CN112521837B - Filler of MOF (Metal organic framework) supported corrosion inhibitor, self-repairing anticorrosive coating and preparation method of self-repairing anticorrosive coating - Google Patents
Filler of MOF (Metal organic framework) supported corrosion inhibitor, self-repairing anticorrosive coating and preparation method of self-repairing anticorrosive coating Download PDFInfo
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Abstract
The invention discloses a filler of an MOF (metal organic framework) load corrosion inhibitor, a self-repairing anticorrosive coating and a preparation method thereof, wherein the filler takes a metal organic framework compound hmt-MOF as a capsule shell and a corrosion inhibitor packaged in the metal organic framework compound as a capsule core, a hmt-MOF compound is formed by assembling two organic polydentate ligands of hexamethylenetetramine and terephthalic acid, an amino nitrogen atom in the hexamethylenetetramine and a carboxyl oxygen atom in the terephthalic acid can react with a functional group in resin, and the composite has good compatibility, is easy to disperse and has high storage stability, can react with a metal substrate to generate an N/O coordinate bond, a hydrogen bond and the like, enhances the adhesion and the anticorrosive performance of a coating and the substrate, and can keep a high self-repairing function for a long time in an acid-alkali environment. The invention has the advantages of easily obtained raw materials, low toxicity, simple production process flow, easy preparation, accordance with the trend of green environmental development, large-scale industrial production and good application prospect.
Description
Technical Field
The invention relates to the technical field of anticorrosive coatings, and particularly relates to a filler of an MOF (metal organic framework) supported corrosion inhibitor, a self-repairing anticorrosive coating and a preparation method thereof.
Background
The metal corrosion refers to the phenomenon that metal is deteriorated and deteriorated due to chemical, electrochemical or physical action between the metal and an environmental medium in which the metal is positioned. Metal corrosion is a security and economic problem which is of great concern to all countries, and not only can it cause serious economic losses, but it can also affect human health. According to the statistics of corrosion protection organization, the economic loss caused by metal corrosion in China accounts for about 4% of the total production value of the nation every year, and the corrosion loss in China exceeds 2 trillion, which is 4 times of the loss of natural disasters. To avoid the serious consequences of metal corrosion, the most economical and effective coatings are often used to protect the building metal by preventing corrosion of the corrosion-inhibiting coating from the corrosive medium and the metal substrate. And public facilities such as highways, bridges, oil pipelines and the like are often in severe environments such as sand and stone splashing, darkness, dampness and the like, are often exposed to acid-base environments, and inevitably generate local damage and microcracks, and then the damage or the microcracks gradually spread and expand, so that the service life and the corrosion resistance of the coating are greatly reduced.
At present, the protection of metal equipment is mainly to coat anticorrosive paint. The traditional anticorrosive paint cannot fully exert the anticorrosive performance because of the defects of film forming substances and certain pores and defects in the coating after film forming. In recent years, self-repairing coatings added with corrosion inhibitor-loaded nano containers are receiving much attention, and when corrosion occurs due to damage of the coatings, the added nano containers can spontaneously release corrosion inhibitor molecules to inhibit corrosion of metals.
Metal Organic Framework (MOF) is an organic-inorganic hybrid material with intramolecular pores formed by self-assembly of organic ligands and metal ions or clusters through coordination bonds, and is widely applied to the fields of biosensing, drug delivery and catalysis due to its highly adjustable porosity, large in-pore volume and abundant action sites. At present, the MOF material serving as a nano microcapsule sealing corrosion inhibitor as a filler for improving the corrosion resistance of the coating is reported, for example, the invention patent CN110551398A discloses a coating containing Fe2+Metal organic framework corrosion inhibitor-hydrogel compound with response characteristic, preparation method and application thereof, and Fe2+The ion-responsive copper-based carboxylic acid metal organic framework is used as a carrier, and 3-mercapto-1, 2, 4-triazole is used as a load object; the copper-based carboxylic acid metal organic framework encapsulated with the 3-mercapto-1, 2, 4-triazole corrosion inhibitor is obtained by combining the copper-based carboxylic acid metal organic framework porous nano material with the 3-mercapto-1, 2, 4-triazole corrosion inhibitor, and Fe2+The ions can expand the outer pore diameter of the frame by being replaced with the hexadecyl trimethyl ammonium cation center of the metal organic framework so as to release the corrosion inhibitor encapsulated inside, but the compound can only be used in the environment of a ferrous matrix. CN110387548A discloses a compound of metal organic framework encapsulation corrosion inhibitor and a preparation method and application thereof, the ZIFs nano-shell has water stability and acidity sensitivity which are not possessed by other MOF types, so that the compound is suitable for corrosion environment of sea water splash zone, the ZIFs can respond to acidic microenvironment at splash zone corrosion induction stage in an acidic dissociation critical point of the ZIFs, and the corrosion inhibitor can be released rapidly to act on corrosion zone. However, the complex can only play a role in an acidic microenvironment, and the application range of the complex is limited. In addition, the corrosion inhibition performance of the microcapsule is greatly limited due to the dispersibility problem of the microcapsule in coatings of epoxy resin and the like.
