CN114292413A - Preparation method and application of self-repairing material based on aromatic carboxylic acids MOFs - Google Patents
Preparation method and application of self-repairing material based on aromatic carboxylic acids MOFs Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 55
- -1 aromatic carboxylic acids Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 95
- 239000011248 coating agent Substances 0.000 claims abstract description 86
- 238000005260 corrosion Methods 0.000 claims abstract description 47
- 230000007797 corrosion Effects 0.000 claims abstract description 45
- 239000013099 nickel-based metal-organic framework Substances 0.000 claims abstract description 44
- 239000003446 ligand Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003112 inhibitor Substances 0.000 claims abstract description 31
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 27
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- 239000012964 benzotriazole Substances 0.000 claims description 63
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 48
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 27
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 23
- 239000010962 carbon steel Substances 0.000 claims description 23
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
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- 241000080590 Niso Species 0.000 claims description 13
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 13
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003973 paint Substances 0.000 claims description 12
- YIAGLTIEICXRQF-UHFFFAOYSA-N 2,5-bis(trifluoromethyl)terephthalic acid Chemical compound OC(=O)C1=CC(C(F)(F)F)=C(C(O)=O)C=C1C(F)(F)F YIAGLTIEICXRQF-UHFFFAOYSA-N 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 239000008393 encapsulating agent Substances 0.000 claims description 8
- VUTICWRXMKBOSF-UHFFFAOYSA-N 2,5-dibromoterephthalic acid Chemical compound OC(=O)C1=CC(Br)=C(C(O)=O)C=C1Br VUTICWRXMKBOSF-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a preparation method and application of a self-repairing material based on aromatic carboxylic acids MOFs, belonging to the technical field of preparation of self-repairing materials, wherein the self-repairing material based on the aromatic carboxylic acids MOFs consists of a packaging agent, a corrosion inhibitor and Ni-MOFs formed by nickel salt and a ligand; the BTA/Ni-MOFs @ TEOS self-repairing material is used as an auxiliary agent, is applied to a water-based acrylic resin coating, and can greatly improve the corrosion resistance and the self-repairing performance of the coating.
Description
Technical Field
The invention belongs to the technical field of self-repairing material preparation, and particularly relates to a preparation method and application of a self-repairing material based on aromatic carboxylic acids MOFs.
Background
At present, the simplest and most effective method for corrosion protection of carbon steel is to coat an organic coating on the surface of the carbon steel. However, the organic coating has the problems of easy cracking, weak mechanical resistance and poor dispersion stability. The addition of some additives to self-healing coatings is an important means to solve these problems. Therefore, in order to prolong the service life of the self-repairing coating, researchers at home and abroad add some self-repairing additives into the coating to develop the self-repairing coating, and the self-repairing performance of the coating can improve the anti-corrosion performance of the coating and prolong the service life. The resin in the self-repairing coating has no self-repairing function, a corrosion inhibitor needs to be coated in a carrier (such as carbon nano tubes, inorganic nano particles, micro/nano capsules, MOFs materials and the like) and added into the coating, and when the coating is stimulated by the outside (such as pH, light, pressure, heat and the like), the corrosion inhibitor is released from a damaged area, so that the damaged coating is repaired.
The substances commonly used as the carriers for loading the corrosion inhibitor at present have some defects. The carbon nano tube has higher specific surface area and good stability, but the defects of nonuniform growth, difficult length control and generation of a large amount of impurities which are difficult to remove often exist in the preparation process, and the stability of the coating is not high often caused by adding the carbon nano tube as a carrier of the self-repairing coating. The inorganic nano particles are not easy to disperse in the coating and are easy to precipitate, so that the weather resistance of the coating is poor, and the coating is easy to age and turn yellow. The preparation process of the microcapsule is complex, the prepared microcapsule has larger size which is usually higher than the nanometer level, so that the microcapsule is not matched with the pores of the coating, the surface is not uniform, the coating is easy to crack, the performance is damaged, the preparation process of the nanocapsule is rigorous and complex, the manufacturing cost is higher, and although the nanocapsule has smaller size, the nanocapsule has many difficulties in preparing the self-repairing coating by using the nanocapsule as a carrier for loading the corrosion inhibitor. The nanoscale MOFs has good compatibility with the coating, is not easy to agglomerate, has good dispersibility, and is an ideal carrier. The MOFs material forms a coordination chemical bond with a metal substrate in the coating, so that the adhesion and water resistance of the coating are enhanced; therefore, the MOFs material is an ideal carrier of the self-repairing coating and is also a better corrosion inhibitor or corrosion prevention aid. In particular, the heterocyclic carboxylic group MOFs material can form a coordination bond with a metal substrate and can be better adsorbed to the metal surface. Compared with other corrosion inhibition aids, the MOFs material not only has the advantages of the traditional inorganic material (such as high porosity, thermal stability and the like), but also has the characteristics of a novel composite material (such as good reaction selectivity and strong loading capacity). At present, the anticorrosive paint in China develops rapidly, the VOC emission can be greatly reduced by the water-based paint, and the method is an important target for popularizing the production field of green paint.
