CN113073160A - Carboxylic acid ligand MOFs nano tanning agent with stable framework structure and preparation method and application thereof - Google Patents
Carboxylic acid ligand MOFs nano tanning agent with stable framework structure and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
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Abstract
The invention discloses a carboxylic acid ligand MOFs nano tanning agent with a stable frame structure, and a preparation method and application thereof, and aims to solve series problems caused by poor stability of a conventional metal tanning agent, such as chromium pollution caused by low utilization rate of a chromium tanning agent, surface over tanning caused by easy hydrolysis and precipitation of a zirconium tanning agent, and a retanning phenomenon caused by infirm combination of an aluminum tanning agent. Firstly, preparing an MOFs nano tanning agent with a stable frame structure by a hydrothermal method under a certain condition through metal salt with tanning property and a low-cost micromolecule ligand with masking effect; the tanning agent is used for tanning leather, the shrinkage temperature of the obtained crust leather is relatively high, and the special framework structure of the tanning agent improves the stability of molecules of the tanning agent, makes up the defect caused by poor stability of the traditional metal tanning agent, and obviously improves the comprehensive performance of the finished leather.
Description
Technical Field
The invention belongs to the field of leather tanning agents, and particularly relates to a carboxylic acid ligand MOFs nano-tanning agent with a stable framework structure, and a preparation method and application thereof.
Background
Tanning refers to the process by which tanning agent molecules penetrate into the skin of a hide and bind to the reactive groups of the collagen molecules of the skin to cause them to become qualitative. After tanning, the leather obtains better wet-heat resistance stability and other properties in a rich and various way. Among them, the chrome tanning agent can endow leather with excellent physical and chemical properties and mature process, and is the most widely used tanning agent. However, research shows that Cr (III) used in the tanning process is easily oxidized into Cr (VI) with potential carcinogenic risk, and the Cr (III) can cause harm to the health of human bodies. Meanwhile, the poor stability of the chrome tanning agent leads to low absorption rate, and a large amount of generated chromium-containing waste is difficult to discharge and treat, thereby causing serious environmental pollution. Therefore, in order to reduce the pollution and harm caused by chrome tanning, less chrome or chrome-free tanning has become an important direction for the future development of the tanning industry. At present, the common chrome-free tanning agent mainly comprises a zirconium tanning agent and an aluminum tanning agent, but because the molecules of the tanning agent have the same poor stability, the tanned leather has some problems, such as hydrolysis precipitation of the zirconium tanning agent is easy to occur, and the tanning agent molecules are over tanned on the surface of the leather to cause the leather to be harder; the binding capacity of the aluminum tanning agent molecules and the leather collagen fibers is weak, and the phenomenon of retanning and the like occur in subsequent water washing.
Metal-organic frameworks (MOFs) materials are hybrid organic-inorganic materials with a stable framework structure formed by self-assembly of inorganic metal ions and organic ligands. MOFs materials have the advantages of controllable metal ions and organic ligands, regular and stable structure, high adsorbability to metal ions, etc. (Journal of Industrial & Engineering Chemistry 2015, 28, 211-216).
Disclosure of Invention
The invention aims to provide a carboxylic acid ligand MOFs nano tanning agent with a stable frame structure, and a preparation method and application thereof, wherein the tanning agent can endow leather with better damp-heat resistance stability after being applied to tanning, and simultaneously makes up the defects of the traditional metal tanning agent, such as improvement of chromium absorptivity to reduce chromium pollution, and solves the problems of surface over-tanning caused by easy hydrolysis and precipitation of zirconium, insecure combination of aluminum and easy tanning withdrawal caused by the insecure combination of aluminum and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of carboxylic acid ligand MOFs nano tanning agent with stable frame structure is characterized in that metal salt and carboxylic acid organic ligand are respectively dissolved in N, N-dimethylformamide to obtain metal salt solution and carboxylic acid organic ligand solution; adding a carboxylic acid organic ligand solution into a metal salt solution to obtain a uniform mixed solution, and carrying out a hydrothermal reaction for 8-36 h; and centrifuging the obtained product solution to obtain a crude product, drying, calcining and activating for 8-36 h to obtain the carboxylic acid ligand MOFs nano tanning agent with a stable frame structure.
