CN111205745B - Self-repairing anticorrosive coating and preparation method thereof - Google Patents
Self-repairing anticorrosive coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of anticorrosive coatings, and particularly relates to a self-repairing anticorrosive coating and a preparation method thereof. The self-repairing anticorrosive coating comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 20-50 parts of epoxy resin; 10-16 parts of a solvent; 0.3-1.5 parts of a dispersing agent; 0.2-1.5 parts of thixotropic agent; 38-56 parts of a filler; 1.5-5.0 parts of corrosion inhibitor microcapsule; the component B comprises the following raw materials in parts by mass: 70-90 parts of a curing agent; 10-30 parts of a solvent. The self-repairing anticorrosive coating provided by the invention has the advantages that the corrosion inhibitor is loaded in the organic-inorganic hybrid carrier and added into the anticorrosive coating, so that the problems of poor compatibility between the corrosion inhibitor microcapsule and a coating substrate, more defects caused by a channel left for a corrosive substance by the corrosion inhibitor carrier after the corrosion inhibitor is released, and poor mechanical strength of corrosion inhibitor particles are solved, the prepared coating has high corrosion resistance, the preparation method is simple, and the coating can be brushed or sprayed and is suitable for large-area construction.
Description
Technical Field
The invention relates to the technical field of anticorrosive coatings, and particularly relates to a self-repairing anticorrosive coating and a preparation method thereof.
Background
Polymer corrosion protection coatings are widely used for metal surface corrosion protection because of their simplicity and economy. However, various defects are generated in the protection process of the coating, and corrosion of the metal substrate is accelerated at the defects due to penetration of a corrosion medium, so that the service life of the coating is influenced, and economic loss is brought.
The self-repairing anticorrosive coating mainly comprises two types: one is that polymer monomer is packaged in a certain container, and when the coating is damaged, the polymer monomer reacts under the action of catalyst or curing agent to form polymer, so as to fill up the damage and prevent the penetration of corrosive medium. Another type is to disperse a container containing a corrosion inhibitor into the coating. When the metal matrix in the coating is corroded, the corrosion inhibitor can react at the corroded position to form a protective film, so that the corrosion of the metal matrix is inhibited.
In the research of the self-repairing anticorrosive coating loaded with the corrosion inhibitor, the carrier loaded with the corrosion inhibitor mainly comprises inorganic and organic carriers, wherein the inorganic carrier mainly comprises halloysite, hydroxyapatite, layered double hydroxide, mesoporous silica and the like, and the inorganic carrier has poor compatibility with the anticorrosive coating matrix and is easy to generate adverse effects on the performance of the coating. The organic carrier is inferior to the inorganic carrier in mechanical strength, and has a relatively high probability of being crushed during storage and transportation.
Chinese patent CN 107474615 a, published as: in 2019, 08 and 02 months, an anticorrosive self-repairing coating and a preparation method thereof are disclosed, wherein the anticorrosive self-repairing coating contains 5-10% of self-repairing components in percentage by mass, the self-repairing components can be microspheres loaded with a slow release agent, and the loading capacity of a corrosion inhibitor is 10-30% of the mass of the microspheres. The corrosion inhibitor has higher loading capacity, and more self-repairing components are added. Too much corrosion inhibitor particles are added to reduce the mechanical properties of the coating.
Chinese patent CN 110079140A, published as 2019, 08 and 02 discloses an intelligent response self-repairing anticorrosive coating material and a preparation method thereof. The coating material comprises zinc oxide microcapsules and a coating matrix; the zinc oxide microcapsule comprises a capsule core and a capsule core carrier, wherein the capsule core is a corrosion inhibitor, and the capsule core carrier is porous zinc oxide; the ZIF-8 membrane is arranged on the outer surface of the capsule core carrier. ZIF-8 membranes are unstable in acidic materials and can decompose. In the invention, under the acidic condition, the used pore-sealing film can be dissolved and remain in the coating, which influences the coating performance, and the microcapsules also need ultrasound when being mixed with the coating matrix, so the invention is not suitable for mass production.
