CN105623475B - A kind of preparation method of the self-healing coating based on environmentally friendly nano container - Google Patents
A kind of preparation method of the self-healing coating based on environmentally friendly nano container Download PDFInfo
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- CN105623475B CN105623475B CN201610194208.0A CN201610194208A CN105623475B CN 105623475 B CN105623475 B CN 105623475B CN 201610194208 A CN201610194208 A CN 201610194208A CN 105623475 B CN105623475 B CN 105623475B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- 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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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention devises a kind of self-healing coating based on environmentally friendly nano container, belongs to anti-corrosive metal coating field.It is characterized in that：Using the method for LBL self-assembly by chitosan and poly-aspartate alternating deposit on nanometer silicon dioxide material surface, by the nanometer silicon dioxide material centrifugation, deionization washing, drying of layer assembly, obtain environmentally friendly nano container, environmentally friendly nano container is mixed according to a certain percentage with diluent, ultrasonic disperse obtains component one；Epoxy resin, dispersant and levelling agent are added in component one, add curing agent after mixing, obtains finely dispersed self-healing coating.It is environmentally protective using the raw material used in self-healing coating produced by the present invention, it is cheap and easy to get；Corrosion inhibiter load capacity in nano container is big；It in coating damage microcell, loads the nano container of corrosion inhibiter and can release inhibitor molecular absorption and form protective film in metal surface, play certain self-healing.
Description
Technical field
The invention belongs to anti-corrosive metal coatings, and in particular to a kind of self-healing coating based on environmentally friendly nano container
Preparation method.
Background technology
In the long-term use, by wearing, wearing away and denuding bubbling, pin hole can easily occur for organic anti-corrosive coating
And phenomena such as micro-crack, so that the metal of small area in corrosive medium, triggers local corrosion, coating is caused to lose in advance
Effect.In recent years, people are directed to the research of intelligent self-healing corrosion-inhibiting coating and increase year by year, during such coating breaks down, are dispersed in coating
In functional microsphere or nano container can discharge consolidant or corrosion inhibiter, metal surface generate protective film, prevent or subtract
Slow corrosion of metal process.Self-healing coating becomes a kind of novel and effective method for improving coating antiseptic effect.
People can substantially be divided into two classes for the research of self-healing corrosion-inhibiting coating：One kind is using polymer microsphere or receives
Rice container encapsulation polymerizer, polymerizer such as bicyclopentadiene, epoxy resin, isocyanates, linseed oil etc. are in catalyst or solid
Under the action of agent, the reactions generation high molecular polymer such as hydrolysis, crosslinking and polymerization occurs and crams at the micro-crack of coating, every
From Korrosionsmedium and metal, corrosion-resistant effect is played；Another kind of is to utilize polymer microsphere or nano container encapsulation corrosion inhibiter
And it distributes it in coating.The electron-donating groups such as N, S, O in inhibitor molecular and metal form co-ordinate covalent bond and generate
Chemisorbed；Charged corrosion inhibiter group generates physical absorption with the metal with opposite charges；Physical absorption and chemisorbed
Collective effect micro inhibitor molecular is made to be covered in metal surface, the gold contacted at protective coating micro-crack with corrosive medium
Belong to matrix.
There are many report at present on the preparation of self-healing corrosion-inhibiting coating, and preparing encapsulation corrosion inhibiter using LBL self-assembly method receives
The method of rice container also has very much, but most using complex polyelectrolyte particle cation（Such as polyethyleneimine PEI）, polyphosphazene polymer
Electrolytic anion（Such as kayexalate PSS）With small molecule corrosion inhibiter（Such as benzotriazole BTA, 8-hydroxyquinoline）It hands over
For being deposited on nano silicon dioxide SiO2Surface prepares nano container.The preparation process of Conventional nano container is excessively cumbersome, adopts
Most of small molecule corrosion inhibiter is noxious material.
The content of the invention
The object of the present invention is to the problem according to present in existing nano container preparation process, the present invention proposes a kind of base
In the preparation method of the self-healing coating of environmentally friendly nano container；Aqueous epoxy resins coating prepared by this method has green
Environmental protection, the features such as preparation process is simple, it can be widely applied to the metal anti-corrosive paints such as shipping industry and Nuclear Power Industry field.