Hexamethylene tetramine (hmt) and terephthalic acid (pta) are rigid polydentate ligands, and a mixed complex formed by the hexamethylene tetramine and transition metal ions is a typical MOF material, so that the MOF material has good application potential in the fields of catalytic reaction, gas storage and separation, chemical sensors and the like, but no relevant report of the application of the MOF material in the aspect of anticorrosive coatings exists so far.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a filler of an MOF loaded corrosion inhibitor, a self-repairing anticorrosive coating and a preparation method thereof, and solves the technical problems of poor filler dispersibility, poor anticorrosive effect and small application range of the conventional anticorrosive coating.
In order to achieve the purpose, the invention adopts the following technical scheme: a filler of MOF supported corrosion inhibitor is prepared by the following steps:
1) dissolving transition metal salt in water to obtain a transition metal salt solution, slowly dropwise adding a hexamethylenetetramine aqueous solution under the condition of stirring at room temperature, continuously stirring, then adding terephthalic acid, uniformly stirring and dispersing, transferring into a reaction kettle, sealing, placing in an oven for high-temperature reaction for a certain time, stopping the reaction, filtering solids in the reaction kettle, and drying the obtained filter cake to obtain the metal organic framework compound hmt-MOF.
2) Dispersing hmt-MOF prepared in the step 1) in a mixed solvent at room temperature, adding a corrosion inhibitor under the stirring condition, continuously stirring for 10-20 h, standing for a period of time, filtering, washing a filter cake with absolute ethyl alcohol and distilled water in sequence, and drying in vacuum at 60 ℃ to obtain the metal organic framework compound corrosion inhibitor-loaded filler.
Preferably, the amount ratio of the hexamethylene tetramine to the terephthalic acid to the transition metal salt is 2: 1-1.5: 1.
Preferably, the transition metal salt may be selected from one or more of copper nitrate, copper chloride, nickel nitrate, nickel chloride, cobalt nitrate and cobalt chloride; the concentration of the transition metal salt solution is 0.04-0.06 mol/L.
Preferably, the reaction temperature in the step 1) is 150-180 ℃, and the reaction time is 48-72 hours; the drying temperature is 100 ℃, and the drying time is 12 h.
Preferably, the mixed solvent is a mixed solution of deionized water and ethanol in an equal volume ratio; the mass-volume ratio of the hmt-MOF to the mixed solvent is 1 g: 20-40 mL; the corrosion inhibitor is an amino corrosion inhibitor, preferably one or a combination of two of hexamethylenetetramine and methylimidazole; the mass ratio of the hmt-MOF to the corrosion inhibitor is 1: 0.02-0.1.
The invention also provides the application of the filler of the MOF supported corrosion inhibitor in anticorrosion coating.
The invention also provides a self-repairing anticorrosive coating, which comprises a component A and a component B in equal mass ratio, wherein the component A comprises the following components in parts by mass: 100 parts of a film-forming material, 1 to 5 parts of the filler according to any one of claims 1 to 6, 5 to 15 parts of an inorganic filler, 20 to 40 parts of a diluent, and 0.5 to 1.5 parts of a defoaming agent; the component B comprises a curing agent and a diluent, and the mass ratio of the curing agent to the diluent is 1: 0.3-0.5.
