CN113122041B - High-efficiency antibacterial leather finishing agent containing double-component halide perovskite and preparation method thereof - Google Patents

High-efficiency antibacterial leather finishing agent containing double-component halide perovskite and preparation method thereof Download PDF

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CN113122041B
CN113122041B CN202110511723.8A CN202110511723A CN113122041B CN 113122041 B CN113122041 B CN 113122041B CN 202110511723 A CN202110511723 A CN 202110511723A CN 113122041 B CN113122041 B CN 113122041B
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halide perovskite
finishing agent
agent containing
leather finishing
component halide
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CN113122041A (en
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范倩倩
卫思颖
马建中
温璐
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides

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Abstract

The invention discloses a high-efficiency antibacterial leather finishing agent containing double-component halide perovskite and a preparation method thereof. According to the invention, the metal ions of the bi-component halide perovskite and the photocatalysis effect thereof can realize efficient synergistic antibacterial, so that the antibacterial property of the traditional leather finishing agent is greatly enhanced. The finishing agent can be used on the surface of base materials such as leather, paper, glass, fabrics and the like to endow the base materials with good antibacterial performance.

Description

High-efficiency antibacterial leather finishing agent containing double-component halide perovskite and preparation method thereof
Technical Field
The invention belongs to the field of functional leather finishing agents, and particularly relates to a high-efficiency antibacterial leather finishing agent containing double-component halide perovskite and a preparation method thereof.
Background
The leather industry is one of the support industries of the light industry in China, leather products are accepted and favored by consumers all the time, and particularly leather products are fashionable, durable, cold-proof and warm-keeping. However, the leather products are easy to breed bacteria after being worn for a long time, which causes certain trouble for consumers. The finishing agent, as a material applied to the surface of leather, often imparts special functionality to the leather. With the increasing demand of people for the hygienic performance of products, the development of a leather finishing agent with high-efficiency antibacterial function is just essential.
Two-component halide perovskite (A)2BIBIIX6，A=CH3NH3 +、CH(NH2)2+Or Cs+Etc., X = Cl-、Br-Or I-，BI=Ag+、Cu+、In+Etc. BII=Bi3+、Sb3+Etc.) as a novel semiconductor material, since it has a strong light-absorbing ability,The advantages of adjustable band gap, low price of raw materials, low toxicity and the like (Angewandte Chemie International Edition, 2019, 58: 7263-.
Disclosure of Invention
The invention aims to provide an efficient antibacterial leather finishing agent containing double-component halide perovskite and a preparation method thereof, and the related perovskite self metal ions and the photocatalysis thereof can realize efficient synergistic antibacterial and greatly enhance the antibacterial property of the traditional leather finishing agent. In addition, the obtained perovskite has adjustable size (from micron level to nanometer level), and the metal ion components are adjustable, so that the requirements of different composite systems can be met, and the problem that the traditional lead-based perovskite is toxic can be avoided.
The technical scheme adopted by the invention is as follows:
a preparation method of a high-efficiency antibacterial leather finishing agent containing double-component halide perovskite comprises the following steps of firstly, adding a series halide metal salt precursor into a glass reaction bottle containing a polar solvent, and carrying out magnetic stirring and ultrasonic treatment to obtain a uniform and transparent precursor solution; then, dropwise adding the precursor solution into a nonpolar solvent in a high-speed stirring state, continuously stirring for a certain time, and centrifuging to obtain a double-component halide perovskite; the obtained perovskite is compounded with a film forming material which is commonly used in leather finishing, and the high-efficiency antibacterial leather finishing agent containing the double-component halide perovskite is obtained.
A preparation method of a high-efficiency antibacterial leather finishing agent containing double-component halide perovskite comprises the following steps:
step one, preparing a precursor solution: first, AX and B are mixedIX and BIIX3Adding into a glass reaction bottle filled with polar solvent, and performing ultrasonic treatment to obtain uniform transparent precursor solution, wherein A = CH3NH3 +、CH(NH2)2+Or Cs+，BI=Ag+、Cu+、Na+、Li+、K+、Rb+、Au+Or In+，BII=Bi3+、In3+、Sb3+、In3+、Ga3+、Sc3+Or Y3+，X=Cl-、Br-Or I-；
Step two, preparing a double-component halide perovskite: dropwise adding a certain amount of precursor solution into isopropanol, dichloromethane, ethanol, toluene or n-hexane under a high-speed stirring state, continuously stirring at room temperature for 5-60 min after dropwise adding, wherein the stirring speed is 200-1000 rpm, centrifuging the product for 10-30 min after the reaction is finished, and taking bottom precipitate to obtain the bi-component halide perovskite;
step three, preparing the high-efficiency antibacterial leather finishing agent containing the double-component halide perovskite: and (3) adding the bi-component halide perovskite obtained in the step two into a film forming material, and compounding for 0.5-3 h by means of magnetic stirring and ultrasonic action to obtain the high-efficiency antibacterial leather finishing agent containing the bi-component halide perovskite.
In the first step, the polar solvent is dimethyl sulfoxide or N, N-dimethylformamide; AX, BIX、BIIX3The mass volume ratio of the polar solvent to the solvent is (6-10 mg), (1-4 mg), (6-10 mg) and (0.6-1.2 mL).
In the second step, the volume ratio of the precursor solution to isopropanol, dichloromethane, ethanol, toluene or n-hexane is (0.1-10): 50-150.
In the third step, the film-forming material is casein, acrylic resin, polyurethane, chitosan, zein, gelatin or nitrocellulose.
The high-efficiency antibacterial leather finishing agent containing the double-component halide perovskite is prepared by the preparation method.
The invention has the following advantages:
1. the invention relates to a high-efficiency antibacterial leather finishing agent containing double-component halide perovskite and a preparation method thereof.
2. By utilizing the metal ions of the bi-component halide perovskite and the photocatalysis effect thereof, the efficient synergistic antibacterial can be realized, and the antibacterial property of the traditional leather finishing agent is greatly enhanced.
Drawings
FIG. 1 is a graph showing the comparison of the antibacterial effect of the leather samples before and after the coating with the highly antibacterial leather finishing agent containing two-component halide perovskite in example 2.
