading the nano silicon of corrosion inhibiter
Metal surface forms diaphragm, plays certain self-repair function.
5. the aqueous epoxy resins coating and plain steel binding ability prepared by the present invention are good.
Brief description of the drawings
Fig. 1 is SiO2Zeta potential distribution map;Fig. 2 is SiO2/ CS Zeta potential distribution map;Fig. 3 is SiO2/CS/
PSS Zeta potential distribution map;Fig. 4 is SiO2/ CS/PSS/ODA Zeta potential distribution map;Fig. 5 is SiO2/CS/PSS/ODA/
PSS Zeta potential distribution map;Fig. 6 is SiO2/ CS/PSS/ODA/PSS/ODA Zeta potential distribution map.
The Zeta potential of the nanometer silicon dioxide material of the layer assembly of table 1
The nano silicon of layer assembly | Zeta potential(mV) |
SiO2 | -29.4 |
SiO2/CS | 39.3 |
SiO2/CS/PSS | -35.8 |
SiO2/CS/PSS/ODA | 35.0 |
SiO2/CS/PSS/ODA/PSS | -45.8 |
SiO2/CS/PSS/ODA/PSS/ODA | 42.0 |
Claims (3)
1. a kind of preparation method of aqueous epoxy resins selfreparing erosion shield, it is characterised in that utilize LBL self-assembly skill
Art prepare load corrosion inhibiter water-based nano silicon dioxide material, and by it is prepared load corrosion inhibiter water-based nano silicon dioxide
Material is dispersed in aqueous epoxy resins coating;Wherein, the water-based nano silicon dioxide material preparation method of corrosion inhibiter is loaded such as
Under:Aqueous Nano-meter SiO_22The aqueous solution, mix, obtain with polycation electrolyte, polyanion electrolyte and corrosion inhibitor solution
The SiO coated layer by layer2Particle;Water nano SiO2Particle diameter is 20nm, water nano SiO2Contained SiO in the aqueous solution2Quality point
Number is 5~10%;Polycation electrolyte solution is using the chitosan solution that concentration is 1~5mg/mL, polyanion electrolysis
Matter solution is using the polyaniline sodium sulfonate or sodium alginate soln that concentration is 2~5mg/mL;Corrosion inhibitor solution using
Concentration is 1~5mg/mL octadecylamine solution.
2. the preparation method of aqueous epoxy resins selfreparing erosion shield according to claim 1, it is characterised in that negative
It is 1 that the nanometer silicon dioxide material of corrosion inhibiter, which is carried, with the mass ratio of aqueous epoxy resins coating:20~1:10.
3. the preparation method of aqueous epoxy resins selfreparing erosion shield according to claim 1, it is characterised in that water
Property epoxy coating be made up of aqueous epoxy resins, curing agent and dispersant, its mass ratio be 20:10:1.
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