CN112679749A - Zeolite-like zinc-based imidazole ester metal organic framework reinforcing steel bar corrosion inhibitor and preparation method and application thereof - Google Patents
Zeolite-like zinc-based imidazole ester metal organic framework reinforcing steel bar corrosion inhibitor and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of reinforcing steel bar rust inhibitors for concrete engineering and discloses a zeolite-zinc-based imidazole ester metal organic framework reinforcing steel bar rust inhibitor and a preparation method and application thereof, wherein zinc ions are used as metal nodes and form the zeolite-zinc-based imidazole ester reinforcing steel bar rust inhibitor by coordination self-assembly with imidazole organic ligands, wherein the MOFs of the zeolite-zinc-based imidazole ester has the structural formula:
wherein R is one of methyl, nitryl and formyl. The invention utilizes the advantages of zeolite-like zinc-based imidazole ester MOFs (metal-organic frameworks) such as high chemical stability under the high-alkalinity condition of concrete, strong adsorption on the surface of a reinforcing steel bar, large hydrophobicity after adsorption film forming and the like, and can be used for treating steel in the concreteThe ribs have high-efficiency rust resistance.
Description
Technical Field
The invention belongs to the field of reinforced concrete rust inhibitors, and particularly relates to a zeolite-like zinc-based imidazole ester metal organic framework steel bar rust inhibitor, and a preparation method and application thereof.
Background
Reinforced concrete is widely applied to the field of construction engineering, but when external aggressive media (especially chloride ions) permeate to the surface of the steel bars through a concrete porous structure and are accumulated, the steel bars in the concrete are corroded and damaged, and the accumulation of corrosion products can further cause the cracking and peeling of the concrete, so that the durability of the reinforced concrete structure is seriously reduced. The organic steel bar rust inhibitor is added into the fresh concrete, is considered as the most economic and efficient technical means for inhibiting the corrosion of the steel bars in the concrete and has the strongest operability, and is widely applied to the field of engineering construction. However, the traditional organic steel bar rust inhibitor has low rust inhibition efficiency, can generate negative effects on the performance of concrete materials and has certain toxicity, so that a novel efficient and environment-friendly organic steel bar rust inhibitor suitable for reinforced concrete is urgently needed.
The Metal Organic Frameworks (MOFs) material is a novel porous crystalline hybrid material, and a regular network structure is formed by coordination and outward topology of metal ions (clusters) serving as nodes and an organic connector. Because MOFs have the unique advantages of supermolecular structure, high porosity, large specific surface area, adjustable pores and the like, MOFs are widely applied to the fields of energy conversion, adsorption separation, molecular transmission and the like. The zeolite-like zinc-based imidazole ester MOFs has the characteristics of stable structure, strong hydrophobicity, environmental friendliness, harmlessness, large content of pi electron systems and other strong adsorption sites, so that the requirement of the construction engineering field on the steel bar rust inhibitor in concrete can be met by regulating the appearance and the size of the material. Lai et al (doi:10.4028/www.scientific.net/AMM.773-774.1133) prepare zeolite-like zinc-based imidazole ester MOFs by a solvothermal synthesis method, but the crystal particle size obtained by the method is too large (about 1 μm), the requirement of strong adsorbability is difficult to meet, and meanwhile, the use of a large amount of non-aqueous solvent does not accord with the development direction of green chemistry; in addition, no relevant report that zeolite-like zinc-based imidazole ester MOFs serving as a steel bar rust inhibitor is applied to the field of concrete is found at present.
Disclosure of Invention
Aiming at the problems that the existing reinforced concrete rust inhibitor has low rust inhibition efficiency, can generate negative influence on the performance of concrete materials and has certain toxicity, the invention aims to provide the zeolite-like zinc-based imidazole ester metal organic framework (MOFs type) reinforced steel rust inhibitor and the preparation method and the application thereof.
In order to achieve the aim, the invention provides a steel bar rust inhibitor based on MOFs, which is characterized in that a zeolite-like zinc-based imidazole ester MOFs material is dried and ground to obtain a powdery steel bar rust inhibitor, the powdery steel bar rust inhibitor is stored in a sealed manner, the powder is weighed according to needs before use and is added into a cementing material for concrete and fully pre-stirred, and then the powdery steel bar rust inhibitor is co-stirred with other raw materials.