FIG. 2 is a graph comparing the sizes of two-component halide perovskites prepared with different volume ratios of precursor solution to isopropanol in example 1.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
A preparation method of a high-efficiency antibacterial leather finishing agent containing double-component halide perovskite comprises the following steps:
the method comprises the following steps: first, AX (a = CH)3NH3 +、CH(NH2)2+Or Cs+Etc., X = Cl-、Br-Or I-）、BIX（BI=Ag+、Cu+、Na+、Li+、K+、Rb+、Au+Or In+，X=Cl-、Br-Or I-) And BIIX3（BII=Bi3+、In3+、Sb3+、In3+、Ga3+、Sc3+Or Y3+，X=Cl-、Br-Or I-) Adding into a glass reaction bottle filled with polar solvent such as dimethyl sulfoxide or N, N-dimethylformamide, etc., and performing ultrasonic treatment to obtain uniform and transparent precursor solution, wherein AX and BIX、BIIX3The mass volume ratio of the polar solvent to the solvent is (6-10 mg), (1-4 mg), (6-10 mg) and (0.6-1.2 mL).
Step two: and (2) transferring a certain amount of precursor solution by using a liquid transfer gun, and dropwise adding the precursor solution into isopropanol, dichloromethane, ethanol, toluene or n-hexane under a high-speed stirring state, wherein the volume ratio of the precursor solution to the isopropanol, the dichloromethane, the ethanol, the toluene or the n-hexane is (0.1-10) to (50-150). And after the dropwise addition is finished, continuously stirring and reacting for 5-60 min at room temperature, wherein the stirring speed is 200-1000 rpm. And after the reaction is finished, centrifuging the product for 10-30 min, and taking the bottom precipitate to obtain the double-component halide perovskite.
Step three: the obtained bi-component halide perovskite is added into film forming materials such as casein, acrylic resin, polyurethane, chitosan, zein, gelatin or nitrocellulose and the like, and is compounded for 0.5-3 hours under the action of magnetic stirring and ultrasonic, so that the high-efficiency antibacterial leather finishing agent containing the bi-component halide perovskite is obtained.
Example 1:
the method comprises the following steps: first, AX (a = Cs)+，X=Br-）、BIX（BI=Ag+，X=I-) And BIIX3（BII=Bi3+，X=I-) Adding into a glass reaction bottle filled with N, N-dimethylformamide for ultrasonic treatment to obtain uniform and transparent precursor solution, wherein AX and BIX、BIIX3The mass-to-volume ratio of N, N-dimethylformamide is 7mg:3mg: 6mg:1 mL.
Step two: and (3) transferring a certain amount of precursor solution by using a liquid transfer gun, and dropwise adding the precursor solution into isopropanol in a high-speed stirring state, wherein the volume ratio of the precursor solution to the isopropanol is 1: 20. After the dropwise addition, the reaction was continued for 30 min at room temperature with stirring at 600 rpm. And after the reaction is finished, centrifuging the product for 20 min, and taking the bottom precipitate to obtain the bi-component halide perovskite.
Step three: the obtained bi-component halide perovskite is added into a gelatin film-forming material, and is compounded for 1h by means of magnetic stirring and ultrasonic action, so that the high-efficiency antibacterial leather finishing agent containing the bi-component halide perovskite is obtained.
Example 2:
the method comprises the following steps: first, AX (a = CH)3NH3 +，X=Br-）、BIX（BI=Cu+，X=Br-) And BIIX3（BII=Bi3+，X=Br-) Adding into a glass reaction bottle filled with dimethyl sulfoxide for ultrasonic treatment to obtain uniform and transparent precursor solution, wherein AX and BIX、BIIX3The mass-to-volume ratio of the total amount of the active carbon to the dimethyl sulfoxide was 6mg:2mg: 7mg:0.8 mL.
Step two: and (3) transferring a certain amount of precursor solution by using a liquid transfer gun, and dropwise adding the precursor solution into ethanol in a high-speed stirring state, wherein the volume ratio of the precursor solution to the ethanol is 3: 700. After the addition, the reaction was continued at room temperature with stirring at 300rpm for 20 min. And after the reaction is finished, centrifuging the product for 10 min, and taking the bottom precipitate to obtain the bi-component halide perovskite.
Step three: the obtained bi-component halide perovskite is added into a casein film forming material, and is compounded for 0.5h under the action of magnetic stirring and ultrasonic, so that the high-efficiency antibacterial leather finishing agent containing the bi-component halide perovskite is obtained.
Example 3:
the method comprises the following steps: first, AX (a = CH (NH)2)2+，X=I-）、BIX（BI=Au+，X=Br-) And BIIX3（BII=Sb3+，X=Cl-) Adding into a glass reaction bottle filled with dimethyl sulfoxide for ultrasonic treatment to obtain uniform and transparent precursor solution, wherein AX and BIX、BIIX3The mass-to-volume ratio of the total amount of the active carbon to the dimethyl sulfoxide was 10mg to 3mg to 7mg to 0.9 mL.
Step two: and (3) transferring a certain amount of precursor solution by using a liquid transfer gun, and dropwise adding the precursor solution into toluene in a high-speed stirring state, wherein the volume ratio of the precursor solution to the toluene is 3: 50. After the dropwise addition, the reaction was continued at room temperature with stirring at 900rpm for 10 min. And after the reaction is finished, centrifuging the product for 15 min, and taking the bottom precipitate to obtain the bi-component halide perovskite.
Step three: the obtained bi-component halide perovskite is added into an acrylic resin film-forming material, and is compounded for 2 hours by means of magnetic stirring and ultrasonic action, so that the high-efficiency antibacterial leather finishing agent containing the bi-component halide perovskite is obtained.
The double-component halide perovskite has an ionic structure, and the components are adjustable, so that the metal ionic component with excellent antibacterial function is introduced into the perovskite structure, and the perovskite structure becomes a high-efficiency antibacterial agent. Based on the above, the high-efficiency antibacterial leather finishing agent containing the double-component halide perovskite can be obtained by compounding the high-efficiency antibacterial leather finishing agent with a film forming material for leather finishing such as casein, polyacrylate or polyurethane.
FIG. 1 is a comparative graph showing the antibacterial effect of leather samples before and after finishing with the highly antibacterial leather finishing agent containing two-component halide perovskite of example 2, and it can be seen that the leather samples after finishing with the leather finishing agent containing two-component halide perovskite has a significant antibacterial effect against Candida albicans.
FIG. 2 is a graph comparing the sizes of the two-component halide perovskite obtained by the method described in example 1 and the two-component halide perovskite obtained under the same process conditions when the volume ratio of the precursor solution to isopropanol is 1: 50 and 1: 5. As can be seen from the figure, the size of the two-component halide perovskite can be controlled from micron-scale to nanometer-scale by adjusting the volume ratio of the precursor solution to the isopropanol.
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 (5)

