CN114292413B - Preparation method and application of self-repairing material based on aromatic carboxylic acid MOFs - Google Patents
Preparation method and application of self-repairing material based on aromatic carboxylic acid MOFs Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 89
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims description 16
- 238000000576 coating method Methods 0.000 claims abstract description 101
- 239000011248 coating agent Substances 0.000 claims abstract description 94
- 239000013099 nickel-based metal-organic framework Substances 0.000 claims abstract description 82
- 238000005260 corrosion Methods 0.000 claims abstract description 54
- 230000007797 corrosion Effects 0.000 claims abstract description 51
- 239000003446 ligand Substances 0.000 claims abstract description 43
- 239000003112 inhibitor Substances 0.000 claims abstract description 35
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000012964 benzotriazole Substances 0.000 claims description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 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 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
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- 239000002904 solvent Substances 0.000 claims description 15
- 241000080590 Niso Species 0.000 claims description 14
- 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 14
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 14
- 230000035484 reaction time Effects 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
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
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- 230000001105 regulatory effect Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229920002396 Polyurea Polymers 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010949 copper Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 2
- 238000005303 weighing Methods 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 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 description 6
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Abstract
The invention relates to a preparation method and application of a self-repairing material based on aromatic carboxylic MOFs, belonging to the technical field of self-repairing material preparation, and the self-repairing material based on aromatic carboxylic 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 provided by the invention is used as an auxiliary agent and applied to a water-based acrylic resin coating, so that the corrosion resistance and self-repairing performance of the coating can be greatly improved.
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 acid MOFs.
Background
The simplest and most effective method for protecting carbon steel against corrosion is to coat an organic coating on the surface of the carbon steel. However, the organic coating has the problems of easy cracking, weak anti-mechanical property and poor dispersion stability. The addition of some adjuvants to self-healing coatings is an important means of solving 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 be improved, so that the corrosion resistance of the coating can be improved, and the service life of the coating can be prolonged. The resin in the self-repairing coating has no self-repairing function, and the corrosion inhibitor needs to be coated in a certain carrier (such as carbon nano tubes, inorganic nano particles, micro/nano capsules, MOFs materials and the like) and added into the coating, so that when the coating is subjected to external stimulus (such as pH, light, pressure, heat and the like), the damaged area releases the corrosion inhibitor, thereby repairing the damaged coating.
The materials commonly used as carriers for loading corrosion inhibitors all have some defects. The carbon nano tube has higher specific surface area and good stability, but the defects of uneven growth, difficult control of length and large amount of impurities which are difficult to remove are often caused in the preparation process, and the addition of the carbon nano tube serving as a carrier of a self-repairing coating often leads to low stability of the 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 microcapsule preparation process is complex, the size of the prepared microcapsule is larger, and is usually higher than the nano-scale, so that the microcapsule is not matched with the coating pore, the surface is uneven, the coating is easy to crack, the performance is destroyed, the nano-capsule is prepared by a severe and complex process, the manufacturing cost is high, and the microcapsule has smaller size, but the microcapsule still has a lot of difficulties when being used as a carrier for loading corrosion inhibitors for preparing self-repairing coatings. The MOFs with nanometer level has good compatibility with the coating, is not easy to agglomerate and has good dispersibility, and is an ideal carrier. MOFs material forms coordination chemical bonds with the metal substrate in the coating, thereby enhancing the coating adhesion and water resistance; therefore, the MOFs material is an ideal carrier for self-repairing coating and is also a better corrosion inhibitor or corrosion inhibitor auxiliary agent. In particular to a heterocyclic carboxylic acid MOFs material which can form coordination bonds with a metal substrate and can be better adsorbed on the metal surface. Compared with other corrosion inhibition aids, MOFs materials have the advantages of traditional inorganic materials (such as high porosity, thermal stability and the like) and the characteristics of novel composite materials (such as good reaction selectivity and strong loading capacity). At present, the anticorrosive paint in China is rapid in development, the paint can be watered, the VOC emission can be greatly reduced, and the anticorrosive paint is an important target for popularizing the green paint production field.
The aqueous acrylic resin (PAA) has the advantages of good weather resistance, ultraviolet irradiation resistance, difficult decomposition and pulverization or yellowing of the surface, and is an environment-friendly and low-cost aqueous coating. However, micropores and microcracks are generated on the surface of the coating due to the evaporation of the solvent during the curing process of the coating, so that the service life of the coating is shortened and economic loss is caused. Meanwhile, the corrosion inhibitor is directly mixed with the coating, and the strong interaction between the corrosion inhibitor and the coating damages the integrity of the coating, so that the protective capability of the coating is damaged.