Chinese patent CN 109608985A, published as 04/12.2019, provides an anticorrosive coating capable of being automatically repaired, which comprises 0.5-5 parts by weight of stimulus-responsive mesoporous silica loaded with a corrosion inhibitor and 95-99.5 parts by weight of resin condensate. When the coating is damaged, a local microenvironment is changed, the stimulation-responsive mesoporous silica shell polymer N-tert-butylcarbonyl loaded with the corrosion inhibitor in the coating is hydrolyzed and separated (under acid stimulation) or disulfide bonds are broken (under the stimulation of a reducing agent), the shell polymer is subjected to hydrophobic-hydrophilic transformation, a mesoporous silica pore passage is exposed, and the loaded corrosion inhibitor is rapidly released to form a protective film, so that the corrosion can be effectively inhibited. In the invention, under the external stimulation, the macromolecule N-tert-butylcarbonyl of the shell layer is hydrolyzed and separated or the disulfide bond is broken, so that small molecules are left in the coating, and the shell layer is subjected to hydrophobic-hydrophilic conversion, thereby providing a channel for the invasion of corrosive media.
Chinese patent CN 105949934A, published as 2016, 09 and 21 provides a microcapsule type self-repairing anticorrosive coating and a preparation method thereof, and the polyurethane microcapsule in the scheme can release active substances only when the coating is damaged by external machinery, and does not have the correspondence after the coating is damaged.
Disclosure of Invention
In order to solve the problem of insufficient anticorrosive performance and mechanical performance in the prior self-repairing coating technology mentioned in the background art, the invention provides a self-repairing anticorrosive coating, which comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by mass:
the component B comprises the following raw materials in parts by mass:
70-90 parts of curing agent
10-30 parts of a solvent;
when the composition is used specifically, the use ratio of the component A to the component B is as follows: 3: 1-7: 1.
On the basis of the technical scheme, further, in the corrosion inhibitor microcapsule, a corrosion inhibitor is a capsule core, and a copolymer is used as a capsule core carrier;
the corrosion inhibitor is one or more of benzotriazole, barium petroleum sulfonate and hexadecylamine;
the capsule core carrier is a copolymer of acrylic acid and octavinyl-cage type silsesquioxane (octavinyl-cage type silsesquioxane is also called octavinyl-POSS) or a copolymer of methacrylic acid and octavinyl-POSS.
On the basis of the technical scheme, the preparation method of the corrosion inhibitor microcapsule comprises the following steps:
step a, taking sodium dodecyl sulfate, a corrosion inhibitor and n-hexadecane to disperse in water, and carrying out ultrasonic treatment for 5-10 min to form an oil-in-water emulsion;
step b, adding a monomer solution I, an initiator KPS aqueous solution and N into the oil-in-water emulsion prepared in the step a2Stirring and reacting for 1-2 h at 60-80 ℃;
step c, respectively dropwise adding the monomer solution II and the initiator KPS aqueous solution into the solution obtained by the reaction in the step b, reacting for 4-8 hours after the dropwise adding is finished, and freeze-drying to obtain corrosion inhibitor particles;
the monomer solution I is acrylic acid or methacrylic acid, and the monomer solution II is the mixture of acrylic acid and octavinyl-POSS or the mixture of methacrylic acid and octavinyl-POSS.
On the basis of the technical scheme, the epoxy resin is bisphenol A epoxy resin.
On the basis of the technical scheme, the dispersing agent is a polymer containing a carboxylic acid copolymer.
On the basis of the technical scheme, the filler is one or more of talcum powder, precipitated barium sulfate, barite powder, ferrophosphorus powder, mica iron oxide, mica powder, sericite powder, zinc phosphate, aluminum tripolyphosphate, feldspar powder, heavy calcium, kaolin and wollastonite powder.