The zeolite zinc-based imidazole ester metal organic framework reinforcing steel bar rust inhibitor has a structural formula shown as the following formula,
and R is one of methyl, nitro and formyl.
The invention provides a preparation method of the zeolite-like zinc-based imidazole ester metal organic framework reinforcing steel bar rust inhibitor, which comprises the following steps:
reacting zincate and imidazole organic ligand as raw materials to generate zeolite-like zinc-based imidazole ester MOFs shown as the following formula:
r is one of methyl, nitro and formyl; in addition, the molar ratio of zinc ions to imidazole organic ligands in the raw materials meets 1: 60-80;
further, the reaction is specifically that a zincate and an imidazole organic ligand are respectively dissolved in corresponding solvents, before the reaction starts, the concentration of zinc ions in a solution system is controlled to be 0.04-0.05 mol/L, the zincate solution is dropwise added into the imidazole organic ligand solution, and the mixture is continuously stirred and reacted for 23-25 hours at 25-27 ℃ to obtain a mixed solution containing the zeolite-zinc-based imidazole ester metal organic framework steel bar rust inhibitor;
further, the mixed solution is placed in a high-speed centrifuge to be centrifuged for 10-15 minutes at the rotating speed of 8000-10000 rpm, and finally, the product is washed for 3-4 times by using a corresponding solvent and is placed in a vacuum drying oven at the temperature of 100-120 ℃ to be dried for 6-10 hours. Wherein, in order to implement the development idea of green chemistry, the solvent is deionized water.
Further, the zinc compound is at least one of zinc sulfate, zinc acetate and zinc nitrate; the imidazole organic ligand is as follows:
wherein R is one of methyl, nitryl and formyl.
Furthermore, the MOFs size of the obtained zeolite-like zinc-based imidazole ester is 80-120 nm, and the mechanical property of a standard cement mortar test piece is not affected.
The invention provides an application of zeolite-like zinc-based imidazole ester MOFs materials in a steel bar rust inhibitor; the material can efficiently delay the occurrence of the corrosion of the steel bar in the concrete, and has the advantages of simple and convenient synthesis process, good chemical stability, high corrosion resistance efficiency, environmental protection and no toxicity.
Further, the zeolite-like zinc-based imidazole ester MOFs material is dried and ground to obtain a powdery reinforcing steel bar rust inhibitor, the powdery reinforcing steel bar rust inhibitor is stored in a sealed manner, the powder is weighed according to needs before use and is added into a cementing material for concrete, the mixture is fully pre-stirred, and then the mixture is co-stirred with other raw materials.
Further, the addition amount of the zeolite-like zinc-based imidazole ester metal organic framework steel bar rust inhibitor in the concrete is 0.1-0.4 wt%
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention also provides zeolite-like zinc-based imidazole ester MOFs and a cementing material for concrete, which are fully pre-stirred when in use, aiming at fully utilizing the stacking gaps among the cementing materials to ensure that the rust inhibitor is uniformly dispersed in a concrete matrix as much as possible, and deionized water is utilized to replace a common organic solvent as a solvent to synthesize the zeolite-like zinc-based imidazole ester MOFs, mainly considering the environmental requirements of environmental protection and no toxicity; secondly, the selection of normal temperature and normal pressure water phase reaction conditions, rather than hydrothermal, solvothermal and other high temperature and high pressure reaction conditions, is also based on the economic aspect of simplifying the synthesis process.
Besides selecting zinc salts from various metal-containing salts, the invention also controls the proportion of a reactant zinc salt and an imidazole organic ligand adopted by the synthesis process of the zeolite-like zinc-based imidazole ester, controls the molar ratio of zinc ions to the imidazole organic ligand in the raw materials to be 1: 60-80, and controls the concentration of the zinc ions to be 0.04-0.05 mol/L, thereby obtaining the MOFs material shown in the following formula.
