CN105440884A - Preparation of waterborne epoxy resin self-repairing anticorrosion coating and application thereof - Google Patents

Preparation of waterborne epoxy resin self-repairing anticorrosion coating and application thereof Download PDF

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CN105440884A
CN105440884A CN201510913352.0A CN201510913352A CN105440884A CN 105440884 A CN105440884 A CN 105440884A CN 201510913352 A CN201510913352 A CN 201510913352A CN 105440884 A CN105440884 A CN 105440884A
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coating
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sio
layer
corrosion inhibitor
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CN105440884B (en
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钱备
宋祖伟
郝龙
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Qingdao Agricultural University
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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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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    • 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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    • 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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Abstract

The invention designs a waterborne epoxy resin self-repairing anticorrosion coating and belongs to the field of metal anticorrosive coatings. The preparation is characterized by the following steps: alternately depositing polyelectrolyte and a corrosion inhibitor on the surface of a waterborne nano-silica material by a layer-by-layer assembly method, centrifuging the nano-silica material wrapped with polyelectrolyte and the corrosion inhibitor layer by layer, washing with water, drying to obtain a nano-silica material loaded with a corrosion inhibitor, mixing the nano-silica material loaded with the corrosion inhibitor, waterborne epoxy resin, a curing agent and a dispersant according to a certain ratio and stirring, and carrying out ultrasonic dispersion to form uniformly dispersed waterborne epoxy resin anticorrosion coating. The prepared waterborne epoxy resin coating has a good corrosion prevention effect on carbon steel. In a damaged micro-area of the coating, the nano-silica loaded with the corrosion inhibitor can release corrosion inhibitor molecules to be adsorbed on metal surface so as to form a protection film. Thus, the coating of the invention has a certain self-repairing effect.