On the basis of the technical scheme, the solvent is one or more of dimethylbenzene, n-butanol, acetone and cyclohexane.
On the basis of the technical scheme, the thixotropic agent is one or more of bentonite type thickening agent, polyamide wax and fumed silica.
On the basis of the technical scheme, the curing agent is one or more of a polyamide curing agent, an aliphatic amine curing agent and a phenolic amine curing agent.
The invention also provides a preparation method of the self-repairing anticorrosive coating, and the preparation method of the component A comprises the following steps:
s100, adding epoxy resin, a solvent and a dispersing agent into a dispersing cylinder, and dispersing for 10min at 1000 rpm;
s200, adding a filler into the mixture obtained in the S100, dispersing for 1-2 hours at 3000rpm, and then adding a thixotropic agent for dispersing for 20-60 min;
s300, adding corrosion inhibitor particles, and dispersing for 10-20 min at 1000rmp to obtain a component A;
the preparation method of the component B comprises the following steps:
and (3) adding a curing agent and a solvent into the dispersion cylinder at the rotating speed of 1000rpm, and dispersing for 10-30 min to obtain the component B.
The self-repairing anticorrosive coating is prepared by designing the corrosion inhibitor microcapsule and designing the whole coating formula, the prepared corrosion inhibitor microcapsule swells under the action of corrosive medium water to release the corrosion inhibitor, so that a protective barrier is formed on the metal surface, the permeation of corrosive substances is reduced, the corrosion inhibitor microcapsule and the coating have good compatibility, and the prepared coating has good flexibility, adhesive force and impact resistance. The anti-corrosion performance of the coating is improved, the preparation method is simple, and the prepared coating can be brushed or sprayed and is suitable for large-area construction.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention also provides the examples (units: parts) shown in the following table:
TABLE 1
Example 1 in the a component: the epoxy resin is 6101 epoxy resin (E44), and the solvent is xylene and n-butanol; the dispersant is EFKA-4310; the thixotropic agent is 140# organic bentonite and Ultra polyamide wax; the filler is talcum powder, precipitated barium sulfate, barite powder, mica powder, sericite powder, aluminum tripolyphosphate and feldspar powder. (ii) a The component B comprises: the curing agent is a BS805 curing agent; the solvent is dimethylbenzene and n-butyl alcohol, wherein the weight ratio of the component A to the component B is 6: 1;
example 2 in the a component: the epoxy resin is 618 epoxy resin (the trade name is E51), and the solvent is xylene and cyclohexanone; the dispersant is BYK-220 s; the thixotropic agent is 140# bentonite; the filler is talcum powder, precipitated barium sulfate, barite powder, mica powder, sericite powder, mica iron oxide and feldspar powder; the component B comprises: the curing agent is MD2015 cashew nut shell oil phenolic aldehyde amine curing agent; the solvent is dimethylbenzene, and the weight ratio of the component A to the component B is 3: 1;
example 3 in the a component: the epoxy resin is a mixture of 6101 epoxy resin and 618 epoxy resin, and the solvent is dimethylbenzene and n-butyl alcohol; the dispersant is BYK-110; the thixotropic agent is 140# organic bentonite and Ultra polyamide wax; the filler is talcum powder, precipitated barium sulfate, barite powder, ferrophosphorus powder, mica iron oxide and feldspar powder; the component B comprises: the curing agent is a mixture of a BS8328 polyamide curing agent and an KDX2015 cashew nut shell oil phenolic aldehyde amine curing agent; the solvent is dimethylbenzene; the weight ratio of the component A to the component B is 4: 1.