The metal salt is chromium nitrate, zirconium chloride, zirconium sulfate, aluminum nitrate and ferric sulfate.
The carboxylic acid organic ligand is terephthalic acid and 2-amino terephthalic acid.
The mass fraction of the metal salt solution is 2-10%; the mass fraction of the carboxylic acid organic ligand solution is 1-30%.
The hydrothermal reaction temperature is 100-220 ℃.
The calcining and activating temperature is 120-300 ℃.
The carboxylic acid ligand MOFs nano tanning agent with the stable framework structure is prepared by the preparation method.
The application of the carboxylic acid ligand MOFs nano tanning agent with the stable frame structure prepared by the preparation method in leather tanning comprises the following steps of:
firstly, weighing the mass of the pickled skin as the reference mass of the tanning process; adding sodium chloride and water into the rotary drum, wherein the mass of the water is 100-200% of the reference, the mass of the sodium chloride is 6-10% of the reference, 0.5-2.5% of formic acid or sulfuric acid solution of the reference is added, the pH value of bath liquid in the rotary drum is adjusted to 1.5-3.5, and the pickled Chinese cabbage is placed in the rotary drum and rotated for 30 min; then adding a standard 0.1-15% MOFs nano tanning agent into the bath lotion, tanning for 0.5-10 h, then adding a standard 0.5-2.5% sodium bicarbonate or sodium formate solution, adjusting the pH value of the bath lotion in the rotary drum to 3.8-6.0, and continuing to rotate for 20-60 min; finally, the drum is stopped overnight, and water is washed out of the drum the next day.
Compared with the prior art, the invention has the following advantages:
1. the invention takes metal salt with certain tanning property and low-cost micromolecule organic ligand as raw materials, prepares the MOFs nano tanning agent by a hydrothermal synthesis method, obtains the nano tanning agent with a stable framework structure, and simultaneously provides an application process thereof.
2. The MOFs nano tanning agent prepared by the invention has a simple synthesis process, wherein metal ions with tanning property and micromolecule ligands with masking effect can be regulated and controlled, and crust leather can obtain better damp-heat resistance stability when the MOFs nano tanning agent is applied to tanning.
3. The metal tanning agent and the masking agent are combined to synthesize the nano tanning agent with a stable structure, so that the stability of the nano tanning agent can be improved, the absorptivity of chromium, the alkali resistance of zirconium, the associativity of aluminum and the like are improved, and the finished leather has good comprehensive performance.
Drawings
FIG. 1 is a graph of the shrinkage temperature of the leathers tanned by the MOFs nano-tanning agent prepared in the example and the unbanning crust leathers.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
According to the invention, the MOFs material is prepared by taking metal salt with tanning property and ligand with strong binding capacity as raw materials, and by utilizing the masking effect of the micromolecule ligand on tanning metal ions, a nano tanning agent with good tanning property is expected to be obtained, the pollution and harm of chromium can be effectively reduced or avoided, and meanwhile, some problems of tanned leather caused by poor stability of the conventional metal tanning agent are solved.