the invention further performs optimal control on the amount of a solvent in the synthesis of the zeolite-like zinc-based imidazole ester MOFs, specific parameter conditions of a water phase reaction and the like, successfully obtains the zeolite-like zinc-based imidazole ester MOFs, and simultaneously further ensures that the particle size of the MOFs is appropriate (80-120 nm), so that the mechanical property of the concrete is not negatively influenced. According to the invention, a zincate and an imidazole organic ligand are used as raw materials, deionized water is used as a solvent to carry out normal-temperature normal-pressure water phase reaction, the continuous stirring time is preferably controlled to be 23-25 hours, then the mixture is centrifuged for 10-15 minutes in a high-speed centrifuge at 10000rpm, finally the product is washed for 3-4 times by the deionized water and is put into a vacuum drying oven at 100-120 ℃ to be dried for 6-10 hours, and the zeolite-like zinc-based imidazole esters MOFs with high-efficiency rust resistance are obtained. The reason why the zincate solution is dropwise added into the imidazole organic ligand solution is to enable the two reactant raw materials to fully react, and the reason why the reaction is continued for 23-25 hours in a stirring state is to enable the size of the obtained MOFs product to be uniformly distributed on the premise of keeping continuous growth, so that the finally obtained crystal is appropriate in size.
The reinforced concrete corrosion inhibitor takes zeolite-like zinc-based imidazole ester MOFs as a main component, can effectively inhibit corrosion damage of chloride ions in concrete pore liquid to reinforcing steel bars, has small usage amount (the usage amount of the corrosion inhibitor in the concrete simulated pore liquid can be as low as 100ppm), and has the characteristics of high-efficiency corrosion inhibition, environmental protection and simple operation. The reinforced concrete corrosion inhibitor has high thermal stability, can be used under different temperature conditions, has no influence on the structure due to the temperature rise effect generated by hydration and heat release of cement in concrete, and has no adverse effect on the mechanical property of the concrete.
Drawings
FIG. 1 is a scanning electron microscope image of the zeolite-like zinc-based imidazole ester MOFs reinforcing steel bar rust inhibitor of example 1.
FIG. 2 is the standard compressive strength of cement mortar after 7 days and 28 days of steel reinforcement corrosion inhibitor internally doped with 0.2 wt.% of the zeolite-zinc-based imidazolate MOFs of example 1, measured according to the national Standard GB/T17671.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In summary, the rust inhibitor in the invention is composed of powder after drying and grinding zeolite-like zinc-based imidazole ester MOFs, and is dispersed by matching with a cementing material for concrete.
The reaction in the preparation process of the rust inhibitor is as follows:
the following are specific examples.
Example 1
5.95g of zinc nitrate is dissolved in 46mL of deionized water, 114.8g of 2-methylimidazole is dissolved in 400mL of deionized water in two beakers respectively, then the zinc nitrate solution is dripped into the 2-methylimidazole solution drop by drop, the mixture is stirred and reacted for 24 hours at 25 ℃, then the mixed solution is placed in a high-speed centrifuge to be centrifuged for 10 minutes at 10000rpm, finally, the product is washed for 3 times by corresponding solvent and is placed in a vacuum drying box at 105 ℃ to be dried for 8 hours, and the product is taken out and fully ground to obtain the powdery zeolite zinc-based imidazole ester MOFs rust inhibitor.
FIG. 1 is a scanning electron microscope morphology of the zeolite-like zinc-based imidazole ester MOFs steel bar corrosion inhibitor prepared according to the steps, and the particle size range of the zeolite-like zinc-based imidazole ester MOFs steel bar corrosion inhibitor is 80-120 nm.
Performance evaluation of the rust inhibitor:
the invention adopts an alternating current impedance spectroscopy electrochemical method to characterize the rust resistance performance, and the experimental test method is based on the following standards: ISO 16773-4, Electrochemical Impedance Spectroscopy (EIS) of paint and varnish-high-resistance coating samples (electrochemical impedance Spectroscopy experiments determine the rust-inhibiting efficiency).