To achieve the above object, the technical solution adopted by the present invention is：
The present invention first uses LBL self-assembly method by chitosan and poly-aspartate alternating deposit in nano silicon dioxide material
Expect surface, obtain environmentally friendly nano container, then environmentally friendly nano container is mixed according to a certain percentage with diluent,
Component one is obtained after ultrasonic disperse；Epoxy resin, dispersant and levelling agent are added in component one, addition is solid after mixing
Agent obtains finely dispersed self-healing coating.
A kind of preparation method of the self-healing coating based on environmentally friendly nano container of the present invention includes environmentally friendly
The preparation of nano container and the preparation of self-healing coating based on environmentally friendly nano container.
The preparation method of the environmentally friendly nano container, process and step（Mass ratio）：
The first step：By 5-10 parts of Nano-meter SiO_2s2It is mixed with 100 parts of deionized waters, SiO is made in magnetic agitation 12h2Colloidal sol coagulates
Sol solution.
Second step：Take SiO made from the first step2The chitosan of sol gel solution and 5mg/mL（CS）5~10 parts of solution
Mixing, magnetic agitation 20min, ultrasonic disperse 20min centrifuge 20min, outwell upper solution after centrifugation, use deionization
Water cleaning lower floor particulate matter, obtains the SiO of cladding CS2Particle：SiO2/CS。
3rd step：SiO prepared by second step2The poly-aspartate of/CS and 2~5mg/mL（PASP）Corrosion inhibiter aqueous solution
5~10 parts of mixing, magnetic agitation 20min, ultrasonic disperse 20min centrifuge 20min, outwell upper solution after centrifugation, use
Deionized water cleaning lower floor particulate matter is coated the SiO of PASP and CS layer by layer2Particle：SiO2/CS/PASP。
4th step：Second step and the 3rd step are repeated, obtains encapsulating the nano container SiO of a large amount of PASP corrosion inhibiter2/CS/
PASP/CS/PASP.It is dry for 24 hours with spare at 50~60 DEG C that final particulate matter is put into baking oven.
The preparation method of the self-healing coating based on environmentally friendly nano container, process and step（Quality
Than）：
The first step：The nano container for encapsulating corrosion inhibiter made from 1~2 part is taken to be mixed with 1 part of diluent, magnetic agitation
10min, ultrasonic disperse 10min obtain component one；
Second step：10~20 parts of epoxy resin, 1 part of dispersant are taken, 1 part of levelling agent is added in component one, magnetic agitation
1h obtains the epoxy resin based on environmentally friendly nano container；
3rd step：5~10 parts of curing agent is taken to be added in the epoxy resin based on environmentally friendly nano container, obtain base
In the self-healing coating of environmentally friendly nano container.
The epoxy resin is bisphenol A type epoxy resin, and epoxide equivalent is 210~240g/eq.
The diluent is that volume ratio is 4:The mix reagent of 1 dimethylbenzene/n-butanol.
The curing agent is polyamide-based curing agent.
The present invention is beneficial to be had technical effect that：
1. the present invention is using the method for LBL self-assembly in Nano-meter SiO_22Surface encapsulation corrosion inhibiter poly-aspartate gathers
Electrolyte cation using chitosan, polyelectrolyte anion use corrosion inhibiter poly-aspartate.
2. the self-healing coating of the present invention can be for the mechanical damage of coating and as the painting break caused by natural environment
It falls into and responds, discharge poly-aspartate corrosion inhibiter, adsorb in metal surface, play self-healing function.
3. the preparation method of the self-healing coating based on environmentally friendly nano container of the present invention is simple, barrier propterty
Well, cost is few, easy to spread.
Description of the drawings
Fig. 1 is the infrared spectrogram of nano container；Fig. 2 is the Zeta potential figure of nano container during LBL self-assembly.
Specific embodiment
With reference to Figure of description, the invention will be further described, and protection scope of the present invention is not only limited to
Following embodiment.