MOFs material is a carrier with a specific pore structure formed by interconnecting metal or metal oxide clusters and organic ligands, has good loading capacity and better compatibility with matrix resin. On one hand, MOFs material can coordinate with hydroxyl and carboxyl in the matrix resin of the self-repairing coating due to unsaturated metal sites, and form coordination chemical bonds between the coating and the metal substrate, so that the adhesive force and the water resistance of the coating are enhanced; on the other hand, MOFs material has enough capacity to encapsulate the corrosion inhibitor and has the capability of controlling the release of the corrosion inhibitor, is an ideal carrier for self-repairing coating, and is also a better corrosion inhibitor or corrosion inhibitor auxiliary agent. At present, many documents are reported on the construction of self-repairing coatings by using self-repairing materials, but few self-repairing coatings constructed by using self-repairing materials prepared from MOFs are reported. Therefore, the application research of MOFs-based materials in self-repairing coatings has certain theoretical and practical significance.
Disclosure of Invention
The invention aims to coat Ni-MOFs loaded with corrosion inhibitors (BTA) by using organic matter TEOS (tetraethoxysilane) sensitive to environment to prepare a self-repairing material (BTA/Ni-MOFs@TEOS) prepared based on aromatic carboxylic acids MOFs, and then adding the self-repairing material serving as an auxiliary agent into a water-based acrylic resin (PAA) self-repairing coating to prepare the super-hydrophobic BTA/Ni-MOFs@TEOS/PAA self-repairing coating, so that the corrosion resistance and self-repairing capability of the coating are improved.
The technical scheme of the invention is as follows:
a self-healing material based on aromatic carboxylic MOFs, consisting of an encapsulant, a corrosion inhibitor, and Ni-MOFs formed from a 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 first and second,
the combination of ligands may be 2, 5-bis (trifluoromethyl) terephthalic acid and 1,10' -phenanthroline;
the combination of ligands may be 2, 5-dibromoterephthalic acid and 1,10' -phenanthroline;
the combination of ligands may also be 2, 5-bis (trifluoromethyl) terephthalic acid, 2, 5-dibromoterephthalic acid, 1,10' -phenanthroline.
As a preferred technical solution, the ratio of primary ligand to secondary ligand is 1:1, a step of;
the invention also discloses a preparation method of the self-repairing material based on the aromatic carboxylic acid MOFs, which specifically comprises the following steps:
(1) Nickel sulfate hexahydrate (NiSO) 4 ·6H 2 Placing O) and a ligand in a container, adding a first solvent, stirring uniformly, heating to 90-140 ℃, reacting for more than 8 hours, and cooling to room temperature to obtain Ni-MOFs;
wherein, the temperature can be selected to be any temperature in 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 this range, for example, 8h,9h,10h,11h,12h,13h,15h,20h,21h,24h,25h,28h,30h,35h, etc.
(2) Stirring Ni-MOFs, corrosion inhibitor and absolute ethyl alcohol in a container to react for 3-10H, and then adding H into the solution 2 O, then dropwise adding sodium hydroxide solution (NaOH), regulating the pH of the solution to be 8-9, then adding ethanol solution containing 15-25% of packaging agent for 1-3 times at intervals of 10-60 min, continuously stirring the mixture, stirring the mixture for more than 8h after the process is finished, centrifuging, washing the mixture with absolute ethanol for multiple times, drying and grinding to obtain the self-repairing material (BTA/Ni-MOFs@TEOS).
Further, the method comprises the steps of,
in step (1), the nickel sulfate hexahydrate (NiSO 4 ·6H 2 O) and formulationBodyThe molar ratio of (2-3): 2;
further, in the step (1), the nickel sulfate hexahydrate (NiSO 4 ·6H 2 The molar ratio of O) to ligand is 1:1, a step of;
in the step (1), the proportion of the ligand to the solvent I is 0.02-0.3 mol/L;
further, in the step (1), the ratio of the ligand to the solvent I is 0.1mol/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 ℃;
the temperature rising rate in the step (1) is 7-15 ℃ h -1 ；
Further, the temperature rising rate in the step (1) is 10 ℃ h -1 ；
The reaction time in the step (1) is 20-30h;
further, the reaction time in the step (1) is 24 hours.