The invention discloses a preparation method of a carboxylic acid ligand MOFs nano tanning agent with a stable framework structure, which comprises the following steps:
respectively dissolving metal salts such as chromium nitrate, zirconium chloride, zirconium sulfate, aluminum nitrate and ferric sulfate and carboxylic acid organic ligands such as terephthalic acid and 2-amino terephthalic acid in N, N-dimethylformamide, and respectively carrying out magnetic stirring to obtain a metal salt solution and an organic ligand solution, wherein the mass fraction of the metal salt solution is 2-10%; the mass fraction of the carboxylic acid organic ligand solution is 1-30%; adding an organic ligand solution into a metal salt solution to obtain a uniform mixed solution, placing the mixed solution into a reaction kettle provided with a polytetrafluoroethylene inner container, setting the temperature of an oven to be 100-220 ℃, and carrying out hydrothermal reaction for 8-36 h; and centrifuging the obtained product solution to obtain a crude product, drying the crude product in a drying oven at the temperature of 50-80 ℃, and calcining and activating for 8-36 hours in a muffle furnace at the temperature of 120-300 ℃ to obtain the carboxylic acid ligand MOFs nano tanning agent with a stable frame structure.
The nano tanning agent prepared by the preparation method is used for tanning leather, and specifically comprises the following steps:
firstly, weighing the mass of the pickled skin as the reference mass of the tanning process; adding sodium chloride and water into the rotary drum, wherein the mass of the water is 100-200% of the reference, the mass of the sodium chloride is 6-10% of the reference, 0.5-2.5% of formic acid or sulfuric acid solution of the reference is added, the pH value of bath liquid in the rotary drum is adjusted to 1.5-3.5, and the pickled Chinese cabbage is placed in the rotary drum and rotated for 30 min; then adding a standard 0.1-15% MOFs nano tanning agent into the bath lotion, tanning for 0.5-10 h, then adding a standard 0.5-2.5% sodium bicarbonate or sodium formate solution, adjusting the pH value of the bath lotion in the rotary drum to 3.8-6.0, and continuing to rotate for 20-60 min; finally, the drum is stopped overnight, and water is washed out of the drum the next day.
Example 1:
preparing the MOFs nano tanning agent:
respectively dissolving chromium nitrate and terephthalic acid in N, N-dimethylformamide, and respectively carrying out magnetic stirring to obtain a metal salt solution and an organic ligand solution, wherein the mass fraction of the metal salt solution is 5%; the mass fraction of the carboxylic acid organic ligand solution is 5%; adding an organic ligand solution into a metal salt solution to obtain a uniform mixed solution, placing the mixed solution into a reaction kettle provided with a polytetrafluoroethylene inner container, setting the temperature of an oven at 220 ℃, and carrying out hydrothermal reaction for 8 hours; and centrifuging the obtained product solution to obtain a crude product, drying the crude product in an oven at the temperature of 80 ℃, and calcining and activating the crude product in a muffle furnace at the temperature of 150 ℃ for 12 hours to obtain the carboxylic acid ligand MOFs nano tanning agent with a stable frame structure.
Application of MOFs nano tanning agent:
firstly, weighing the mass of the pickled skin as the reference mass of the tanning process; adding sodium chloride and water into the rotary drum, wherein the mass of the water is 150% of the reference, the mass of the sodium chloride is 8% of the reference, adding formic acid or sulfuric acid solution to adjust the pH value of bath liquid in the rotary drum to be 2.5, and placing the acid skin in the rotary drum to rotate for 30 min; then adding 6 percent of MOFs nano tanning agent into the bath liquid, tanning for 4 hours, adding sodium bicarbonate or ammonium formate solution to adjust the pH value of the bath liquid in the rotary drum to 4.0, and continuing to rotate for 30 min; finally, the drum is stopped overnight, and water is washed out of the drum the next day.
Example 2:
preparing the MOFs nano tanning agent:
respectively dissolving zirconium chloride and terephthalic acid in N, N-dimethylformamide, and respectively carrying out magnetic stirring to obtain a metal salt solution and an organic ligand solution, wherein the mass fraction of the metal salt solution is 2%; the mass fraction of the carboxylic acid organic ligand solution is 2.4%; adding an organic ligand solution into a metal salt solution to obtain a uniform mixed solution, placing the mixed solution into a reaction kettle provided with a polytetrafluoroethylene inner container, setting the temperature of an oven at 120 ℃, and carrying out hydrothermal reaction for 24 hours; and centrifuging the obtained product solution to obtain a crude product, drying the crude product in a 60 ℃ oven, and calcining and activating the crude product for 18 hours in a 200 ℃ muffle furnace to obtain the carboxylic acid ligand MOFs nano tanning agent with a stable frame structure.