The water-based acrylic resin (PAA) has the advantages of good weather resistance, ultraviolet irradiation resistance and difficult decomposition, pulverization or yellowing of the surface, and is an environment-friendly and low-cost water-based paint. However, in the curing process of the coating, micro-pores and micro-cracks are generated on the surface of the coating due to the evaporation of the solvent, thereby shortening the life of the coating and causing economic loss. Meanwhile, the corrosion inhibitor is directly mixed with the coating, and the integrity of the coating is damaged by the strong interaction between the corrosion inhibitor and the coating, so that the protective capability of the coating is damaged.
The MOFs material is a carrier with a specific pore structure formed by mutually connecting metal or metal oxide clusters and organic ligands, has good loading capacity and is better in compatibility with matrix resin. On one hand, due to the existence of unsaturated metal sites, the MOFs material can coordinate with hydroxyl and carboxyl in matrix resin of the self-repairing coating, and a coordination chemical bond is formed between the MOFs material and a metal substrate in the coating, so that the adhesion and water resistance of the coating are enhanced; on the other hand, the MOFs material has enough capacity to encapsulate the corrosion inhibitor and has the ability to control the release of the corrosion inhibitor, so that the MOFs material is an ideal carrier of a self-repairing coating and is also a better corrosion inhibitor or corrosion prevention aid. At present, many documents report on the construction of self-repairing coatings by using self-repairing materials, but the self-repairing coatings constructed by using self-repairing materials prepared from MOFs are rarely reported. Therefore, the research of the application of the MOFs-based material in the self-repairing coating has certain theoretical and practical significance.
Disclosure of Invention
The invention aims to coat Ni-MOFs loaded with corrosion inhibitors (BTA) by using an organic substance TEOS (tetraethoxysilane) sensitive to environment to prepare a self-repairing material (BTA/Ni-MOFs @ TEOS) prepared based on aromatic carboxylic acid MOFs, and then the self-repairing material is added into a water-based acrylic resin (PAA) self-repairing coating as an auxiliary agent to prepare a super-hydrophobic BTA/Ni-MOFs @ TEOS/PAA self-repairing coating, so that the corrosion resistance and the self-repairing capability of the coating are improved.
The technical scheme of the invention is as follows:
the self-repairing material based on the aromatic carboxylic acid MOFs comprises an encapsulant, a corrosion inhibitor and Ni-MOFs formed by nickel salt and a ligand;
wherein the packaging agent is one or two of Tetraethoxysilane (TEOS) and polyurea formaldehyde (PUF);
wherein the corrosion inhibitor is one or more of Benzotriazole (BTA), Polydimethylsiloxane (PDMS) and 2-Mercaptobenzimidazole (MBI);
the ligand comprises a main ligand and an auxiliary ligand, wherein the main ligand is one or two of 2, 5-bis (trifluoromethyl) terephthalic acid and 2, 5-dibromoterephthalic acid, and the auxiliary ligand is 1, 10' -phenanthroline.
That is to say that the position of the first electrode,
the combination of ligands may be 2, 5-bis (trifluoromethyl) terephthalic acid and 1, 10' -phenanthroline;
the combination of the ligands can be 2, 5-dibromoterephthalic acid and 1, 10' -phenanthroline;
the combination of ligands can also be 2, 5-bis (trifluoromethyl) terephthalic acid, 2, 5-dibromoterephthalic acid, 1, 10' -phenanthroline.
As a preferred solution, the ratio of primary ligand to secondary ligand is 1: 1;
the invention also discloses a preparation method of the self-repairing material based on the aromatic carboxylic acids MOFs, which specifically comprises the following steps:
(1) taking nickel sulfate hexahydrate (NiSO)4·6H2O) and a ligand are placed in a container, then a first solvent is added, the mixture is stirred uniformly, then the mixture is heated to 90-140 ℃, the reaction time is more than 8 hours, and then the mixture is cooled to room temperature, so that Ni-MOFs are obtained;
wherein the temperature can be selected from any temperature within the range of 90-140 ℃, such as 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃ and 140 ℃.
The reaction time may be any time within the range, for example, 8h, 9h, 10h, 11h, 12h, 13h, 15h, 20h, 21h, 24h, 25h, 28h, 30h, 35h, and the like.
(2) Taking Ni-MOFs, a corrosion inhibitor and absolute ethyl alcohol, stirring and reacting for 3-10 hours in a container, and then adding H into the solution2And O, dropwise adding a sodium hydroxide solution (NaOH), adjusting the pH value of the solution to be 8-9, adding an ethanol solution containing 15-25% of an encapsulant for 1-3 times at intervals of 10-60 min each time, continuously stirring the solution in the process, stirring the mixed solution for more than 8 hours after the addition is finished, centrifuging the mixed solution, washing the mixed solution with absolute ethanol for multiple times, drying and grinding the washed solution to obtain the self-repairing material (BTA/Ni-MOFs @ TEOS).