Embodiment 1
It takes 5 parts of Nano-meter SiO_2s2It is mixed with 100 parts of deionized waters, SiO is made in magnetic agitation 12h2Sol gel solution takes
SiO obtained2The chitosan of sol gel solution and 5mg/mL（CS）5 parts of mixing of solution, magnetic agitation 20min, ultrasonic disperse
20min centrifuges 20min, outwells upper solution after centrifugation, lower floor's particulate matter is cleaned with deionized water, obtains cladding CS
SiO2Particle：SiO2/CS.By the SiO of preparation2The poly-aspartate of/CS and 2mg/mL（PASP）5 parts of corrosion inhibiter aqueous solution is mixed
It closes, magnetic agitation 20min, ultrasonic disperse 20min, centrifuges 20min, upper solution is outwelled after centrifugation, uses deionized water
Lower floor's particulate matter is cleaned, is coated the SiO of PASP and CS layer by layer2Particle：SiO2/CS/PASP.It repeats the above steps, is received
Rice container SiO2/CS/PASP/CS/PASP.It is dry for 24 hours with spare at 50~60 DEG C that final particulate matter is put into baking oven.
The nano container for encapsulating corrosion inhibiter made from 1 part is taken to be mixed with 1 part of diluent, magnetic agitation 10min, ultrasonic disperse
10min obtains component one；10 parts of epoxy resin, 1 part of dispersant are taken, 1 part of levelling agent is added in component one, magnetic agitation 1h,
Obtain the epoxy resin based on environmentally friendly nano container；5 parts of curing agent is taken to be added to based on environmentally friendly nano container
Epoxy resin in, obtain the self-healing coating based on environmentally friendly nano container.
Coating is coated in carbon steel test piece with bar spreader（70mm╳50mm╳2mm）On, it is 3.5% in mass fraction
Its antiseptic property is tested in NaCl solution, and passes through coating scratch experiment and tests its self-healing performance.
Embodiment 2
It takes 10 parts of Nano-meter SiO_2s2It is mixed with 100 parts of deionized waters, SiO is made in magnetic agitation 12h2Sol gel solution,
Take SiO obtained2The chitosan of sol gel solution and 5mg/mL（CS）10 parts of mixing of solution, magnetic agitation 20min, ultrasound point
20min is dissipated, 20min is centrifuged, upper solution is outwelled after centrifugation, lower floor's particulate matter is cleaned with deionized water, is coated
The SiO of CS2Particle：SiO2/CS.By the SiO of preparation2The poly-aspartate of/CS and 5mg/mL（PASP）10 parts of corrosion inhibiter aqueous solution
Mixing, magnetic agitation 20min, ultrasonic disperse 20min centrifuge 20min, outwell upper solution after centrifugation, use deionization
Water cleaning lower floor particulate matter is coated the SiO of PASP and CS layer by layer2Particle：SiO2/CS/PASP.It repeats the above steps, obtains
Nano container SiO2/CS/PASP/CS/PASP.It is dry for 24 hours with spare at 50~60 DEG C that final particulate matter is put into baking oven.
The nano container for encapsulating corrosion inhibiter made from 2 parts is taken to be mixed with 2 parts of diluents, magnetic agitation 10min, ultrasonic disperse
10min obtains component one；20 parts of epoxy resin, 2 parts of dispersants are taken, 1 part of levelling agent is added in component one, magnetic agitation 1h,
Obtain the epoxy resin based on environmentally friendly nano container；10 parts of curing agent is taken to be added to based on environmentally friendly nano container
Epoxy resin in, obtain the self-healing coating based on environmentally friendly nano container.
Coating is coated in carbon steel test piece with bar spreader（70mm╳50mm╳2mm）On, it is 3.5% in mass fraction
Its antiseptic property is tested in NaCl solution, and passes through coating scratch experiment and tests its self-healing performance.
Above-mentioned specific embodiment is in order to illustrate the features of the present invention, and case study on implementation describes inventive concept, experiment
The time of reaction and operating method, but the claim of the present invention can not be defined, it is other any without departing from this hair
Bright technical solution is included within protection scope of the present invention.