Further, in the step (2),
the mole ratio of Ni-MOFs, corrosion inhibitor and packaging agent is (10-30): (80-120): (4:8);
further, the molar ratio of Ni-MOFs, corrosion inhibitor and encapsulant was 25:100:6.
further, the reaction time in the step (2) is 5-8 hours;
further, the reaction time in the step (2) is 6h;
further, the dropping mode in the step (2) is dropwise adding.
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 1mol/L;
the concentration of the ethanol solution of the packaging agent in the step (2) is 20 percent;
in the step (2), the number of times of adding the packaging agent is 3, and each time is separated by 30 minutes;
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 acid MOFs comprises the following steps:
(1) 0.263g of nickel sulfate hexahydrate (NiSO) 4 ·6H 2 O), 0.302g of 2, 5-bis (trifluoromethyl) terephthalic acid (H 2 btftpa) and 0.180g of 1,10 '-phenanthroline (1, 10' -phen) were placed in a 25mL beaker and 9mL of N, N-Dimethylformamide (DMF) and 7mL of distilled water (H 2 O), magnetically stirring for 40min at room temperature, pouring into a reaction kettle, and putting into an oven to heat to 110 ℃ for reaction for 24h. At 10 ℃ h -1 Cooling to room temperature at a rate of (2) to obtain Ni-MOFs;
(2) 0.1g of Ni-MOFs, 0.4g of Benzotriazole (BTA) and 50mL of absolute ethyl alcohol were weighed and stirred in a beaker for reaction for 6 hours, and 10mL of H was added to the solution 2 O, dropwise adding 1mol/L sodium hydroxide (NaOH) to adjust the pH of the solution to 8-9 for three timesAdding 20% tetraethyl silicate (TEOS) ethanol solution, 20 mu L each time for 30min each time, continuously stirring, stirring the mixed solution for 12h again after the addition, centrifuging, washing with absolute ethanol for multiple times, drying, and grinding to obtain self-repairing material (BTA/Ni-MOFs@TEOS).
The invention also discloses application of the self-repairing material based on the aromatic carboxylic MOFs, and the self-repairing material based on the aromatic carboxylic MOFs is applied to the aqueous acrylic resin coating. The self-repairing material based on aromatic carboxylic MOFs is used as an auxiliary agent.
Further, the self-repairing material based on the aromatic carboxylic MOFs is 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 MOFs is 0.1-1wt%;
further, the addition amount of the self-repairing material based on the aromatic carboxylic MOFs is 0.5wt%;
further, adding the self-repairing material based on aromatic carboxylic MOFs into aqueous acrylic resin, uniformly dispersing, then adding aqueous coating dispersion auxiliary agent into the mixed solution, uniformly stirring, uniformly coating on the polished substrate material, and curing to obtain the self-repairing coating;
in this curing step, a curing agent may be added, and the selection and addition amount of the curing agent may be referred to as curing agents commonly used in the art, without limitation.
Further, the matrix 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 aqueous paint dispersant is not limited herein, and aqueous paint dispersants commonly used in the art may be used.
The amount of the aqueous coating dispersion to be added is not limited, and may be any amount commonly used in the art.
Still further, the method further comprises the steps of,
adding 0.025g of BTA/MOFs@TEOS self-repairing material into 5g of aqueous acrylic resin, carrying out ultrasonic treatment, mixing and stirring to uniformly disperse the self-repairing material, adding 10 mu L of polyamide curing agent into the mixed solution, uniformly stirring to obtain self-repairing material (BTA/Ni-MOFs@TEOS), uniformly coating 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.
The self-repairing material (BTA/Ni-MOFs@TEOS) prepared based on the aromatic carboxylic acid MOFs disclosed by the invention is prepared by coating Ni-MOFs loaded with corrosion inhibitors (BTA) by using organic substance TEOS (tetraethoxysilane) sensitive to environment, and the preparation method is simple.
The application of the self-repairing material (BTA/Ni-MOFs@TEOS) based on the aromatic carboxylic acid MOFs in the aqueous acrylic resin coating is good in dispersibility, and the application method is very simple and easy to operate. And the coating has good stability, excellent corrosion resistance and strong self-repairing capability after the anti-corrosion coating is formed on the metal matrix. Compared with the water-based acrylic resin serving as an anti-corrosion coating, the anti-corrosion effect is greatly improved.