Preferably, the film-forming material is epoxy resin E-51, and the epoxy value is 0.48-0.54 mol/100 g; the inorganic filler is coupled gas phase white carbon black; the diluent is a mixed solvent of ethanol and n-butanol; the defoaming agent is a commercially available BYK-055 defoaming agent; the curing agent is 650 low-molecular-weight polyamide, the amine value is 220 +/-20 mg KOH/g, the viscosity is 15000-20000 mPa-s (40 ℃), and the active hydrogen equivalent is 195; the diluent is a mixed solvent of N-butanol and N-methyl-2-pyrrolidone, and preferably, the volume ratio of the N-butanol to the N-methyl-2-pyrrolidone in the diluent is 1: 1.5.
Another object of the present invention is to provide a method for preparing the self-repairing anticorrosive coating, which comprises: and mixing the film-forming material, the filler of the MOF-loaded corrosion inhibitor, the inorganic filler, the diluent and the defoaming agent to form a component A, and then uniformly mixing and stirring the component A and a component B consisting of the curing agent and the diluent to obtain the self-repairing anticorrosive coating.
The invention also aims to provide a self-repairing anticorrosive coating formed by curing the self-repairing anticorrosive coating at the temperature of 45-65 ℃ for 3-5 hours.
Compared with the prior art, the invention has the following beneficial effects:
1. the filler provided by the invention takes a metal organic framework compound hmt-MOF as a capsule shell and a corrosion inhibitor encapsulated in the metal organic framework compound as a capsule core, and the hmt-MOF compound is assembled by two organic polydentate ligands of hexamethylenetetramine and terephthalic acid, contains rich amino and carboxyl, is good in compatibility with organic resin, is easy to disperse, and has high storage stability. In addition, the amino nitrogen atom in the hexamethylenetetramine and the carboxyl oxygen atom in the terephthalic acid can react with the functional group in the resin to improve the performance of the coating, and can react with the metal substrate to generate a metal-N/O coordination bond, a hydrogen bond and the like, so that the corrosion resistance of the coating is improved, and the adhesive force between the coating and the substrate is enhanced.
2. The filler of the MOF loaded corrosion inhibitor in the self-repairing anticorrosive coating formed by the self-repairing anticorrosive coating prepared by the invention has good stability, can fill pores in the coating, hinder and avoid permeation of corrosive medium oxygen and aqueous solution, and improve the anticorrosive performance of the coating. In addition, when the coating is damaged, particularly acid-base corrosion occurs, the hmt-MOF compound is dissociated to send the encapsulated corrosion inhibitor hexamethylenetetramine to a metal corrosion area, targeted recognition and release are realized, an insoluble protective film is formed on the surface of a corrosion substrate, and the reaction of the metal substrate and a corrosion medium is inhibited, so that a high self-repairing function can be kept for a long time in an acid-base environment, the conditions that the self-repairing function of a common self-repairing anticorrosive coating in the environment is rapidly attenuated and the like are avoided, and the anti-corrosion performance is greatly high.
3. The self-repairing anticorrosive coating provided by the invention takes hexamethylenetetramine and terephthalic acid as raw materials, the raw materials are easy to obtain and low in toxicity, the production process flow is simple, the preparation is easy, the self-repairing anticorrosive coating accords with the trend of green environmental protection development, and the large-scale industrial production can be realized.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The following examples are not intended to specifically show that the reagents used are those which are generally commercially available and the methods used are conventional.
Example 1
1. Preparation method of filler of metal organic framework compound loaded with corrosion inhibitor
1) 0.004 mol of copper nitrate trihydrate (Cu (NO)3)2·3H2O) is dissolved in 100mL of deionized water, 10mL of aqueous solution containing 0.008 mol of hexamethylenetetramine is slowly dripped under the condition of stirring at room temperature, the stirring is continued for 30 minutes, then 0.004 mol of terephthalic acid is added, the mixture is uniformly stirred and dispersed, the mixture is transferred into a polytetrafluoroethylene reaction kettle, the reaction kettle is sealed and placed in a drying oven at 150 ℃ for reaction for 48 hours, the reaction is stopped, the solid in the reaction kettle is filtered, and the filter cake is dried for 12 hours at 100 ℃, so that the metal organic framework compound hmt-MOF is obtained.