In each example, the corrosion inhibitor microcapsule is prepared by the following preparation method:
step 1: dispersing 0.2g of sodium dodecyl sulfate, 15g of barium petroleum sulfonate and 0.8g of n-hexadecane in 80mL of water, and performing ultrasonic treatment for 5-10 min to form an oil-in-water emulsion;
step 2: to the oil-in-water emulsion prepared in step 1 was added 5g of an acrylic acid solution, 002g of aqueous solution of initiator KPS, N2Under the condition of 60-80 ℃, stirring and reacting for 1-2 h, wherein the KPS concentration in the initiator KPS aqueous solution is 0.01 g/mL;
and step 3: respectively dropwise adding 5g of acrylic acid, 5g of octavinyl-POSS monomer solution and 0.06g of KPS aqueous solution as an initiator into the solution obtained by the reaction in the step 2, reacting for 4-8 h after the dropwise addition is finished, and freeze-drying to obtain corrosion inhibitor particles; in the initiator KPS aqueous solution, the concentration of KPS is 0.01 g/mL.
The preparation method of the self-repairing anticorrosive coating of each embodiment comprises the following steps:
the component A comprises the following steps:
s100, adding epoxy resin, a solvent and a dispersing agent into a dispersing cylinder, and dispersing for 10min at 1000 rpm;
s200, adding a filler into the mixture obtained in the S100, dispersing for 1-2 hours at 3000rpm, and then adding a thixotropic agent for dispersing for 20-60 min;
s300, adding corrosion inhibitor particles, and dispersing for 10-20 min at 1000rmp to obtain a component A;
the preparation method of the component B comprises the following steps:
and (3) adding a curing agent and a solvent into the dispersion cylinder at the rotating speed of 1000rpm, and dispersing for 10-30 min to obtain the component B.
The invention also provides the following comparative examples:
comparative example 1: on the basis of example 3, comparative example 1 is an anticorrosive coating without adding a corrosion inhibitor, and the rest components and the preparation method are the same as those of example 3;
comparative example 2: on the basis of example 3, comparative example 2 is an anticorrosive coating without a load of directly adding a corrosion inhibitor, and the rest of the components and the preparation method are the same as those of example 3;
comparative example 3: on the basis of the example 3, the comparative example 2 is an anticorrosive coating adopting a silica supported corrosion inhibitor, and the rest components and the preparation method are the same as those of the example 3;
the above examples and comparative examples were subjected to performance tests, and the test results are shown in table 2:
table 2 examples performance results
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Detection method |
| Adhesion, MPA | ≥10 | ≥10 | ≥10 | ≥10 | ≥10 | ≥10 | GB/T 5210 |
| Sagging property, μm | 275 | 275 | 275 | 250 | 250 | 225 | GB/T 9264 |
| Flexibility, mm | ≤1 | ≤1 | ≤1 | ≤1 | ≤1 | ≤2 | GB/T 1731 |
| Impact resistance, cm | ≥50 | ≥50 | ≥50 | ≥45 | ≥45 | ≥50 | GB/T 1732 |
| Salt spray resistance, h | 1000 | 800 | 900 | 450 | 500 | 600 | GB/T 1771 |
| Sea water resistance, d | 50 | 50 | 50 | 25 | 30 | 35 | GB/T 1763 |
As can be seen from the above examples and comparative examples 1 and 2, in the self-repairing anticorrosive coating provided by the invention, the corrosion inhibitor microcapsule loads the corrosion inhibitor into the organic-inorganic hybrid carrier and adds the corrosion inhibitor into the anticorrosive coating, so that the problems that the compatibility between the corrosion inhibitor microcapsule and the coating substrate is poor, the corrosion inhibitor carrier leaves a channel for corrosive substances after the corrosion inhibitor is released, more defects are caused, and the mechanical strength of corrosion inhibitor particles is poor are solved, and the POSS rigid structure in the corrosion inhibitor microcapsule is favorable for improving the impact resistance; it can be seen from comparative example 3 that the mechanical properties and corrosion resistance of the silica-supported corrosion inhibitor of the prior art are far from those provided by the present invention.