Further, the air conditioner is provided with a fan,
in the step (1), the nickel sulfate hexahydrate (NiSO)4·6H2O) and preparationBodyThe molar ratio of (2-3): 2;
further, in the step (1), the nickel sulfate hexahydrate (NiSO)4·6H2O) and ligand in a molar ratio of 1: 1;
in the step (1), the ratio of the ligand to the first solvent is 0.02-0.3 mol/L;
further, in the step (1), the ratio of the ligand to the first solvent is 0.1 mol/L;
in the step (1), the first solvent is a mixed solution of N, N-Dimethylformamide (DMF) and distilled water;
further, in the step (1), the volume ratio of the N, N-Dimethylformamide (DMF) to the distilled water is 3: 2.
further, the reaction temperature in the step (1) is 100-130 ℃;
further, the reaction temperature in the step (1) is 110 ℃;
in the step (1), the heating rate is 7-15 ℃ h-1；
Further, the temperature rise rate in the step (1) is 10 ℃ h-1；
The reaction time in the step (1) is 20-30 h;
further, the reaction time in step (1) is 24 h.
Further, in the step (2),
the molar ratio of the Ni-MOFs to the corrosion inhibitor to the packaging agent is (10-30): (80-120): (4: 8);
further, the molar ratio of the Ni-MOFs, the corrosion inhibitor and the packaging agent is 25: 100: 6.
further, the reaction time in the step (2) is 5-8 h;
further, the reaction time in the step (2) is 6 hours;
further, the dropping manner in the step (2) is dropwise dropping.
Further, the concentration of the sodium hydroxide solution in the step (2) is 0.5-2 mol/L;
further, the concentration of the sodium hydroxide solution in the step (2) is 1 mol/L;
in the step (2), the concentration of the ethanol solution of the packaging agent is 20 percent;
in the step (2), the number of times of adding the packaging agent is 3, and the interval is 30min each time;
further, in the step (2), after the addition was completed, the mixed solution was stirred again for 12 hours.
Further, as a preferred technical scheme, the preparation method of the self-repairing material based on the aromatic carboxylic acids MOFs comprises the following steps:
(1) 0.263g of nickel sulfate hexahydrate (NiSO) is weighed4·6H2O), 0.302g of 2, 5-bis (trifluoromethyl) terephthalic acid (H)2btftpa) and 0.180g of 1,10 '-orthophenanthroline (1, 10' -phen) were placed in a 25mL beaker and 9mL of N, N-Dimethylformamide (DMF) and 7mL of distilled water (H)2O), magnetically stirring for 40min at room temperature, pouring into a reaction kettle, putting into an oven, heating to 110 ℃, and reacting for 24 h. At 10 ℃ h-1Cooling to room temperature at the rate of (2) to obtain Ni-MOFs;
(2) 0.1g of Ni-MOFs, 0.4g of Benzotriazole (BTA) and 50mL of absolute ethyl alcohol are weighed in a beaker and stirred for reaction for 6 hours, and 10mL of H is added into the solution2And O, dropwise adding 1mol/L sodium hydroxide (NaOH) dropwise, adjusting the pH value of the solution to be between 8 and 9, adding an ethanol solution containing 20% tetraethyl silicate (TEOS) for three times, wherein the volume of the ethanol solution is 20 mu L each time, the interval is 30min each time, continuously stirring the solution in the process, stirring the mixed solution for 12h again after the addition is finished, centrifuging the mixed solution, washing the mixed solution for multiple times by using absolute ethyl alcohol, drying and grinding the washed mixed solution to obtain the self-repairing material (BTA/Ni-MOFs @ TEOS).
The invention also discloses an application of the self-repairing material based on the aromatic carboxylic acids MOFs, and the self-repairing material based on the aromatic carboxylic acids MOFs is applied to the waterborne acrylic resin coating. The self-repairing material based on the aromatic carboxylic acid MOFs is used as an auxiliary agent.
Further, the self-repairing material based on the aromatic carboxylic acid MOFs is dispersed in the aqueous acrylic resin and coated on the substrate.
Further, in the aqueous acrylic resin, the addition amount of the self-repairing material based on the aromatic carboxylic acids MOFs is 0.1-1 wt%;
further, the addition amount of the self-repairing material based on the aromatic carboxylic acid MOFs is 0.5 wt%;
further, adding the self-repairing material based on the aromatic carboxylic acid MOFs into the aqueous acrylic resin, uniformly dispersing, then adding the aqueous paint dispersing auxiliary agent into the mixed solution, uniformly stirring, then uniformly coating on the polished substrate material, and curing to obtain the self-repairing coating;
in the curing step, a curing agent can be added, and the selection and addition amount of the curing agent can refer to the curing agent commonly used in the prior art, and are not limited herein.
Further, the base material can be carbon steel, copper sheets, aluminum sheets and the like,
further, the curing time is more than 1 day;
preferably, the curing time is 4 days.
The water-based paint dispersant is not limited herein, and may be any water-based paint dispersant commonly used in the art.
The amount of the aqueous coating dispersant added is not limited herein, and may be an amount commonly used in the art.