Application of MOFs nano tanning agent:
firstly, weighing the mass of the pickled skin as the reference mass of the tanning process; adding sodium chloride and water into the rotary drum, wherein the mass of the water is 150% of the reference, the mass of the sodium chloride is 10% of the reference, adding formic acid or sulfuric acid solution to adjust the pH value of bath liquid in the rotary drum to be 2.5, and placing the acid skin in the rotary drum to rotate for 30 min; then adding a standard 5% MOFs nano tanning agent into the bath liquid, tanning for 5 h, then adding sodium bicarbonate or sodium formate solution to adjust the pH value of the bath liquid in the rotary drum to 4.5, and continuing to rotate for 30 min; finally, the drum is stopped overnight, and water is washed out of the drum the next day.
Example 3:
preparing the MOFs nano tanning agent:
respectively dissolving aluminum sulfate and terephthalic acid in N, N-dimethylformamide, and respectively carrying out magnetic stirring to obtain a metal salt solution and an organic ligand solution, wherein the mass fraction of the metal salt solution is 2%; the mass fraction of the carboxylic acid organic ligand solution is 4%; adding the organic ligand solution into the metal salt solution to obtain a uniform mixed solution, placing the mixed solution into a reaction kettle provided with a polytetrafluoroethylene inner container, setting the temperature of an oven to be 190 ℃, and carrying out hydrothermal reaction for 26 hours; and centrifuging the obtained product solution to obtain a crude product, drying the crude product in a 50 ℃ oven, and calcining and activating for 8 hours in a muffle furnace at the temperature of 270 ℃ to obtain the carboxylic acid ligand MOFs nano tanning agent with a stable frame structure.
Application of MOFs nano tanning agent:
firstly, weighing the mass of the pickled skin as the reference mass of the tanning process; adding sodium chloride and water into the rotary drum, wherein the mass of the water is 150% of the reference, the mass of the sodium chloride is 10% of the reference, adding formic acid or sulfuric acid solution to adjust the pH value of bath liquid in the rotary drum to be 3, and placing the acid skin in the rotary drum to rotate for 30 min; adding 10% MOFs nano tanning agent into the bath liquid, tanning for 3 h, adding sodium bicarbonate or sodium formate solution, adjusting the pH value of the bath liquid in the rotary drum to 4.2, and continuing to rotate for 30 min; finally, the drum is stopped overnight, and water is washed out of the drum the next day.
Referring to FIG. 1, the shrinkage temperature profiles of leather tanned by the MOFs nano-tanning agents prepared in examples 1, 2 and 3 and pure crust leather are shown, wherein Cr-MOF is shown in example 1, Zr-MOF is shown in example 2, and Al-MOF is shown in example 3. As can be seen from the figure, when the MOFs nano-tanning agent prepared in the example 1 is applied to leather tanning, compared with pure crust leather, the shrinkage temperature of a leather sample tanned by the MOFs nano-tanning agent can be increased by about 25 ℃, and the MOFs nano-tanning agent has better wet-heat stability.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (8)
1. A preparation method of carboxylic acid ligand MOFs nano tanning agent with stable framework structure is characterized in that:
respectively dissolving metal salt and carboxylic acid organic ligand in N, N-dimethylformamide to obtain metal salt solution and carboxylic acid organic ligand solution; adding a carboxylic acid organic ligand solution into a metal salt solution to obtain a uniform mixed solution, and carrying out a hydrothermal reaction for 8-36 h; and centrifuging the obtained product solution to obtain a crude product, drying, calcining and activating for 8-36 h to obtain the carboxylic acid ligand MOFs nano tanning agent with a stable frame structure.