According to the invention, through creative design, the surface of the prepared corrosion inhibitor microcapsule is provided with a hydrophilic acrylic acid chain segment, and the prepared corrosion inhibitor microcapsule is contacted with corrosive medium water to swell in the presence of water, namely when corrosion occurs, so that the corrosion inhibitor is released, the controllable release of the corrosion inhibitor is realized, the released corrosion inhibitor is adsorbed to the metal surface to form a film, and the protection is generated, so that the slow release effect has responsiveness, and the corrosion prevention time of the coating is greatly delayed; when the coating is not corroded and is not contacted with outside water, the capsule is closed, the corrosion inhibitor is not released, and the long-term use of the corrosion inhibitor microcapsule is ensured. In addition, the octavinyl-POSS carried on the surface of the corrosion inhibitor microcapsule has a crosslinking effect, so that the condition that a high-molecular shell is dissolved and remains in a coating to generate adverse effect on the coating is avoided, and the silicon-oxygen bond in the octavinyl-POSS has hydrophobicity, repels a water-soluble electrolyte and further generates protection. In addition, the corrosion inhibitor microcapsule prepared by the invention has good compatibility with resin in the coating, and the prepared coating has good flexibility, adhesion and impact resistance.
The capsule core carrier loaded with the corrosion inhibitor is a copolymer of acrylic acid and octavinyl-POSS or a copolymer of methacrylic acid and octavinyl-POSS, wherein polyacrylic acid or polymethacrylic acid has good compatibility with a coating resin matrix, and an inorganic cage-shaped part of the octavinyl-POSS has rigidity, so that the mechanical strength of the corrosion inhibitor microcapsule can be increased, and the probability of being broken when corrosion inhibitor particles are added into an anticorrosive coating and during the storage and transportation processes of the coating is reduced, so that the prepared coating is suitable for spraying and is suitable for large-area production.
According to the invention, the polymer monomer is initiated on the surface of the corrosion inhibitor, so that the corrosion inhibitor microcapsule with the corrosion inhibitor as a capsule core and the polymer as a shell is prepared, the corrosion inhibitor encapsulation is realized, the content of the corrosion inhibitor in the microcapsule can be controlled by the adding amount of the corrosion inhibitor and the polymer monomer, and the problem of low corrosion inhibitor loading rate is solved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. The self-repairing anticorrosive coating is characterized by comprising a component A and a component B, wherein the component A comprises the following raw materials in parts by weight:
20-50 parts of epoxy resin
10-16 parts of solvent
0.3 to 1.5 parts of dispersant
0.2 to 1.5 parts of thixotropic agent
38-56 parts of filler
1.5-5.0 parts of corrosion inhibitor microcapsule;
the component B comprises the following raw materials in parts by mass:
70-90 parts of curing agent
10-30 parts of a solvent;
in the corrosion inhibitor microcapsule, a corrosion inhibitor is a capsule core, and a copolymer is used as a capsule core carrier;
the corrosion inhibitor is one or more of benzotriazole, barium petroleum sulfonate and hexadecylamine;
the capsule core carrier is a copolymer of acrylic acid and octavinyl-POSS or a copolymer of methacrylic acid and octavinyl-POSS;
the preparation method of the corrosion inhibitor microcapsule comprises the following steps:
step a, taking sodium dodecyl sulfate, a corrosion inhibitor and n-hexadecane to disperse in water, and carrying out ultrasonic treatment for 5-10 min to form an oil-in-water emulsion;
step b, adding a monomer solution I, an initiator KPS aqueous solution and N into the oil-in-water emulsion prepared in the step a2Stirring and reacting for 1-2 h at 60-80 ℃;
step c, respectively dropwise adding the monomer solution II and the initiator KPS aqueous solution into the solution obtained by the reaction in the step b, reacting for 4-8 hours after the dropwise adding is finished, and freeze-drying to obtain the corrosion inhibitor microcapsule;
the monomer solution I is acrylic acid or methacrylic acid, and the monomer solution II is the mixture of acrylic acid and octavinyl-POSS or the mixture of methacrylic acid and octavinyl-POSS.