Claims (5)
1. a kind of preparation method of the self-healing coating based on environmentally friendly nano container, which is characterized in that utilize layer by layer certainly
Package technique prepares environmentally friendly nano container, and environmentally friendly nano container is dispersed in epoxy coating；Institute
Stating epoxy coating includes diluent, and used diluent is that volume ratio is 4:The mixing examination of 1 dimethylbenzene/n-butanol
Agent；The preparation method of the environmentally friendly nano container is as follows：Take Nano-meter SiO_22Sol gel solution, will be with positive electricity
Chitosan solution and poly-aspartate solution alternating deposit with negative electricity are in Nano-meter SiO_22Surface obtains the ring of encapsulation corrosion inhibiter
Border friendly nano container.
2. the preparation method of the self-healing coating according to claim 1 based on environmentally friendly nano container, feature
Be, the chitosan solution concentration with positive electricity is 5mg/mL, the poly-aspartate solution concentration with negative electricity for 2~
5mg/mL。
3. the preparation method of the self-healing coating according to claim 1 based on environmentally friendly nano container, feature
It is, the Nano-meter SiO_22Contained SiO in sol gel solution2Mass fraction be 5~10%.
4. the preparation method of the self-healing coating according to claim 1 based on environmentally friendly nano container, feature
It is, the mass ratio of the environmentally friendly nano container and epoxy coating is 1:20~1:10.
5. the preparation method of the self-healing coating according to claim 1 based on environmentally friendly nano container, feature
It is, the self-healing coating is made of nano container, epoxy resin, diluent, curing agent, levelling agent and dispersant.
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| CN201610194208.0A CN105623475B (en) | 2016-03-31 | 2016-03-31 | A kind of preparation method of the self-healing coating based on environmentally friendly nano container |
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| CN105623475B true CN105623475B (en) | 2018-06-01 |
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| CN106497194B (en) * | 2016-11-25 | 2018-10-30 | 北京建筑大学 | A kind of composite coating of preventing metal corrosion and preparation method thereof |
| CN106966511A (en) * | 2017-04-27 | 2017-07-21 | 深圳市创艺工业技术有限公司 | A kind of environment friendly biological pretreated water device |
| CN107201140A (en) * | 2017-06-17 | 2017-09-26 | 常州福隆工控设备有限公司 | A kind of self-healing coatings and preparation method thereof |
| CN107674548B (en) * | 2017-11-01 | 2019-09-13 | 青岛农业大学 | A kind of preparation method based on magnetic gradient self-healing corrosion-inhibiting coating |
| CN107760163B (en) * | 2017-11-05 | 2020-02-21 | 青岛农业大学 | Self-repairing anticorrosive coating with antifouling function and preparation method thereof |
| CN107629638A (en) * | 2017-11-10 | 2018-01-26 | 青岛农业大学 | A kind of preparation method of self-healing epoxy powder anti-corrosion coating |
| CN112553610A (en) * | 2019-09-10 | 2021-03-26 | 天津大学 | Carbon steel surface in-situ self-assembly metal-polyaspartic acid anticorrosive film and preparation method and application thereof |
| CN111359441B (en) * | 2020-03-25 | 2022-02-15 | 青岛科技大学 | Preparation method of chlorine-resistant reverse osmosis membrane filled with alkaline pH-responsive polymer nano container |
| CN112852262A (en) * | 2021-01-15 | 2021-05-28 | 上海大学 | Lignocellulose-containing anti-corrosion self-repairing coating and preparation method thereof |
| CN114806367B (en) * | 2022-03-30 | 2023-04-28 | 哈尔滨工程大学 | Preparation method of chitosan modified graphene oxide composite coating |
| CN116425445A (en) * | 2023-03-07 | 2023-07-14 | 天津大学 | Alkali response self-healing agent and preparation method and application thereof |
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|---|---|---|---|---|
| CN101613543A (en) * | 2009-07-20 | 2009-12-30 | 北京科技大学 | A kind of preparation method with coating of metal surface corrosion inhibition and self-repair function |
| CN105047955A (en) * | 2015-05-28 | 2015-11-11 | 东南大学 | Preparation method of carbon paper coating for fuel cell based on layer-by-layer self-assembly technique |
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