Drawings
FIG. 1 is an infrared spectrogram of a BTA/Ni-MOFs@TEOS self-repairing material;
FIG. 2 XRD pattern for BTA/Ni-MOFs@TEOS self-repairing material;
FIG. 3 time-potential curves for bare carbon steel and self-repairing coatings coated with PAA, ni-MOFs/PAA, BTA/Ni-MOFs@TEOS/PAA;
FIG. 4 is a graph of electrokinetic polarization of bare carbon steel and coated with PAA, ni-MOFs/PAA, BTA/Ni-MOFs@TEOS/PAA self-healing coatings;
FIG. 5 is a scanning electron microscope image of the scratch area of the pure water acrylic resin coating and BTA/Ni-MOFs@TEOS/PAA self-repairing coating after soaking in cooling water for 30 d;
FIG. 6 EDS spectra of a pure water acrylic coating and a BTA/Ni-MOFs@TEOS/PAA self-healing coating after 30d immersion in cooling water.
Detailed Description
The invention is further illustrated by the following specific examples, which should be understood to those skilled in the art that variations and modifications can be made without departing from the principles of the invention, and these should also be considered to be within the scope of the invention.
A self-healing material based on aromatic carboxylic MOFs, consisting of an encapsulant, a corrosion inhibitor, and Ni-MOFs formed from a 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 first and second,
the combination of ligands may be 2, 5-bis (trifluoromethyl) terephthalic acid and 1,10' -phenanthroline;
the combination of ligands may be 2, 5-dibromoterephthalic acid and 1,10' -phenanthroline;
the combination of ligands may also be 2, 5-bis (trifluoromethyl) terephthalic acid, 2, 5-dibromoterephthalic acid, 1,10' -phenanthroline. As a preferred technical solution, the ratio of primary ligand to secondary ligand is 1:1, a step of;
in some embodiments, the preparation method of the self-repairing material based on the aromatic carboxylic acid MOFs specifically comprises the following steps:
(1) Nickel sulfate hexahydrate (NiSO) 4 ·6H 2 Placing O) and a ligand in a container, adding a first solvent, stirring uniformly, heating to 90-140 ℃, reacting for more than 8 hours, and cooling to room temperature to obtain Ni-MOFs;
wherein the temperature may be selected to be any temperature in the range of 90-140 ℃, for example, in some embodiments, the heating temperature may be selected to be 90 ℃,95 ℃,100 ℃,105 ℃,110 ℃,115 ℃,120 ℃,125 ℃,130 ℃,135 ℃,140 ℃.
In some embodiments, the rate of temperature increase in step (1) is 7-15℃h -1 The method comprises the steps of carrying out a first treatment on the surface of the For example: 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 the range, for example, in some embodiments, 8h,9h,10h,11h,12h,13h,15h,20h,21h,24h,25h,28h,30h,35h, etc.
In some embodiments, in step (1), the nickel sulfate hexahydrate (NiSO 4 ·6H 2 The molar ratio of O) to the ligand is (2-3): 2;
in some embodiments, in step (1), the nickel sulfate hexahydrate (NiSO 4 ·6H 2 O) and formulationBodyThe molar ratio of (2) is 1:1, a step of;
in some embodiments, in step (1), the ratio of the ligand to solvent one is from 0.02 to 0.3mol/L;
as a preferred embodiment, in some embodiments, the ratio of the ligand to solvent one is 0.1mol/L;
in some embodiments, in step (1), solvent one is a mixture of N, N-Dimethylformamide (DMF) and distilled water;
as a preferred embodiment, in some embodiments, the volume ratio of N, N-Dimethylformamide (DMF) to distilled water is 3:2.
the above is only a preferred embodiment of the present invention and is not limited to the present invention.
(2) Stirring Ni-MOFs, corrosion inhibitor and absolute ethyl alcohol in a container to react for 3-10H, and then adding H into the solution 2 O, then dropwise adding sodium hydroxide solution (NaOH), regulating the pH of the solution to be 8-9, and then adding ethanol containing 15-25% of packaging agent for 1-3 timesAnd (3) continuously stirring the solution at intervals of 10-60 min each time, stirring the mixed solution for more than 8 hours after the addition, centrifuging, washing with absolute ethyl alcohol for multiple times, drying and grinding to obtain the self-repairing material.
In some embodiments, in step (2), the molar ratio of Ni-MOFs, corrosion inhibitor and 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 from 5 to 8 hours; for example 5h,6h,7h,8h.
Preferably, in some embodiments, the reaction time in step (2) is 6 hours;
in some embodiments, the dropping in step (2) is dropwise.