2) Dispersing 1.0 g of hmt-MOF in 20 mL of mixed solvent of deionized water and ethanol (v: v = 1: 1) at room temperature, adding 0.03 g of hexamethylenetetramine under stirring, continuing stirring for 10h, standing for a period of time, filtering, washing a filter cake with absolute ethyl alcohol and distilled water in sequence, and drying in vacuum at 60 ℃ to obtain the metal organic framework compound supported corrosion inhibitor MOF-in.
2. Preparation of self-repairing anticorrosive coating
1) 100g of epoxy resin E-51, 1.0 g of MOF-in prepared in the example, 15 g of coupled fumed silica, 33.5 g of a mixed solvent of ethanol and n-butanol (v: v = 1: 1) and 0.5g of BYK-055 antifoaming agent were dispersed in a dispersion machine at high speed for 10 minutes at room temperature, and then filtered to prepare component A.
2) 100g of 650 g of low molecular weight polyamide and 50 g of a mixed solvent of N-butanol and N-methyl-2-pyrrolidone (v: v = 1: 1.5) were mixed and stirred at room temperature to prepare two components B.
3) When in use, the A, B two components are uniformly stirred and mixed according to the mass ratio of 1: 1 to obtain the self-repairing anticorrosive paint.
Example 2
1. Preparation method of filler of metal organic framework compound loaded with corrosion inhibitor
1) 0.005mol of nickel nitrate hexahydrate (Ni (NO)3)2·6H2O) is dissolved in 100mL of deionized water, 10mL of aqueous solution containing 0.01mol of hexamethylenetetramine is slowly dripped under the condition of stirring at room temperature, the stirring is continued for 30 minutes, then 0.0075 mol of terephthalic acid is added, the mixture is uniformly stirred and dispersed, the mixture is transferred into a polytetrafluoroethylene reaction kettle, the reaction kettle is sealed and placed in an oven at 170 ℃ for reaction for 56 hours, the reaction is stopped, the solid in the reaction kettle is filtered, and the filter cake is dried at 100 ℃ for 12 hours, thus obtaining the metal organic framework compound hmt-MOF.
2) Dispersing 1 g of hmt-MOF in 30 mL of mixed solvent of deionized water and ethanol (v: v = 1: 1) at room temperature, adding 0.03 g of hexamethylenetetramine under stirring, continuing stirring for 12h, standing for a period of time, filtering, washing a filter cake with absolute ethyl alcohol and distilled water in sequence, and drying in vacuum at 60 ℃ to obtain the metal-organic framework compound supported corrosion inhibitor MOF-in.
2. Preparation of self-repairing anticorrosive coating
1) 100g of epoxy resin E-51, 2.5 g of MOF-in, 12.5 g of coupled fumed silica, 34 g of a mixed solvent of ethanol and n-butanol (v: v = 1: 1) and 1.0 g of BYK-055 antifoaming agent were dispersed in a dispersion machine at high speed for 10 minutes at room temperature, and then filtered to prepare component A.
2) Mixing and stirring 108 g of 650 g of low molecular weight polyamide and 42 g of mixed solvent of N-butanol and N-methyl-2-pyrrolidone (v: v = 1: 1.5) at room temperature to prepare a component B.
3) When in use, the A, B two components are uniformly stirred and mixed according to the mass ratio of 1: 1 to obtain the self-repairing anticorrosive paint.
Example 3
1. Preparation method of filler of metal organic framework compound loaded with corrosion inhibitor
1) 0.006 mol of nickel chloride hexahydrate (NiCl)2·6H2O) was dissolved in 100mL of deionized water, and a solution containing 0.012 m was slowly added dropwise with stirring at room temperatureAnd (2) continuously stirring 10mL of an ol hexamethylene tetramine aqueous solution for 30 minutes, then adding 0.008 mol of terephthalic acid, uniformly stirring and dispersing, transferring into a polytetrafluoroethylene reaction kettle, sealing, placing in a 170 ℃ drying oven for reacting for 65 hours, stopping the reaction, filtering the solid in the reaction kettle, and drying the filter cake for 12 hours at 100 ℃ to obtain the metal organic framework compound hmt-MOF.
2) Dispersing 1 g of hmt-MOF in 30 mL of mixed solvent of deionized water and ethanol (v: v = 1: 1) at room temperature, adding 0.07 g of 2-methylimidazole under the stirring condition, continuing stirring for 14h, standing for a period of time, filtering, washing a filter cake with absolute ethyl alcohol and distilled water in sequence, and drying in vacuum at 60 ℃ to obtain the metal organic framework compound supported corrosion inhibitor MOF-in.