Further, in the present invention,
adding 0.025g of BTA/MOFs @ TEOS self-repairing material into 5g of water-based acrylic resin, performing ultrasonic treatment, mixing and stirring to uniformly disperse the BTA/MOFs @ TEOS self-repairing material, then adding 10 mu L of polyamide curing agent into the mixed solution, uniformly stirring to obtain the self-repairing material (BTA/Ni-MOFs @ TEOS), uniformly coating the BTA/Ni-MOFs @ TEOS/PAA on the polished carbon steel sheet, and curing for 4 days to obtain a self-repairing coating BTA/Ni-MOFs @ TEOS/PAA.
The invention discloses a self-repairing material (BTA/Ni-MOFs @ TEOS) prepared based on aromatic carboxylic acids MOFs, which is prepared by coating Ni-MOFs loaded with a corrosion inhibitor (BTA) by using an environmentally sensitive organic matter TEOS (tetraethoxysilane), and the preparation method is simple.
The invention discloses an application of a self-repairing material (BTA/Ni-MOFs @ TEOS) based on aromatic carboxylic acids MOFs in a water-based acrylic resin coating. And the coating is used for corrosion prevention of a metal matrix, and after an anticorrosive coating is formed on the metal matrix, the coating has good stability, excellent corrosion prevention performance and strong self-repairing capability. Compared with the water-based acrylic resin as an anticorrosive coating, the anticorrosive effect is greatly improved.
Drawings
FIG. 1 is an infrared spectrum of BTA/Ni-MOFs @ TEOS self-repairing material;
FIG. 2 is an XRD diagram of a BTA/Ni-MOFs @ TEOS self-repairing material;
FIG. 3 time-potential curves for bare carbon steel and coated with PAA, Ni-MOFs/PAA, BTA/Ni-MOFs @ TEOS/PAA self-healing coatings;
FIG. 4 is a potentiodynamic polarization plot for bare carbon steel and self-healing coatings coated with PAA, Ni-MOFs/PAA, BTA/Ni-MOFs @ TEOS/PAA;
FIG. 5 is a scanning electron microscope image of a scratch area of a pure waterborne acrylic resin coating and a BTA/Ni-MOFs @ TEOS/PAA self-repairing coating after being soaked in cooling water for 30 d;
FIG. 6 EDS spectra of scratch area of pure water acrylic resin coating and BTA/Ni-MOFs @ TEOS/PAA self-repairing coating after soaking in cooling water for 30 d.
Detailed Description
The present invention is further illustrated by the following specific examples, it should be noted that, for those skilled in the art, variations and modifications can be made without departing from the principle of the present invention, and these should also be construed as falling within the scope of the present invention.
The self-repairing material based on the aromatic carboxylic acid MOFs comprises an encapsulant, a corrosion inhibitor and Ni-MOFs formed by nickel salt and a ligand;
wherein the packaging agent is one or two of Tetraethoxysilane (TEOS) and polyurea formaldehyde (PUF);
wherein the corrosion inhibitor is one or more of Benzotriazole (BTA), Polydimethylsiloxane (PDMS) and 2-Mercaptobenzimidazole (MBI);
the ligand comprises a main ligand and an auxiliary ligand, wherein the main ligand is one or two of 2, 5-bis (trifluoromethyl) terephthalic acid and 2, 5-dibromoterephthalic acid, and the auxiliary ligand is 1, 10' -phenanthroline.
That is to say that the position of the first electrode,
the combination of ligands may be 2, 5-bis (trifluoromethyl) terephthalic acid and 1, 10' -phenanthroline;
the combination of the ligands can be 2, 5-dibromoterephthalic acid and 1, 10' -phenanthroline;
the combination of ligands can also be 2, 5-bis (trifluoromethyl) terephthalic acid, 2, 5-dibromoterephthalic acid, 1, 10' -phenanthroline. As a preferred solution, the ratio of primary ligand to secondary ligand is 1: 1;
in some embodiments, the preparation method of the self-repairing material based on the aromatic carboxylic acids MOFs specifically includes the following steps:
(1) taking nickel sulfate hexahydrate (NiSO)4·6H2O) and a ligand are placed in a container, then a first solvent is added, the mixture is stirred uniformly, then the mixture is heated to 90-140 ℃, the reaction time is more than 8 hours, and then the mixture is cooled to room temperature, so that Ni-MOFs are obtained;
the temperature can be selected to be any temperature within the range of 90-140 ℃, for example, in some embodiments, the heating temperature can be selected to be 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃ and 140 ℃.
In some embodiments, the rate of temperature increase in step (1) is from 7 to 15 ℃. h-1(ii) a For example: at 7 ℃ h-1；8℃·h-1；9℃·h-1；10℃·h-1；11℃·h-1；12℃·h-1；13℃·h-1；14℃·h-1；15℃·h-1。
The reaction time may be selected to be any time within this range, for example, in some embodiments, the reaction time may be selected to be 8h, 9h, 10h, 11h, 12h, 13h, 15h, 20h, 21h, 24h, 25h, 28h, 30h, 35h, and the like.