In some embodiments, the sodium hydroxide solution concentration in step (2) is 0.5 to 2mol/L;
preferably, in some embodiments, the sodium hydroxide solution concentration in step (2) is 1mol/L;
the concentration of the ethanol solution of the packaging agent in the step (2) is 20 percent;
in the step (2), the number of times of adding the packaging agent is 3, and each time is separated by 30 minutes;
in some embodiments, in step (2), after the addition is completed, the mixed solution is stirred for 12 hours again.
Further, as a preferred embodiment, the preparation method of the self-repairing material based on the aromatic carboxylic acid MOFs comprises the following steps:
(1) 0.263g of nickel sulfate hexahydrate (NiSO) 4 ·6H 2 O), 0.302g of 2, 5-bis (trifluoromethyl) terephthalic acid (H 2 btftpa) and 0.180g of 1,10 '-phenanthroline (1, 10' -phen) were placed in a 25mL beaker and 9mL of N, N-Dimethylformamide (DMF) and 7mL of distilled water (H 2 O), magnetically stirring for 40min at room temperature, pouring into a reaction kettle, and putting into an oven to heat to 110 ℃ for reaction for 24h. At 10 ℃ h -1 Cooling to room temperature at a rate ofNi-MOFs；
(2) 0.1g of Ni-MOFs, 0.4g of Benzotriazole (BTA) and 50mL of absolute ethyl alcohol were weighed and stirred in a beaker for reaction for 6 hours, and 10mL of H was added to the solution 2 O, dropwise adding 1mol/L sodium hydroxide (NaOH) after the addition, regulating the pH of the solution to be 8-9, adding an ethanol solution containing 20% tetraethyl silicate (TEOS) for three times, each time of 20 mu L, and each time for 30min, keeping continuous stirring, stirring the mixed solution for 12h again after the addition, centrifuging, washing with absolute ethanol for multiple times, drying and grinding 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 MOFs, and the self-repairing material based on the aromatic carboxylic MOFs is applied to the aqueous acrylic resin coating.
Specifically, the self-repairing material based on aromatic carboxylic MOFs is dispersed in an aqueous acrylic resin and coated on a substrate. In a specific embodiment, the matrix material may be carbon steel, copper sheet, aluminum sheet, etc.,
in some embodiments, the amount of added self-healing material based on aromatic carboxylic MOFs in the aqueous acrylic resin is 0.1-1wt%;
preferably, in some embodiments, the self-healing material based on aromatic carboxylic MOFs is added in an amount of 0.5wt%;
in some embodiments, adding the self-repairing material based on aromatic carboxylic MOFs into the aqueous acrylic resin, uniformly dispersing, adding the aqueous coating dispersing auxiliary into the mixed solution, uniformly stirring, uniformly coating on the polished substrate material, and curing to obtain the self-repairing coating;
in this curing step, a curing agent may be added, and the selection and addition amount of the curing agent may be referred to as curing agents commonly used in the art, without limitation.
In some embodiments, the cure time is 1 day or more;
preferably, in some embodiments, the cure time is 4 days.
The aqueous paint dispersant is not limited herein, and aqueous paint dispersants commonly used in the art may be used.
The amount of the aqueous coating dispersion to be added is not limited, and may be any amount commonly used in the art.
The invention is illustrated below by means of specific examples.
Example 1
(1) 0.263g of nickel sulfate hexahydrate (NiSO) 4 ·6H 2 O), 0.302g of 2, 5-bis (trifluoromethyl) terephthalic acid (H 2 btftpa) and 0.180g of 1,10 '-phenanthroline (1, 10' -phen) were placed in a 25mL beaker and 9mL of N, N-Dimethylformamide (DMF) and 7mL of distilled water (H 2 O), magnetically stirring for 40min at room temperature, pouring into a reaction kettle, and putting into an oven to heat to 110 ℃ for reaction for 24h. At 10 ℃ h -1 Cooling to room temperature at a rate of (2) to obtain Ni-MOFs;
(2) 0.1g of Ni-MOFs, 0.4g of Benzotriazole (BTA) and 50mL of absolute ethyl alcohol were weighed and stirred in a beaker for reaction for 6 hours, and 10mL of H was added to the solution 2 O, dropwise adding 1mol/L sodium hydroxide (NaOH) after the addition, regulating the pH of the solution to be 8-9, adding an ethanol solution containing 20% tetraethyl silicate (TEOS) for three times, each time of 20 mu L, and each time for 30min, keeping continuous stirring, stirring the mixed solution for 12h again after the addition, centrifuging, washing with absolute ethanol for multiple times, drying and grinding 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 the aqueous 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:
carbon steel test pieces having a size of 4 cm. Times.13 cm and a thickness of 0.5cm were used as a substrate. Adding 0.025g of BTA/MOFs@TEOS self-repairing material into 5g of aqueous acrylic resin, carrying out ultrasonic treatment, mixing and stirring to uniformly disperse the self-repairing material, adding 10 mu L of aqueous coating dispersion auxiliary agent into the mixed solution, uniformly stirring to obtain a self-repairing material (BTA/Ni-MOFs@TEOS), uniformly coating BTA/Ni-MOFs@TEOS/PAA on the polished carbon steel sheet, and curing for 4d to obtain a self-repairing coating BTA/Ni-MOFs@TEOS/PAA.