1. A preparation method of a high-efficiency antibacterial leather finishing agent containing bi-component halide perovskite is characterized by comprising the following steps:
firstly, adding a series of halide metal salt precursors into a glass reaction bottle containing a polar solvent for magnetic stirring and ultrasonic treatment to obtain a uniform and transparent precursor solution; then, dropwise adding the precursor solution into a nonpolar solvent in a high-speed stirring state, continuously stirring for a certain time, and centrifuging to obtain a double-component halide perovskite; compounding the obtained perovskite with a film forming material commonly used in leather finishing to obtain the high-efficiency antibacterial leather finishing agent containing the double-component halide perovskite;
the method specifically comprises the following steps:
step one, preparing a precursor solution: first, AX and B are mixedIX and BIIX3Adding into a glass reaction bottle filled with polar solvent, and performing ultrasonic treatment to obtain uniform transparent precursor solution, wherein A = CH3NH3 +、CH(NH2)2+Or Cs+，BI=Ag+、Cu+、Na+、Li+、K+、Rb+、Au+Or In+，BII=Bi3+、In3+、Sb3+、In3+、Ga3+、Sc3+Or Y3+，X=Cl-、Br-Or I-；
Step two, preparing a double-component halide perovskite: dropwise adding a certain amount of precursor solution into isopropanol, dichloromethane, ethanol, toluene or n-hexane under a high-speed stirring state, continuously stirring at room temperature for 5-60 min after dropwise adding, wherein the stirring speed is 200-1000 rpm, centrifuging the product for 10-30 min after the reaction is finished, and taking bottom precipitate to obtain the bi-component halide perovskite;
step three, preparing the high-efficiency antibacterial leather finishing agent containing the double-component halide perovskite: and (3) adding the bi-component halide perovskite obtained in the step two into a film forming material, and compounding for 0.5-3 h by means of magnetic stirring and ultrasonic action to obtain the high-efficiency antibacterial leather finishing agent containing the bi-component halide perovskite.
2. The preparation method of the high-efficiency antibacterial leather finishing agent containing the double-component halide perovskite as claimed in claim 1 is characterized by comprising the following steps:
in the first step, the polar solvent is dimethyl sulfoxide or N, N-dimethylformamide; AX, BIX、BIIX3The mass-to-volume ratio of the polar solvent to the solvent is 6-10 mg: 1-4 mg: 6-10 mg: 0.6-1.2 mL.
3. The preparation method of the high-efficiency antibacterial leather finishing agent containing the double-component halide perovskite as claimed in claim 2, which is characterized by comprising the following steps:
in the second step, the volume ratio of the precursor solution to isopropanol, dichloromethane, ethanol, toluene or n-hexane is 0.1-10: 50-150.
4. The preparation method of the high-efficiency antibacterial leather finishing agent containing the double-component halide perovskite as claimed in claim 3, which is characterized by comprising the following steps:
in the third step, the film-forming material is casein, acrylic resin, polyurethane, chitosan, zein, gelatin or nitrocellulose.
5. The high-efficiency antibacterial leather finishing agent containing the double-component halide perovskite prepared by the preparation method as claimed in claim 1.
CN202110511723.8A 2021-05-11 2021-05-11 High-efficiency antibacterial leather finishing agent containing double-component halide perovskite and preparation method thereof Active CN113122041B (en)