2. Preparation of self-repairing anticorrosive coating
1) 100g of epoxy resin E-51, 3.5 g of MOF-in prepared in the example, 10.5 g of coupled fumed silica, 35g of a mixed solvent of ethanol and n-butanol (v: v = 1: 1), and 1.0 g of BYK-055 antifoaming agent were dispersed in a dispersion machine at high speed for 10 minutes at room temperature, and then filtered to prepare component A.
2) Mixing 650 g of low molecular polyamide and 35g of mixed solvent of N-butanol and N-methyl-2-pyrrolidone (v: v = 1: 1.5) at room temperature, and stirring to obtain component B.
3) When in use, the A, B two components are uniformly stirred and mixed according to the mass ratio of 1: 1 to obtain the self-repairing anticorrosive paint.
Example 4
1. Preparation method of filler of metal organic framework compound loaded with corrosion inhibitor
1) 0.005mol of cobalt chloride hexahydrate (CoCl)2·6H2O) is dissolved in 100mL deionized water, 10mL of aqueous solution containing 0.01mol of hexamethylenetetramine is slowly dripped under the condition of stirring at room temperature, the mixture is continuously stirred for 30 minutes, then 0.006 mol of terephthalic acid is added, the mixture is uniformly stirred and dispersed, the mixture is transferred into a polytetrafluoroethylene reaction kettle, the reaction kettle is sealed and placed in a 180 ℃ oven for reaction for 72 hours, the reaction is stopped, the solid in the reaction kettle is filtered, and the filter cake is dried for 12 hours at 100 ℃ to obtain the metal organic framework compound hmt-MOF。
2) Dispersing 1 g of hmt-MOF in 30 mL of mixed solvent of deionized water and ethanol (v: v = 1: 1) at room temperature, adding 0.1 g of 2-methylimidazole under the stirring condition, continuing stirring for 16h, standing for a period of time, filtering, washing a filter cake with absolute ethyl alcohol and distilled water in sequence, and drying in vacuum at 60 ℃ to obtain the metal organic framework compound supported corrosion inhibitor MOF-in.
2. Preparation of self-repairing anticorrosive coating
1) 100g of epoxy resin E-51, 5g of MOF-in, 10 g of coupled fumed silica, a mixed solvent of 33.5 g of ethanol and n-butanol (v: v = 1: 1) and 1.5 g of BYK-055 antifoaming agent were dispersed in a dispersion machine at high speed for 10 minutes at room temperature, and then filtered to prepare a component A.
2) Mixing 650 g of low molecular polyamide and 39 g of mixed solvent of N-butanol and N-methyl-2-pyrrolidone (v: v = 1: 1.5) at room temperature, and stirring to obtain component B.
3) When in use, the A, B two components are uniformly stirred and mixed according to the mass ratio of 1: 1 to obtain the self-repairing anticorrosive paint.
Example 5
1. Preparation method of filler of metal organic framework compound loaded with corrosion inhibitor
1) 0.005mol of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) is dissolved in 100mL of deionized water, 10mL of aqueous solution containing 0.01mol of hexamethylenetetramine is slowly dripped under the condition of stirring at room temperature, the stirring is continued for 30 minutes, then 0.007 mol of terephthalic acid is added, the mixture is uniformly stirred and dispersed, the mixture is transferred into a polytetrafluoroethylene reaction kettle, the reaction kettle is sealed and placed in an oven at 170 ℃ for reaction for 66 hours, the reaction is stopped, the solid in the reaction kettle is filtered, and the filter cake is dried for 12 hours at 100 ℃, so that the metal organic framework compound hmt-MOF is obtained.
2) Dispersing 1 g of hmt-MOF in 30 mL of mixed solvent of deionized water and ethanol (v: v = 1: 1) at room temperature, adding 0.08 g of 2-methylimidazole under the stirring condition, continuing stirring for 20 h, standing for a period of time, filtering, washing a filter cake with absolute ethyl alcohol and distilled water in sequence, and drying in vacuum at 60 ℃ to obtain the metal organic framework compound supported corrosion inhibitor MOF-in.