Infrared spectrogram test analysis
The Ni-MOFs and BTA/Ni-MOFs@TEOS self-repairing material obtained in example 1 were subjected to infrared spectroscopic analysis, and as shown in FIG. 1, the Ni-MOFs have four characteristic peaks at 3416cm-1, 1609cm-1, 1065cm-1 and 724cm-1, which correspond to the vibration absorption peaks of O-H, C=O, C-F and Ni-O of the Ni-MOFs, respectively. The infrared characteristic absorption peak of the Ni-MOFs appears in the FTIR spectrum of the self-repairing material of BTA/Ni-MOFs@TEOS, which proves the existence of the Ni-MOFs in the self-repairing material. In addition, a new absorption peak at 1112cm-1, corresponding to the characteristic peak at O-Si-O of TEOS, also appears in the red spectrogram of BTA/Ni-MOFs@TEOS, compared with Ni-MOFs. The above FTIR spectral analysis results show that Ni-MOFs and BTA/Ni-MOFs@TEOS self-repairing materials were successfully prepared.
XRD pattern test analysis
The phase structure of the powder Ni-MOFs and BTA/Ni-MOFs@TEOS self-repairing material obtained in example 1 above was studied by XRD testing, and the results are shown in FIG. 2. From the Ni-MOFs spectra, it can be seen that 2 theta has many diffraction peaks between 5 and 50 deg. 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, because of the coating of the TEOS, the diffraction peak of the Ni-MOFs is weakened, and meanwhile, the BTA/Ni-MOFs@TEOS self-repairing material can be judged to be successfully prepared.
Time-potential curve analysis
Open circuit potential of bare carbon steel and carbon steel sheet coated with pure water acrylic resin self-repairing coating PAA and Ni-MOFs/PAA, BTA/Ni-MOFs@TEOS/PAA in hydropower plant cooling water at room temperature (E ocp ) A graph of soak time is shown in fig. 3. For all samples, including bare carbon steel, the open circuit potential was shifted forward to varying degrees and reached steady state after about 2400 s. Eocp value of bare carbon steel is-0.7436V, E of pure water acrylic resin coating ocp Has a value of-0.5499V, ni-MOFs/PAA, BTA/Ni-E of MOFs@TEOS/PAA coating ocp The values were-0.4260, -0.3218, respectively. E coating aqueous acrylic self-healing coating containing Ni-MOFs and BTA/Ni-MOFs@TEOS ocp The values are higher than those of blank bare carbon steel and pure water acrylic resin coating, especially the corrosion potential value of the self-repairing coating coated with BTA/Ni-MOFs@TEOS/PAA is highest. The BTA/Ni-MOFs@TEOS/PAA self-repairing coating has better corrosion resistance, so that the coating shows a higher open circuit potential value, and 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 curve
The electrokinetic polarization curves of bare carbon steel and carbon steel sheets coated with pure water-based acrylic resin self-repairing coating PAA and Ni-MOFs/PAA and BTA/Ni-MOFs@TEOS/PAA in cooling water of hydropower plants are shown in figure 4. Compared with bare carbon steel, the polarization curves of the self-repairing coating coated with PAA, ni-MOFs/PAA and BTA/Ni-MOFs@TEOS/PAA all move downwards, the corrosion current is reduced, the corrosion potential moves forward, and the carbon steel is protected and the corrosion rate is reduced.