In some embodiments, in step (1), the nickel sulfate hexahydrate (NiSO)4·6H2O) and the ligand in a molar ratio of (2-3): 2;
as a preferred technical methodIn some embodiments, in step (1), the nickel sulfate hexahydrate (NiSO)4·6H2O) and preparationBodyIn a molar ratio of 1: 1;
in some embodiments, in step (1), the ratio of the ligand to the first solvent is 0.02-0.3 mol/L;
as a preferred technical solution, in some embodiments, the ratio of the ligand to the first solvent is 0.1 mol/L;
in some embodiments, in step (1), the first solvent is a mixture of N, N-Dimethylformamide (DMF) and distilled water;
as a preferred solution, in some embodiments, the volume ratio of N, N-Dimethylformamide (DMF) to distilled water is 3: 2.
the above are merely preferred embodiments of the present invention, and are not intended to limit the present invention.
(2) Taking Ni-MOFs, a corrosion inhibitor and absolute ethyl alcohol, stirring and reacting for 3-10 hours in a container, and then adding H into the solution2And O, dropwise adding a sodium hydroxide solution (NaOH), adjusting the pH value of the solution to be 8-9, adding an ethanol solution containing 15-25% of an encapsulant for 1-3 times at intervals of 10-60 min each time, continuously stirring in the process, stirring the mixed solution for more than 8 hours again after the addition is finished, centrifuging, washing with absolute ethanol for multiple times, drying, and grinding to obtain the self-repairing material.
In some embodiments, in step (2), the molar ratio of the Ni-MOFs, the corrosion inhibitor and the encapsulant is (10-30): (80-120): (4: 8);
as a preferred solution, in some embodiments, the molar ratio of Ni-MOFs, corrosion inhibitor and encapsulant is 25: 100: 6.
in some embodiments, the reaction time in step (2) is 5-8 h; for example 5h, 6h, 7h, 8 h.
As a preference, in some embodiments, the reaction time in step (2) is 6 h;
in some embodiments, the dropwise manner in step (2) is dropwise.
In some embodiments, the concentration of the sodium hydroxide solution in the step (2) is 0.5-2 mol/L;
as a preferable mode, in some embodiments, the concentration of the sodium hydroxide solution in the step (2) is 1 mol/L;
in the step (2), the concentration of the ethanol solution of the packaging agent is 20 percent;
in the step (2), the number of times of adding the packaging agent is 3, and the interval is 30min each time;
in some embodiments, in step (2), after the addition is completed, the mixed solution is stirred for another 12 hours.
Further, as a preferred embodiment, the preparation method of the self-repairing material based on the aromatic carboxylic acids MOFs comprises the following steps:
(1) 0.263g of nickel sulfate hexahydrate (NiSO) is weighed4·6H2O), 0.302g of 2, 5-bis (trifluoromethyl) terephthalic acid (H)2btftpa) and 0.180g of 1,10 '-orthophenanthroline (1, 10' -phen) were placed in a 25mL beaker and 9mL of N, N-Dimethylformamide (DMF) and 7mL of distilled water (H)2O), magnetically stirring for 40min at room temperature, pouring into a reaction kettle, putting into an oven, heating to 110 ℃, and reacting for 24 h. At 10 ℃ h-1Cooling to room temperature at the rate of (2) to obtain Ni-MOFs;
(2) 0.1g of Ni-MOFs, 0.4g of Benzotriazole (BTA) and 50mL of absolute ethyl alcohol are weighed in a beaker and stirred for reaction for 6 hours, and 10mL of H is added into the solution2And O, dropwise adding 1mol/L sodium hydroxide (NaOH) dropwise, adjusting the pH value of the solution to be between 8 and 9, adding an ethanol solution containing 20% tetraethyl silicate (TEOS) for three times, wherein the volume of the ethanol solution is 20 mu L each time, the interval is 30min each time, continuously stirring the solution in the process, stirring the mixed solution for 12h again after the addition is finished, centrifuging the mixed solution, washing the mixed solution for multiple times by using absolute ethyl alcohol, drying and grinding the washed mixed solution to obtain the self-repairing material (BTA/Ni-MOFs @ TEOS).
In other embodiments, the invention also discloses application of the self-repairing material based on the aromatic carboxylic acids MOFs, and the self-repairing material based on the aromatic carboxylic acids MOFs is applied to a water-based acrylic resin coating.
Specifically, the self-repairing material based on the aromatic carboxylic acids MOFs is dispersed in an aqueous acrylic resin and coated on a substrate. In specific embodiments, the base material may be carbon steel, copper sheet, aluminum sheet, etc.,
in some embodiments, the self-repairing material based on the aromatic carboxylic acids MOFs is added into the aqueous acrylic resin in an amount of 0.1-1 wt%;
preferably, in some embodiments, the self-repairing material based on the aromatic carboxylic acids MOFs is added in an amount of 0.5 wt%;
as a preferable scheme, in some embodiments, the self-repairing material based on the aromatic carboxylic acids MOFs is added into the aqueous acrylic resin, uniformly dispersed, then the aqueous paint dispersing aid is added into the mixed solution, uniformly stirred, then uniformly coated on the ground substrate material, and cured to obtain the self-repairing coating;
in the curing step, a curing agent can be added, and the selection and addition amount of the curing agent can refer to the curing agent commonly used in the prior art, and are not limited herein.