Description

A kind of preparations and applicatio of aqueous epoxy resins selfreparing erosion shield
Technical field
The invention belongs to anti-corrosive metal coating, be specifically related to a kind of preparation of aqueous epoxy resins selfreparing erosion shield.
Background technology
Metallic corrosion can reduce the intensity of metallic substance, shortens the work-ing life of hardware, researches and develops effective corrosion protection steps and have great importance.Anti-corrosive metal coating is the most widely used process for corrosion control of one, and coating can occur aging in life-time service process, and coat inside forms tiny crack, further expands and extend along with tiny crack, and coating bubbling can occur and peels off, and finally causes coating failure.In recent years, the study hotspot that " having the coating of self-reparing capability " becomes anti-corrosive metal coating field is developed.
At present, the main method developing coatings has three kinds: consolidant or inhibiter are encapsulated in polymer (urea-formaldehyde, carbamide, urethane, the polystyrene etc.) spherical shell of micro-nano-scale by (1), are then distributed in coating.During coating breaks down, the consolidant be encapsulated in micro-nano ball flows out, and plays crosslinked action to the solidification again of coating; Inhibiter flows out, and plays a protective role to exposed metallic matrix in corrosive medium.(2) consolidant or inhibiter are encapsulated in the material (Mierocrystalline cellulose, glass fibre) with micro-vascular structures, then micro-vascular structures material are evenly spread in coating, form the self-healing coating system with biomimetic features.During coating breaks down, consolidant or inhibiter move along micro-vascular structures passage to the microcell that breaks, and play healing and to break coating, the effect of protection metallic matrix.(3) adopt the method for (layerbylayer) self-assembly layer by layer, polyelectrolyte is deposited on nano material (SiO successively 2, ZnO, TiO 2, CeO 2, CaCO 3deng) surface, then small molecules inhibiter is encapsulated in polyelectrolyte interlayer, finally the nano material of load inhibiter is distributed in coating.When coating breaks down, inhibiter is slow releasing from polyelectrolyte interlayer, is adsorbed on metallic surface, makes metal avoid contacting with corrosive medium, reaches the effect of healing holiday.It is pointed out that and at present solvent-based coating system is concentrated on mostly for the research of self-healing coating, little to the self-healing performance study of aqueous epoxy resins coating.
Aqueous epoxy resins coating is not containing organic solvent, and non-environmental-pollution, the proportion accounted in heavy many corrosion protection coatings rises day by day, finally will replace traditional solvent-borne epoxy coating.But the corrosion prevention effect of aqueous epoxy resins coating is poor, major cause is that the film forming properties of aqueous coating is poor, hydrophilic radical residual and easily occurs dodging rust etc.Therefore, the antiseptic property improving aqueous epoxy resins coating has great importance.Above-mentioned research is most for solvent-based coating, and the aqueous epoxy resins coating that research has self-reparing capability has great importance.
Summary of the invention
The object of the invention is the antiseptic property improving aqueous epoxy resins, a kind of preparation method of aqueous epoxy resins selfreparing erosion shield is provided, the standby aqueous epoxy resins coating of this legal system has the features such as environmental protection, preparation technology be simple, can be widely used in the metal anti-corrosive paint such as shipping industry and Nuclear Power Industry field.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for aqueous epoxy resins selfreparing erosion shield, it comprises:
The first step: the water nano SiO by particle diameter being 20nm 2mix by weight 1:20 ~ 1:10 with deionized water, uniform stirring 10 ~ 30min in magnetic stirring apparatus, then in ultrasonic disperser, disperse 10 ~ 20min.
Second step: get water nano SiO prepared by 20 ~ 50mL the first step 2dispersion liquid mixes with chitosan (CS) solution 5 ~ 10mL of 1 ~ 5mg/mL, uniform stirring 10 ~ 20min in magnetic stirring apparatus, then in ultrasonic disperser, 10 ~ 20min is disperseed, finally be separated 10 ~ 20min with whizzer, after centrifugal, upper solution is outwelled, by washed with de-ionized water lower floor particulate matter, obtain the SiO of coated CS 2particle: SiO 2/ CS.Wherein water nano SiO 2particle is with electronegativity, and CS is the Natural polycations ionogen with positive electricity.
3rd step: SiO prepared by second step 2polyaniline sodium sulfonate (PSS) or alginates (AG) aqueous solution 5 ~ 10mL of/CS and 2 ~ 5mg/mL mix, uniform stirring 10 ~ 20min in magnetic stirring apparatus, then in ultrasonic disperser, 10 ~ 20min is disperseed, finally be separated 10 ~ 20min with whizzer, after centrifugal, upper solution is outwelled, by washed with de-ionized water lower floor particulate matter, obtain the SiO of coated PSS or AG, CS layer by layer 2particle: SiO 2/ CS/PSS or SiO 2/ CS/AG.Wherein PSS and AG is polyanion electrolyte.
4th step: SiO prepared by the 3rd step 2/ CS/PSS or SiO 2/ CS/AG mixes with stearylamine (ODA) aqueous solution 20 ~ 40mL of 1 ~ 5mg/mL, uniform stirring 10 ~ 20min in magnetic stirring apparatus, then in ultrasonic disperser, 10 ~ 20min is disperseed, finally be separated 10 ~ 20min with whizzer, after centrifugal, upper solution is outwelled, by washed with de-ionized water lower floor particulate matter, obtain the SiO of coated ODA, PSS or AG and CS layer by layer 2particle: SiO 2/ CS/PSS/ODA or SiO 2/ CS/AG/ODA.Wherein ODA is inhibiter, has good metallic surface filming function.
5th step: SiO prepared by the 4th step 2/ CS/PSS/ODA or SiO 2/ CS/AG/ODA mixes with PSS or the AG aqueous solution 5 ~ 10mL of 2 ~ 5mg/mL, uniform stirring 10 ~ 20min in magnetic stirring apparatus, then in ultrasonic disperser, 10 ~ 20min is disperseed, finally be separated 10 ~ 20min with whizzer, after centrifugal, upper solution is outwelled, by washed with de-ionized water lower floor particulate matter, obtain the SiO of coated ODA, PSS or AG, CS layer by layer 2particle: SiO 2/ CS/PSS/ODA/PSS or SiO 2/ CS/AG/ODA/AG.
6th step: SiO prepared by the 5th step 2/ CS/PSS/ODA/PSS or SiO 2stearylamine (ODA) aqueous solution 20 ~ 40mL of/CS/AG/ODA/AG and 1mg/mL mixes, uniform stirring 10 ~ 20min in magnetic stirring apparatus, then in ultrasonic disperser, 10 ~ 20min is disperseed, finally be separated 10 ~ 20min with whizzer, after centrifugal, upper solution is outwelled, by washed with de-ionized water lower floor particulate matter, obtain the SiO of coated ODA, PSS or AG, CS layer by layer 2particle: SiO 2/ CS/PSS/ODA/PSS/ODA or SiO 2/ CS/AG/ODA/AG/ODA, final particulate matter is put into baking oven at 50 ~ 60 DEG C dry 24h with for subsequent use.
7th step: SiO coated layer by layer prepared by the 6th step 2particle mixes with 1:20 ~ 1:10 according to weight ratio with aqueous epoxy resins coating (aqueous epoxy resins, solidifying agent, dispersion agent mix with 10:10:1), makes aqueous epoxy resins corrosion protection coating.
The technique effect that the present invention is useful is:
1. adopt the method for LBL self-assembly at water nano SiO 2surface encapsulation inhibiter stearylamine, the chitosan of what polyelectrolyte positively charged ion adopted is asepsis environment-protecting, what polyelectrolyte negatively charged ion adopted is polyaniline sodium sulfonate.
2. the Nano-meter SiO_2 of LBL self-assembly prepared of the present invention 2particle chargeding performance is good, can avoid reuniting, and can disperse, realize the structural advantage of nano material in coated filler at aqueous epoxy resins coating camber.
3. the water nano SiO of the present invention's employing 2particle can directly adopt deionized water to disperse, and reduces the usage quantity of organic solvent.
4., at coating damage microcell, the nano silicon of load inhibiter can discharge inhibitor molecular and be adsorbed on metallic surface formation protective membrane, plays certain self-repair function.
5. the aqueous epoxy resins coating prepared by the present invention and plain steel bonding properties good.
Accompanying drawing explanation
Fig. 1 is SiO 2zeta potential distribution plan; Fig. 2 is SiO 2the Zeta potential distribution plan of/CS; Fig. 3 is SiO 2the Zeta potential distribution plan of/CS/PSS; Fig. 4 is SiO 2the Zeta potential distribution plan of/CS/PSS/ODA; Fig. 5 is SiO 2the Zeta potential distribution plan of/CS/PSS/ODA/PSS; Fig. 6 is SiO 2the Zeta potential distribution plan of/CS/PSS/ODA/PSS/ODA.
The Zeta potential of the nanometer silicon dioxide material of table 1 layer assembly
The nano silicon of layer assembly Zeta potential (mV)
SiO 2 -29.4
SiO 2/CS 39.3
SiO 2/CS/PSS -35.8
SiO 2/CS/PSS/ODA 35.0
SiO 2/CS/PSS/ODA/PSS -45.8
SiO 2/CS/PSS/ODA/PSS/ODA 42.0