Scanning electron microscope analysis
Scratches were etched with a utility knife on the aqueous acrylic coating and BTA/Ni-MOFs@TEOS/PAA self-healing coating, and the following tests were performed to find: after soaking the scratch area of the pure water-based acrylic resin coating in cooling water for 30 days, severely corroding the surface of Q235 of the scratch area, covering the surface with iron rust with loose structure, and filling the scratch area with corrosion products, so that the coating is detached from the surface of Q235 carbon steel, and the protective effect of the coating is invalid; FIG. 5 shows that after the scratch area of the BTA/Ni-MOFs@TEOS/PAA self-repairing coating is soaked in cooling water for 30 days, the surface of Q235 carbon steel in the scratch area is slightly corroded, and only a small amount of corrosion products exist in the scratch area, which indicates that the BTA corrosion inhibitor is successfully released by the BTA/Ni-MOFs@TEOS/PAA self-repairing coating in the scratch 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 scratch area is slowed down. The EDS analysis results of the coating scratch area product of the figure 6 show that the product of the pure water acrylic coating scratch area is almost iron oxide, N element appears in the product of the BTA/Ni-MOFs@TEOS/PAA coating scratch area product, the EDS results prove that the corrosion inhibitor BTA in the coating is released in the scratch area, and the released BTA corrosion inhibitor effectively slows down the corrosion condition of the scratch area.
The foregoing is merely a preferred embodiment of the present invention and is not limited thereto. Other variations or modifications of the above description will be apparent to those of skill in the art. It is not necessary or nor practical to exemplify all embodiments herein. While obvious variations or modifications of the solution are still within the scope of the invention.
Claims (13)
1. A self-healing material based on aromatic carboxylic MOFs, characterized in that: the self-repairing material consists of a packaging agent, a corrosion inhibitor and Ni-MOFs formed by nickel salt and ligand;
wherein, the packaging agent is one or two of tetraethoxysilane TEOS and polyurea formaldehyde PUF;
wherein the corrosion inhibitor is one or two of benzotriazole BTA and 2-mercaptobenzimidazole MBI;
wherein the ligands comprise a primary ligand and a secondary ligand, wherein the primary ligand is 2, 5-bis (trifluoromethyl) terephthalic acid and the secondary ligand is 1,10' -phenanthroline;
the preparation method comprises the following steps:
(1) Taking nickel sulfate hexahydrate NiSO 4 ·6H 2 Placing O and ligand in a container, adding solvent I, stirring, heating to 110deg.C, reacting for more than 8 hr, and adding solvent I at 10deg.C -1 Cooling to room temperature to obtain Ni-MOFs;
the nickel sulfate hexahydrate NiSO 4 ·6H 2 The mol ratio of O to the ligand is 2-3: 2;
the proportion of the ligand to the solvent I is 0.02-0.3 mol/L;
the first solvent is a mixed solution of N, N-dimethylformamide DMF and distilled water;
the volume ratio of the N, N-dimethylformamide DMF to the distilled water is 3:2;
(2) Stirring Ni-MOFs, corrosion inhibitor and absolute ethyl alcohol in a container for reaction for 3-10H, and then adding H into the solution 2 O, dropwise adding a NaOH solution of sodium hydroxide, regulating the pH value of the solution to be 8-9, adding an ethanol solution containing 15-25% of packaging agent for 1-3 times at intervals of 10-60 min each time, continuously stirring, stirring the mixed solution for more than 8 hours after the addition, centrifuging, washing with absolute ethanol for multiple times, drying and grinding to obtain a self-repairing material;
wherein, the mole ratio of the Ni-MOFs, the corrosion inhibitor and the packaging agent is 10-30: 80-120: 4-8.
2. A method for preparing the self-repairing material based on aromatic carboxylic acid MOFs according to claim 1, comprising the following steps:
(1) Taking nickel sulfate hexahydrate NiSO 4 ·6H 2 Placing O and a ligand in a container, adding a solvent I, stirring uniformly, heating to 90-140 ℃, reacting for more than 8 hours, and cooling to room temperature to obtain Ni-MOFs;
(2) Stirring Ni-MOFs, corrosion inhibitor and absolute ethyl alcohol in a container for reaction for 3-10H, and then adding H into the solution 2 O, dropwise adding a NaOH solution of sodium hydroxide, regulating the pH value of the solution to be 8-9, adding an ethanol solution containing 15-25% of packaging agent for 1-3 times, keeping stirring continuously every time for 10-60 min, stirring the mixed solution for more than 8 hours after the adding is finished, centrifuging, washing with absolute ethanol for multiple times, drying and grinding to obtain the self-repairing material.