In some embodiments, the curing time is 1 day or more;
preferably, in some embodiments, the curing time is 4 days.
The water-based paint dispersant is not limited herein, and may be any water-based paint dispersant commonly used in the art.
The amount of the aqueous coating dispersant added is not limited herein, and may be an amount commonly used in the art.
The present invention will be described below with reference to specific examples.
Example 1
(1) 0.263g of nickel sulfate hexahydrate (NiSO) is weighed4·6H2O), 0.302g of 2, 5-bis (trifluoromethyl) terephthalic acid (H)2btftpa) and 0.180g of 1,10 '-orthophenanthroline (1, 10' -phen) were placed in a 25mL beaker and 9mL of N, N-Dimethylformamide (DMF) and 7mL of distilled water (H)2O), magnetically stirring for 40min at room temperature, pouring into a reaction kettle, putting into an oven, heating to 110 ℃, and reacting for 24 h. At 10 ℃ h-1Cooling to room temperature at the rate of (2) to obtain Ni-MOFs;
(2) weighing 0.1g of Ni-MOFs, 0.4g of Benzotriazole (BTA) and 50mL absolute ethyl alcohol is stirred in a beaker for 6 hours, 10mL of H is added into the solution2And O, dropwise adding 1mol/L sodium hydroxide (NaOH) dropwise, adjusting the pH value of the solution to be between 8 and 9, adding an ethanol solution containing 20% tetraethyl silicate (TEOS) for three times, wherein the volume of the ethanol solution is 20 mu L each time, the interval is 30min each time, continuously stirring the solution in the process, stirring the mixed solution for 12h again after the addition is finished, centrifuging the mixed solution, washing the mixed solution for multiple times by using absolute ethyl alcohol, drying and grinding the washed mixed solution to obtain the self-repairing material (BTA/Ni-MOFs @ TEOS).
Example 2
The self-repairing material (BTA/Ni-MOFs @ TEOS) prepared in the embodiment 1 is used as an auxiliary agent and applied to a water-based acrylic resin coating, so that the corrosion resistance and the self-repairing performance of the coating can be greatly improved, and the preparation process of the coating is as follows:
a carbon steel test piece having a size of 4cm X13 cm and a thickness of 0.5cm was used as a base material. Adding 0.025g of BTA/MOFs @ TEOS self-repairing material into 5g of water-based acrylic resin, performing ultrasonic treatment, mixing and stirring to uniformly disperse the BTA/MOFs @ TEOS self-repairing material, then adding 10 mu L of water-based paint dispersing aid into the mixed solution, uniformly stirring to obtain the self-repairing material (BTA/Ni-MOFs @ TEOS), uniformly coating the BTA/Ni-MOFs @ TEOS/PAA on the polished carbon steel sheet, and curing for 4d to obtain the self-repairing coating BTA/Ni-MOFs @ TEOS/PAA.
Infrared spectrogram test analysis
As shown in the attached figure 1, the Ni-MOFs has four characteristic peaks at 3416cm-1, 1609cm-1, 1065cm-1 and 724cm-1, which correspond to vibration absorption peaks of O-H, C-O, C-F and Ni-O of the Ni-MOFs. And the infrared characteristic absorption peaks of the Ni-MOFs appear in an FTIR spectrogram of the BTA/Ni-MOFs @ TEOS self-repairing material, which proves that the Ni-MOFs exist in the self-repairing material. In addition, compared with Ni-MOFs, BTA/Ni-MOFs @ TEOS shows a new absorption peak at 1112cm-1 in the red spectrum, which corresponds to the characteristic peak at O-Si-O of TEOS. The FTIR spectrum analysis result shows that the Ni-MOFs and BTA/Ni-MOFs @ TEOS self-repairing materials are successfully prepared.
XRD pattern test analysis
XRD tests are utilized to study the phase structures of the Ni-MOFs powder and the BTA/Ni-MOFs @ TEOS self-repairing material obtained in the above example 1, and the results are shown in the attached figure 2. It can be seen from the Ni-MOFs pattern that 2 θ has many diffraction peaks from 5 to 50 ° due to the ordered porous structure of Ni-MOFs. The diffraction peak of the BTA/Ni-MOFs @ TEOS self-repairing material is almost consistent with that of the Ni-MOFs, but the diffraction intensity is weakened, the Ni-MOFs diffraction peak is weakened due to the fact that the TEOS is coated, and meanwhile, the BTA/Ni-MOFs @ TEOS self-repairing material can be preliminarily judged to be successfully prepared.