2. The self-repairing anticorrosive coating of claim 1, characterized in that: the epoxy resin is bisphenol A type epoxy resin.
3. The self-repairing anticorrosive coating of claim 1, characterized in that: the dispersant is a polymer containing a carboxylic acid copolymer.
4. The self-repairing anticorrosive coating of claim 1, characterized in that: the filler is one or more of talcum powder, precipitated barium sulfate, ferrophosphorus powder, mica iron oxide, mica powder, zinc phosphate, aluminum tripolyphosphate, feldspar powder, heavy calcium, kaolin and wollastonite powder.
5. The self-repairing anticorrosive coating of claim 1, characterized in that: the solvent is one or more of dimethylbenzene, n-butanol, acetone and cyclohexane.
6. The self-repairing anticorrosive coating of claim 1, characterized in that: the thixotropic agent is one or more of bentonite thickener, polyamide wax and fumed silica.
7. The self-repairing anticorrosive coating of claim 1, characterized in that: the curing agent is one or more of polyamide curing agent, fatty amine curing agent and phenolic aldehyde amine curing agent.
8. The preparation method of the self-repairing anticorrosive coating according to any one of claims 1 to 7, characterized in that the preparation method of the component A comprises the following steps:
s100, adding epoxy resin, a solvent and a dispersing agent into a dispersing cylinder, and dispersing for 10min at 1000 rpm;
s200, adding a filler into the mixture obtained in the S100, dispersing for 1-2 hours at 3000rpm, and then adding a thixotropic agent for dispersing for 20-60 min;
s300, adding a corrosion inhibitor microcapsule, and dispersing for 10-20 min at 1000rmp to obtain a component A;
the preparation method of the component B comprises the following steps:
and (3) adding a curing agent and a solvent into the dispersion cylinder at the rotating speed of 1000rpm, and dispersing for 10-30 min to obtain the component B.
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| CN202010022790.9A CN111205745B (en) | 2020-01-09 | 2020-01-09 | Self-repairing anticorrosive coating and preparation method thereof |
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| CN202010022790.9A CN111205745B (en) | 2020-01-09 | 2020-01-09 | Self-repairing anticorrosive coating and preparation method thereof |
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| CN111205745A CN111205745A (en) | 2020-05-29 |
| CN111205745B true CN111205745B (en) | 2021-04-20 |
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| CN111943840B (en) * | 2020-07-27 | 2022-08-23 | 浙江建业化工股份有限公司 | Treatment process of n-propyl acetate bed charge |
| CN112521837B (en) * | 2020-12-30 | 2022-05-20 | 四川轻化工大学 | Filler of MOF (Metal organic framework) supported corrosion inhibitor, self-repairing anticorrosive coating and preparation method of self-repairing anticorrosive coating |
| CN112920689A (en) * | 2021-03-11 | 2021-06-08 | 荆楚理工学院 | Heavy-duty anticorrosive paint with self-healing function and preparation and use methods thereof |
| CN113245166A (en) * | 2021-03-24 | 2021-08-13 | 吉林大学 | Bionic intelligent repeatable self-repairing coating and drop coating process method thereof |
| CN113122111B (en) * | 2021-04-28 | 2022-05-06 | 广东中申建筑工程有限公司 | Preparation method of composite novel building anticorrosive material |
| CN113980553A (en) * | 2021-11-29 | 2022-01-28 | 国网山东省电力公司电力科学研究院 | Self-repairing water-based anticorrosive coating, preparation method and application thereof |
| CN116622260A (en) * | 2022-02-14 | 2023-08-22 | 中国石油化工股份有限公司 | Sulfur-containing environment antibacterial coating and preparation method thereof |
| CN115011159B (en) * | 2022-07-28 | 2023-04-14 | 中北大学 | Self-repairing material based on pH response |
| CN115322613B (en) * | 2022-08-23 | 2023-04-07 | 南京工业大学 | Bio-based microcapsule and preparation method and application thereof |
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