3. The method for producing a self-repairing material based on aromatic carboxylic MOFs according to claim 2, characterized in that,
in step (1), the nickel sulfate hexahydrate NiSO 4 ·6H 2 The molar ratio of O to ligand is 1:1, a step of;
in the step (1), the ratio of the ligand to the solvent I is 0.1mol/L.
4. The method for producing a self-repairing material based on aromatic carboxylic MOFs according to claim 2, characterized in that,
the reaction temperature in the step (1) is 100-130 ℃;
the temperature rising rate in the step (1) is 7-15 ℃ h -1 ；
The reaction time in the step (1) is 20-30h.
5. The method for producing a self-repairing material based on aromatic carboxylic MOFs according to claim 4, wherein,
the temperature rising rate in the step (1) is 10 ℃ h -1 ；
The reaction time in step (1) was 24h.
6. The method for producing a self-repairing material based on aromatic carboxylic acid MOFs according to claim 2, wherein in step (2),
the mole ratio of Ni-MOFs, corrosion inhibitor and packaging agent is 25:100:6.
7. the method for producing a self-repairing material based on aromatic carboxylic MOFs according to claim 2, characterized in that,
the reaction time in the step (2) is 5-8 hours;
the dropping mode in the step (2) is dropwise adding.
8. The method for producing a self-repairing material based on aromatic carboxylic MOFs according to claim 7, characterized in that,
the reaction time in step (2) was 6h.
9. The method for producing a self-repairing material based on aromatic carboxylic MOFs according to claim 2, characterized in that,
the concentration of the sodium hydroxide solution in the step (2) is 1mol/L;
the concentration of the ethanol solution of the packaging agent in the step (2) is 20 percent;
in the step (2), the number of times of adding the packaging agent is 3, and each time is separated by 30 minutes;
in the step (2), after the addition was completed, the mixed solution was stirred again for 12 hours.
10. The preparation method of the self-repairing material based on the aromatic carboxylic MOFs is characterized by comprising the following steps of:
(1) Weigh 0.263g nickel sulfate hexahydrate NiSO 4 ·6H 2 O, 0.302g of 2, 5-bis (trifluoromethyl) terephthalic acid H 2 btftpa and 0.180g of 1,10 '-phenanthroline 1,10' -phen were placed in a 25mL beaker and 9mL of LN, N-dimethylformamide DMF and 7mL of distilled water H were added 2 O, magnetically stirring at room temperature for 40min, pouring into a reaction kettle, putting into an oven, heating to 110 ℃ for reaction for 24h at 10 ℃ and h -1 Cooling to room temperature at a rate of (2) to obtain Ni-MOFs;
(2) Weighing 0.1gNi-MOFs, 0.4g benzotriazole BTA and 50mL absolute ethyl alcohol, stirring and reacting for 6h in a beaker, adding 10mLH to the solution 2 O, dropwise adding 1mol/L NaOH, regulating the pH of the solution to 8-9, adding 20% TEOS ethanol solution for three times, 20 mu L each time, 30min each time, continuously stirring, stirring the mixed solution for 12h again after the addition, centrifuging, washing with absolute ethyl alcohol for multiple times, drying, and grinding to obtain the self-repairing material BTA/Ni-MOFs@TEOS.
11. The use of the self-healing material based on aromatic carboxylic acid MOFs according to claim 1, wherein the self-healing material based on aromatic carboxylic acid MOFs is applied in an aqueous acrylic resin coating.
12. The use of the self-healing material based on aromatic carboxylic acid MOFs according to claim 11, wherein the self-healing material based on aromatic carboxylic acid MOFs is dispersed in an aqueous acrylic resin and coated on a substrate;
in the aqueous acrylic resin, the addition amount of the self-repairing material based on the aromatic carboxylic MOFs is 0.1-1wt%;
adding the self-repairing material based on aromatic carboxylic MOFs into water-based acrylic resin, uniformly dispersing, adding a water-based paint dispersing auxiliary into the mixed solution, uniformly stirring, uniformly coating on the polished substrate material, and curing to obtain a self-repairing coating;
the matrix material is carbon steel, copper sheet, aluminum sheet,
the curing time is more than 1 day.
13. The use of the self-healing material based on MOFs of aromatic carboxylic acid type according to claim 12, characterized in that,
in the aqueous acrylic resin, the addition amount of the self-repairing material based on the aromatic carboxylic MOFs is 0.5wt%;
the curing time was 4 days.
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