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CN108645895A (en) * 2018-06-01 2018-10-12 中国石油大学(华东) A kind of porphyrin modified perovskite nanometer grain preparation method and its gas sensor
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CN111644200A (en) * 2020-04-30 2020-09-11 北京理工大学 Modified organic-metal halide perovskite photocatalyst, preparation method and application thereof
CN112680953A (en) * 2020-12-17 2021-04-20 陕西科技大学 Antibacterial fabric based on perovskite quantum dots and preparation method thereof

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CN1813539A (en) * 2006-01-13 2006-08-09 暨南大学 Inorganic compound antibacterial agent, and its preparing method and use
CN106634327A (en) * 2016-10-25 2017-05-10 齐鲁工业大学 Antibacterial leather finishing agent and preparation method thereof
CN107934916A (en) * 2017-11-16 2018-04-20 中山大学 It is a kind of to stablize the nanocrystalline preparation methods of unleaded full-inorganic double-perovskite A2BB ' X6
CN108217718A (en) * 2018-03-13 2018-06-29 南方科技大学 ABX3Synthesis method of perovskite nanocrystalline and product and application thereof
CN108645895A (en) * 2018-06-01 2018-10-12 中国石油大学(华东) A kind of porphyrin modified perovskite nanometer grain preparation method and its gas sensor
CN109569727A (en) * 2018-12-14 2019-04-05 北京化工大学 A kind of preparation and application of double halides perovskite photochemical catalysts of highly effective hydrogen yield
CN111644200A (en) * 2020-04-30 2020-09-11 北京理工大学 Modified organic-metal halide perovskite photocatalyst, preparation method and application thereof
CN112680953A (en) * 2020-12-17 2021-04-20 陕西科技大学 Antibacterial fabric based on perovskite quantum dots and preparation method thereof

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