Time-potential curve analysis
Open circuit potential (E) of bare carbon steel and carbon steel sheet coated with pure water acrylic resin self-repairing coating PAA, Ni-MOFs/PAA, BTA/Ni-MOFs @ TEOS/PAA in cooling water of hydraulic power plant at room temperatureocp) The graph of the relationship with the soaking time is shown in fig. 3. The open circuit potential shifted positively to different degrees for all samples, including bare carbon steel, and reached steady state after about 2400 s. E value of bare carbon steel of-0.7436V, pure water acrylic resin coatingocpE with a value of-0.5499V, Ni-MOFs/PAA, BTA/Ni-MOFs @ TEOS/PAA coatingocpValues of-0.4260, -0.3218, respectively. E coating water-based acrylic self-repairing coating containing Ni-MOFs and BTA/Ni-MOFs @ TEOSocpThe values are higher than the values of the bare carbon steel and pure water acrylic resin coatings, and particularly the corrosion potential value of the BTA/Ni-MOFs @ TEOS/PAA self-repairing coating is the highest. The BTA/Ni-MOFs @ TEOS/PAA self-repairing coating has better anti-corrosion performance, so that the coating has a higher open-circuit potential value, which shows that the BTA/Ni-MOFs @ TEOS/PAA self-repairing coating has a better function of protecting carbon steel from being corroded by corrosive media.
Analysis of potential polarization curves
The potentiodynamic polarization curve graph of bare carbon steel, carbon steel sheets coated with pure water acrylic resin self-repairing coating PAA, Ni-MOFs/PAA, BTA/Ni-MOFs @ TEOS/PAA in cooling water of a hydraulic power plant is shown in an attached figure 4. Compared with bare carbon steel, the polarization curves coated with PAA, Ni-MOFs/PAA and BTA/Ni-MOFs @ TEOS/PAA self-repairing coatings are all moved downwards, the corrosion current is reduced, the corrosion potential is moved forwards, and the carbon steel is protected and the corrosion rate is reduced.
Analysis by scanning Electron microscope
Scratches were etched on the waterborne acrylic coatings and the BTA/Ni-MOFs @ TEOS/PAA self-healing coatings using a utility knife and the following tests were conducted to find: after the scratch area of the pure water acrylic resin coating is soaked in cooling water for 30 days, the Q235 surface of the scratch area is seriously corroded, the surface is covered with iron rust with a loose structure, the scratch area is filled with corrosion products, the coating is shown to fall off from the surface of Q235 carbon steel, and the protective effect of the coating is ineffective; FIG. 5 shows that after the scratched area of the BTA/Ni-MOFs @ TEOS/PAA self-repairing coating is soaked in cooling water for 30 days, slight corrosion occurs on the surface of Q235 carbon steel in the scratched area, and only a small amount of corrosion products exist in the scratched area, which indicates that the BTA/Ni-MOFs @ TEOS/PAA self-repairing coating successfully releases a BTA corrosion inhibitor in the scratched area, and the corrosion inhibitor effectively forms a protective film on the surface of the Q235 carbon steel, so that the corrosion condition of the scratched area is slowed down. EDS analysis of the product in the scratched area of the coating of FIG. 6 shows that the product in the scratched area of the pure acrylic coating is almost iron oxide, while N element appears in the product in the scratched area of the BTA/Ni-MOFs @ TEOS/PAA coating, and the EDS results confirm that BTA in the coating is released in the scratched area, and the released BTA corrosion inhibitor effectively slows down the corrosion of the scratched area.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Variations or modifications in other variations may occur to those skilled in the art based upon the foregoing description. Not all embodiments need be illustrated or described herein. And obvious variations or modifications of this embodiment may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A self-repairing material based on aromatic carboxylic acids MOFs is characterized in that: the self-repairing material consists of an encapsulant, a corrosion inhibitor and Ni-MOFs formed by nickel salt and a ligand;
wherein the packaging agent is one or two of Tetraethoxysilane (TEOS) and polyurea formaldehyde (PUF);
wherein the corrosion inhibitor is one or more of Benzotriazole (BTA), Polydimethylsiloxane (PDMS) and 2-Mercaptobenzimidazole (MBI);
the ligand comprises a main ligand and an auxiliary ligand, wherein the main ligand is one or two of 2, 5-bis (trifluoromethyl) terephthalic acid and 2, 5-dibromoterephthalic acid, and the auxiliary ligand is 1, 10' -phenanthroline.
2. The preparation method of the self-repairing material based on the aromatic carboxylic acids MOFs according to claim 1, characterized by comprising the following steps:
(1) taking nickel sulfate hexahydrate (NiSO)4·6H2O) and a ligand are placed in a container, then a first solvent is added, the mixture is stirred uniformly, then the mixture is heated to 90-140 ℃, the reaction time is more than 8 hours, and then the mixture is cooled to room temperature, so that Ni-MOFs are obtained;
(2) taking Ni-MOFs, a corrosion inhibitor and absolute ethyl alcohol, stirring and reacting for 3-10 hours in a container, and then adding H into the solution2And O, dropwise adding a sodium hydroxide solution (NaOH), adjusting the pH value of the solution to be 8-9, adding an ethanol solution containing 15-25% of an encapsulant for 1-3 times at intervals of 10-60 min each time, continuously stirring in the process, stirring the mixed solution for more than 8 hours again after the addition is finished, centrifuging, washing with absolute ethanol for multiple times, drying, and grinding to obtain the self-repairing material.