The experimental material is Q235 building plain steel bar; the rust-resisting medium is the zeolite-like zinc-based imidazole ester MOFs steel bar rust inhibitor prepared in the embodiment 1, and the addition amount is 100-400 ppm; the experimental environment is a concrete simulated pore solution added with 3.5 wt.% of sodium chloride (the concrete simulated pore solution used in the following experiments is a cement leaching solution obtained by mixing P.O 42.5.5 cement and deionized water according to the mass ratio of 1:1 and oscillating for 24 hours), and the dosage is 100 mL; the steel bar electrode was immersed in the above-described ambient medium at an experimental temperature of 25 ℃, pH 12.8, and for 24 hours. The reinforced concrete rust inhibitor of the invention is used for obtaining the rust inhibition efficiency through experimental tests according to the given determination mode, and the result is shown in table 1;
TABLE 1
As can be seen from the experimental data in table 1, in the above evaluation system, the corrosion inhibitor of the present invention has a significant inhibition effect on corrosion of steel bars;
and according to the determination of national standard GB/T17671, when the content of the zeolite-like zinc-based imidazole ester MOFs steel bar rust inhibitor is 0.2 wt.%, the standard compressive strength of the cement mortar in 7 days and 28 days is equivalent to the standard compressive strength of the steel bar rust inhibitor sample (shown in figure 2), which indicates that the zeolite-like zinc-based imidazole ester MOFs steel bar rust inhibitor has no adverse effect on the mechanical properties of concrete.
Example 2
The present embodiment is the same as embodiment 1 except for the following features;
in the preparation process of the zeolite-like zinc-based imidazole ester MOFs rust inhibitor, the molar ratio of zinc ions to 2-nitroimidazole satisfies 1: 60; before the reaction starts, the concentration of zinc ions in a solution system is controlled to be 0.05 mol/L; after mixing, the reaction was continued with stirring for 25 hours.
The test results of this example are similar to example 1.
Example 3
The present embodiment is the same as embodiment 1 except for the following features;
in the preparation process of the zeolite-like zinc-based imidazole ester MOFs rust inhibitor, the molar ratio of zinc ions to 2-formylimidazole satisfies 1: 80; before the reaction starts, the concentration of zinc ions in a solution system is controlled to be 0.04 mol/L; after mixing, the reaction was continued for 23 hours with stirring.
The test results of this example are similar to example 1.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The zeolite-like zinc-based imidazole ester metal organic framework reinforcing steel bar rust inhibitor is characterized by having a structural formula shown as the following formula,
and R is one of methyl, nitro and formyl.
2. The method for preparing the zeolite-like zinc-based imidazole ester metal organic framework steel bar rust inhibitor of claim 1,
the zinc compound and the imidazole organic ligand are used as raw materials to react to generate the zeolite-like zinc-based imidazole ester metal organic framework steel bar rust inhibitor shown as the following formula:
r is one of methyl, nitro and formyl; and the molar ratio of the zinc ions to the imidazole organic ligands in the raw materials meets 1: 60-80.
3. The preparation method according to claim 2, wherein the reaction is specifically to dissolve the zincate and the imidazole organic ligand in corresponding solvents respectively, before the reaction starts, the concentration of zinc ions in a solution system is controlled to be 0.04-0.05 mol/L, the zincate solution is dropwise added into the imidazole organic ligand solution, and the mixture containing the zeolite-like zinc-based imidazole ester metal organic framework steel bar rust inhibitor is obtained by continuously stirring and reacting for 23-25 hours at 25-27 ℃.
4. The preparation method according to claim 3, wherein the mixed solution is placed in a high speed centrifuge and centrifuged at 8000-10000 rpm for 10-15 minutes, and finally the product is washed 3-4 times with corresponding solvent and dried in a vacuum drying oven at 100-120 ℃ for 6-10 hours.
5. The preparation method according to claim 2, wherein the zinc compound is at least one of zinc sulfate, zinc acetate and zinc nitrate; the imidazole organic ligand is as follows:
and R is one of methyl, nitro and formyl.
6. The preparation method according to claim 3, wherein the solvent used in the reaction is deionized water.
7. The preparation method of claim 2, wherein the obtained zeolite-like zinc-based imidazole ester metal organic framework steel bar rust inhibitor has a size of 80-120 nm.
8. The application of the zeolite-like zinc-based imidazole ester metal organic framework steel bar rust inhibitor in claim 1 in steel bar rust inhibition.
9. The application of claim 8, wherein the zeolite zinc-based imidazole ester metal organic framework steel bar rust inhibitor is dried and ground to obtain a powdery steel bar rust inhibitor, the powdery steel bar rust inhibitor is hermetically stored, the powder is weighed according to needs before use, is added into a cementing material for concrete and is fully pre-stirred, and then is co-stirred with other raw materials.
10. The application of claim 8, wherein the zeolite-like zinc-based imidazole ester metal organic framework steel bar rust inhibitor is added into the concrete in an amount of 0.1-0.4 wt.%.
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