2. The preparation method of carboxylic acid ligand MOFs nano-tanning agent with stable framework structure as claimed in claim 1, characterized in that:
the metal salt is chromium nitrate, zirconium chloride, zirconium sulfate, aluminum nitrate and ferric sulfate.
3. The preparation method of carboxylic acid ligand MOFs nano-tanning agent with stable framework structure according to claim 2, characterized by that:
the carboxylic acid organic ligand is terephthalic acid and 2-amino terephthalic acid.
4. The preparation method of carboxylic acid ligand MOFs nano-tanning agent with stable framework structure according to claim 3, characterized by comprising the following steps:
the mass fraction of the metal salt solution is 2-10%; the mass fraction of the carboxylic acid organic ligand solution is 1-30%.
5. The preparation method of carboxylic acid ligand MOFs nano-tanning agent with stable framework structure according to claim 4, characterized by comprising the following steps:
the hydrothermal reaction temperature is 100-220 ℃.
6. The preparation method of carboxylic acid ligand MOFs nano-tanning agent with stable framework structure as claimed in claim 5, characterized in that:
the calcining and activating temperature is 120-300 ℃.
7. The preparation method of the carboxylic acid ligand MOFs nano-tanning agent with the stable framework structure is prepared by the preparation method of claim 1.
8. The application of the carboxylic acid ligand MOFs nano tanning agent with stable frame structure prepared by the preparation method of claim 1 in leather tanning is characterized in that:
the specific tanning comprises the following steps, wherein the following fractions are mass fractions:
firstly, weighing the mass of the pickled skin as the reference mass of the tanning process; adding sodium chloride and water into the rotary drum, wherein the mass of the water is 100-200% of the reference, the mass of the sodium chloride is 6-10% of the reference, 0.5-2.5% of formic acid or sulfuric acid solution of the reference is added, the pH value of bath liquid in the rotary drum is adjusted to 1.5-3.5, and the pickled Chinese cabbage is placed in the rotary drum and rotated for 30 min; then adding a standard 0.1-15% MOFs nano tanning agent into the bath lotion, tanning for 0.5-10 h, then adding a standard 0.5-2.5% sodium bicarbonate or sodium formate solution, adjusting the pH value of the bath lotion in the rotary drum to 3.8-6.0, and continuing to rotate for 20-60 min; finally, the drum is stopped overnight, and water is washed out of the drum the next day.
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| CN113480905A (en) * | 2021-08-04 | 2021-10-08 | 陕西科技大学 | Leather coating with fluorescent response to benzene-series VOCs and preparation method thereof |
| CN114574637A (en) * | 2022-03-18 | 2022-06-03 | 陕西科技大学 | Non-chromium tanning process based on POSS-COONa and non-chromium metal salt |
| CN116397058A (en) * | 2023-05-12 | 2023-07-07 | 陕西科技大学 | Bimetal-based metal-organic framework loaded non-chromium metal salt tanning agent and preparation method thereof |
| CN116397057A (en) * | 2023-05-12 | 2023-07-07 | 陕西科技大学 | Tanning method for in-situ growth of metal-organic framework nano tanning agent between collagen fibers |
| CN116426699A (en) * | 2023-03-25 | 2023-07-14 | 嘉兴宏麟皮化有限公司 | Environment-friendly tanning agent and preparation method thereof |
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| CN113480905A (en) * | 2021-08-04 | 2021-10-08 | 陕西科技大学 | Leather coating with fluorescent response to benzene-series VOCs and preparation method thereof |
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| CN116397057A (en) * | 2023-05-12 | 2023-07-07 | 陕西科技大学 | Tanning method for in-situ growth of metal-organic framework nano tanning agent between collagen fibers |
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| CN116397057B (en) * | 2023-05-12 | 2024-02-02 | 陕西科技大学 | Tanning method for in-situ growth of metal-organic framework nano tanning agent between collagen fibers |
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Application publication date: 20210706 |