Claims (7)

1. the preparation of an aqueous epoxy resins selfreparing erosion shield and application thereof, it is characterized in that, utilize layer-by-layer to prepare the water-based nano silicon dioxide material of load inhibiter, and the nanometer silicon dioxide material of prepared load inhibiter is dispersed in aqueous epoxy resins coating.
2. the water-based nano silicon dioxide material preparation method of load inhibiter according to claim 1 is as follows: aqueous Nano-meter SiO_2 2the aqueous solution, mixes with polycation electrolyte, polyanion electrolyte and corrosion inhibitor solution, obtains SiO coated layer by layer 2particle.
3. water nano SiO according to claim 2 2particle diameter is 20nm, water nano SiO 2contained SiO in the aqueous solution 2massfraction be 5 ~ 10%.
4. what polycation electrolyte solution according to claim 2 adopted is concentration is the chitosan solution of 1 ~ 5mg/mL, and what polyanion electrolyte solution adopted is concentration is polyaniline sodium sulfonate or the sodium alginate soln of 2 ~ 5mg/mL.
5. what corrosion inhibitor solution according to claim 2 adopted is concentration is the stearylamine solution of 1 ~ 5mg/mL.
6. the nanometer silicon dioxide material of load inhibiter according to claim 1 and the mass ratio of aqueous epoxy resins coating are 1:20 ~ 1:10.
7. aqueous epoxy resins coating according to claim 1 is made up of aqueous epoxy resins, solidifying agent and dispersion agent, and its mass ratio is 20:10:1.
CN201510913352.0A 2015-12-12 2015-12-12 A kind of preparation and application of aqueous epoxy resins selfreparing erosion shield Expired - Fee Related CN105440884B (en)

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Cited By (14)

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Publication number Priority date Publication date Assignee Title
CN105623475A (en) * 2016-03-31 2016-06-01 青岛农业大学 Method for preparing self-healing coating based on environment-friendly nanometer container
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
CN107502133A (en) * 2017-08-11 2017-12-22 北京师范大学 Possesses corrosion-inhibiting coating of self-reparing capability and its preparation method and application
CN107674548A (en) * 2017-11-01 2018-02-09 青岛农业大学 A kind of preparation method based on magnetic gradient self-healing corrosion-inhibiting coating
CN109251582A (en) * 2018-09-04 2019-01-22 衢州市华顺钙业有限公司 A kind of compound powdered whiting of high-performance nano and preparation method thereof
CN109627826A (en) * 2018-11-29 2019-04-16 江南大学 A kind of compound shell material microcapsules and preparation method thereof with dual corrosion proof function
CN110142190A (en) * 2019-05-31 2019-08-20 中国科学院大学 Selfreparing composite coating and its application and anticorrosion material and preparation method thereof
CN111826074A (en) * 2020-07-09 2020-10-27 北京科技大学 Titanium nitride photo-thermal response based dual self-repairing coating and preparation method thereof
WO2020221378A1 (en) * 2019-04-30 2020-11-05 中山大学 Stimulus response-type self-repairing anti-corrosion coating material and preparation method
CN112647139A (en) * 2019-10-11 2021-04-13 中国科学院海洋研究所 Corrosion inhibitor coated core-shell fiber toughened organic coating and preparation method thereof
CN113444364A (en) * 2021-07-28 2021-09-28 上海应用技术大学 Layer-by-layer self-assembly pH response type silicon dioxide nano container, preparation thereof and application thereof in composite silane film
CN113462199A (en) * 2021-05-17 2021-10-01 北京化工大学 Preparation method of inorganic oxide pigment filler loaded with composite corrosion inhibitor
CN115011159A (en) * 2022-07-28 2022-09-06 中北大学 Self-repairing material based on pH response
CN116426193A (en) * 2023-04-06 2023-07-14 郑州艾洁环保设备科技有限公司 Water-based environment-friendly anticorrosive paint

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Cited By (24)

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CN105623475B (en) * 2016-03-31 2018-06-01 青岛农业大学 A kind of preparation method of the self-healing coating based on environmentally friendly nano container
CN105623475A (en) * 2016-03-31 2016-06-01 青岛农业大学 Method for preparing self-healing coating based on environment-friendly nanometer container
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
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