3. The method for preparing the self-repairing material based on the aromatic carboxylic acids MOFs according to claim 2, wherein,
in the step (1), the nickel sulfate hexahydrate (NiSO)4·6H2O) and the ligand in a molar ratio of (2-3): 2;
further, in the step (1), the nickel sulfate hexahydrate (NiSO)4·6H2O) and ligand in a molar ratio of 1: 1;
in the step (1), the ratio of the ligand to the first solvent is 0.02-0.3 mol/L;
further, in the step (1), the ratio of the ligand to the first solvent is 0.1 mol/L;
in the step (1), a first solvent is a mixed solution of N, N-Dimethylformamide (DMF) and distilled water;
further, in the step (1), the volume ratio of the N, N-Dimethylformamide (DMF) to the distilled water is 3: 2.
4. the method for preparing the self-repairing material based on the aromatic carboxylic acids MOFs according to claim 2, wherein,
the reaction temperature in the step (1) is 100-130 ℃;
further, the reaction temperature in the step (1) is 110 ℃;
in the step (1), the heating rate is 7-15 ℃ h-1；
Further, the temperature rise rate in the step (1) is 10 ℃ h-1；
The reaction time in the step (1) is 20-30 h;
further, the reaction time in step (1) is 24 h.
5. The method for preparing the self-repairing material based on the aromatic carboxylic acids MOFs according to claim 2, wherein,
in the step (2),
the molar ratio of the Ni-MOFs to the corrosion inhibitor to the packaging agent is (10-30): (80-120): (4: 8);
further, the molar ratio of the Ni-MOFs, the corrosion inhibitor and the packaging agent is 25: 100: 6.
6. the method for preparing the self-repairing material based on the aromatic carboxylic acids MOFs according to claim 2, wherein,
the reaction time in the step (2) is 5-8 h;
further, the reaction time in the step (2) is 6 hours;
further, the dropping manner in the step (2) is dropwise dropping.
7. The method for preparing the self-repairing material based on the aromatic carboxylic acids MOFs according to claim 2, wherein,
the concentration of the sodium hydroxide solution in the step (2) is 0.5-2 mol/L;
further, the concentration of the sodium hydroxide solution in the step (2) is 1 mol/L;
in the step (2), the concentration of the ethanol solution of the packaging agent is 20 percent;
in the step (2), the number of times of adding the packaging agent is 3, and the interval is 30min each time;
further, in the step (2), after the addition was completed, the mixed solution was stirred again for 12 hours.
8. The preparation method of the self-repairing material based on the aromatic carboxylic acids MOFs according to any one of claims 2 to 7, characterized by comprising the following steps:
(1) 0.263g of nickel sulfate hexahydrate (NiSO) is weighed4·6H2O), 0.302g of 2, 5-bis (trifluoromethyl) terephthalic acid (H)2btftpa) and 0.180g of 1,10 '-orthophenanthroline (1, 10' -phen) were placed in a 25mL beaker and 9mL of N, N-Dimethylformamide (DMF) and 7mL of distilled water (H)2O), magnetically stirring for 40min at room temperature, pouring into a reaction kettle, putting into an oven, heating to 110 ℃, and reacting for 24 h. At 10 ℃ h-1Cooling to room temperature at the rate of (2) to obtain Ni-MOFs;
(2) 0.1g of Ni-MOFs, 0.4g of Benzotriazole (BTA) and 50mL of absolute ethyl alcohol are weighed in a beaker and stirred for reaction for 6 hours, and 10mL of H is added into the solution2And O, dropwise adding 1mol/L sodium hydroxide (NaOH) dropwise, adjusting the pH value of the solution to be between 8 and 9, adding an ethanol solution containing 20% tetraethyl silicate (TEOS) for three times, wherein the volume of the ethanol solution is 20 mu L each time, the interval is 30min each time, continuously stirring the solution in the process, stirring the mixed solution for 12h again after the addition is finished, centrifuging the mixed solution, washing the mixed solution for multiple times by using absolute ethyl alcohol, drying and grinding the washed mixed solution to obtain the self-repairing material (BTA/Ni-MOFs @ TEOS).
9. The application of the self-repairing material based on the aromatic carboxylic acids MOFs is characterized in that the self-repairing material based on the aromatic carboxylic acids MOFs is applied to a water-based acrylic resin coating.
10. The application of the self-repairing materials based on the aromatic carboxylic acids MOFs according to claim 9, wherein the self-repairing materials based on the aromatic carboxylic acids MOFs are dispersed in an aqueous acrylic resin and coated on a substrate;
further, in the aqueous acrylic resin, the addition amount of the self-repairing material based on the aromatic carboxylic acids MOFs is 0.1-1 wt%;
further, the addition amount of the self-repairing material based on the aromatic carboxylic acid MOFs is 0.5 wt%;
further, adding the self-repairing material based on the aromatic carboxylic acid MOFs into the aqueous acrylic resin, uniformly dispersing, then adding the aqueous paint dispersing auxiliary agent into the mixed solution, uniformly stirring, then uniformly coating on the polished substrate material, and curing to obtain the self-repairing coating;
further, the base material can be carbon steel, copper sheets, aluminum sheets and the like,
further, the curing time is more than 1 day;
preferably, the curing time is 4 days.
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