3) Preparation of self-repairing anticorrosive coating
1) 100g of epoxy resin E-51, 4 g of MOF-in, 11 g of coupled fumed silica, 34 g of a mixed solvent of ethanol and n-butanol (v: v = 1: 1) and 1 g of BYK-055 antifoaming agent were dispersed in a dispersion machine at a high speed for 10 minutes at room temperature, and then filtered to prepare a component A.
2) Mixing 650 g of low molecular polyamide and 35g of mixed solvent of N-butanol and N-methyl-2-pyrrolidone (v: v = 1: 1.5) at room temperature, and stirring to obtain component B.
3) When in use, the A, B two components are uniformly stirred and mixed according to the mass ratio of 1: 1 to obtain the self-repairing anticorrosive paint.
Second, performance detection
In order to research the performance of the self-repairing anticorrosive coating provided by the invention, the self-repairing anticorrosive coatings prepared in the embodiments 1 to 5 are sprayed on the tinplate substrate in a spraying mode, then the self-repairing anticorrosive coatings are respectively cured for 4 hours at the temperature of 45 to 65 ℃, the thickness of the coatings is 60 +/-5 microns, and then the performance of the obtained anticorrosive coatings is tested.
And (3) adhesive force detection: the adhesion of the anticorrosive coatings obtained in examples 1-5 was determined according to GB/T9286-1998, and the test results are shown in Table 1.
And (3) flexibility detection: the corrosion-resistant coatings obtained in examples 1 to 5 were tested for flexibility according to GB/T1731-1993, and the test results are shown in Table 1.
And (3) impact resistance detection: the anticorrosive coatings obtained in examples 1-5 were tested for impact resistance according to GB/T1732-1993, and the test results are shown in Table 1.
And (3) neutral salt spray resistance detection: the neutral salt spray resistance of the anticorrosive coatings obtained in examples 1-5 was determined according to GB/T10125-.
Acid mist resistance detection: the anti-corrosion coatings obtained in examples 1-5 were tested for acetate fog resistance according to GB/T10125-.
And (3) alkali resistance detection: the sodium hydroxide solution resistance of the anticorrosive coatings obtained in examples 1-5 was determined according to the method GB 9274-1988, and the test results are shown in Table 1.
And (3) detecting the aging resistance: the anti-corrosion coatings obtained in examples 1-5 were tested for aging resistance according to GB/T1865-2009, the test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the coating prepared by the invention has good storage stability, and the coating has the characteristics of good adhesion, high flexibility, impact resistance, salt mist resistance and strong aging resistance. And the high self-repairing function can be kept for a long time in an acid-base environment, the conditions that the self-repairing function of the traditional anticorrosive coating and the common self-repairing anticorrosive coating in the environment is rapidly attenuated and the like are avoided, and the anti-corrosion performance is greatly high.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (8)
1. The filler of the MOF supported corrosion inhibitor is characterized by being prepared by the following steps:
1) dissolving a transition metal salt in water to obtain a transition metal salt solution, slowly dropwise adding the transition metal salt solution into an aqueous solution of hexamethylenetetramine under the condition of stirring at room temperature, continuously stirring, then adding terephthalic acid, uniformly stirring and dispersing, transferring into a reaction kettle, sealing, placing into an oven for reacting for a certain time, stopping the reaction, filtering solids in the reaction kettle, and drying the obtained filter cake to obtain a metal organic framework compound hmt-MOF;
2) dispersing hmt-MOF prepared in the step 1) in a mixed solvent at room temperature, adding a corrosion inhibitor under stirring, continuously stirring for 10-20 h, standing for a period of time, washing a filter cake obtained by filtering with absolute ethyl alcohol and distilled water in sequence, and drying in vacuum at 60 ℃ to obtain a filler of a metal organic framework compound loaded with the corrosion inhibitor; the corrosion inhibitor is an amino corrosion inhibitor;
the mass ratio of the hexamethylene tetramine to the terephthalic acid to the transition metal salt is 2: 1-1.5: 1;
the transition metal salt is selected from one or more of copper nitrate, copper chloride, nickel nitrate, nickel chloride, cobalt nitrate and cobalt chloride; the concentration of the transition metal salt solution is 0.04-0.06 mol/L.
2. The filler of the MOF supported corrosion inhibitor according to claim 1, wherein the reaction temperature in the step 1) is 150-180 ℃, and the reaction time is 48-72 hours; the drying temperature is 100 ℃, and the drying time is 12 h.
3. The MOF corrosion inhibitor-loaded filler according to claim 1, wherein the mixed solvent is a mixed solution of deionized water and ethanol in equal volume ratio; the mass-volume ratio of the hmt-MOF to the mixed solvent is 1 g: 20-40 mL; the corrosion inhibitor is one or the combination of two of hexamethylenetetramine and methylimidazole; the mass ratio of the hmt-MOF to the corrosion inhibitor is 1: 0.02-0.1.
4. Use of a filler of an MOF-supported corrosion inhibitor according to any one of claims 1 to 3 in an anticorrosive coating.
5. The self-repairing anticorrosive coating is characterized by comprising a component A and a component B in equal mass ratio, wherein the component A comprises the following components in parts by mass: 100 parts of a film forming material, 1-5 parts of a filler of the MOF-supported corrosion inhibitor of any one of claims 1-3, 5-15 parts of an inorganic filler, 20-40 parts of a diluent A and 0.5-1.5 parts of a defoamer; the component B comprises a curing agent and a diluent B, and the mass ratio of the curing agent to the diluent B is 1: 0.3-0.5.
6. The self-repairing anticorrosive coating according to claim 5, wherein the film-forming substance is epoxy resin E-51, and the epoxy value is 0.48-0.54 mol/100 g; the inorganic filler is coupled gas phase white carbon black; the diluent A is a mixed solvent of ethanol and n-butanol; the defoaming agent is a commercially available BYK-055 defoaming agent; the curing agent is 650 low-molecular-weight polyamide, the amine value is 220 +/-20 mg KOH/g, the viscosity is 15000-20000 mPa & s at 40 ℃, and the equivalent weight of active hydrogen is 195; the diluent B is a mixed solvent of N-butanol and N-methyl-2-pyrrolidone, and the volume ratio of the N-butanol to the N-methyl-2-pyrrolidone in the diluent B is 1: 1.5.
7. A method of making a self-healing anticorrosion coating as recited in claim 5 or 6, comprising: and mixing the film-forming material, the filler of the MOF loaded corrosion inhibitor, the inorganic filler, the diluent A and the defoaming agent to form a component A, and then uniformly mixing and stirring the component A and a component B consisting of the curing agent and the diluent B to obtain the self-repairing anticorrosive coating.
8. The self-repairing anticorrosive coating formed by curing the self-repairing anticorrosive coating of claim 5 or 6 at 45-65 ℃ for 3-5 hours.
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| CN113105719B (en) * | 2021-04-21 | 2022-10-25 | 深圳市鑫荣进绝缘材料有限公司 | Environment-friendly flame-retardant high-thermal-conductivity metal-based copper-clad plate |
| CN115806765A (en) * | 2021-09-14 | 2023-03-17 | 中国石油化工股份有限公司 | Nano catalytic anticorrosive coating and preparation method thereof |
| CN113999588A (en) * | 2021-10-29 | 2022-02-01 | 合肥工业大学 | Sintered NdFeB magnet surface corrosion-resistant composite coating and preparation method thereof |
| CN113913045B (en) * | 2021-11-25 | 2022-10-14 | 江苏科技大学 | 2-chloromethyl benzimidazole-loaded MIL-88 material and preparation method thereof |
| CN114292413B (en) * | 2021-12-31 | 2023-10-27 | 贵州乌江水电开发有限责任公司思林发电厂 | Preparation method and application of self-repairing material based on aromatic carboxylic acid MOFs |
| CN114133840B (en) * | 2022-01-04 | 2022-08-05 | 中国科学院金属研究所 | ZIF-L-based epoxy resin composite coating, preparation method and coating product |
| CN114539870B (en) * | 2022-01-06 | 2023-03-31 | 内江师范学院 | Self-healing coating based on covalent organic framework material and preparation method thereof |
| CN114481136B (en) * | 2022-01-11 | 2023-08-22 | 内江师范学院 | Vapor phase corrosion inhibitor based on metal organic framework material and preparation method thereof |
| CN114686085B (en) * | 2022-04-02 | 2023-11-03 | 山东科技大学 | Corrosion self-diagnosis coating based on ion exchange and preparation method thereof |
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