CN115283227A - Preparation method of antibacterial antistatic anti-ultraviolet polyurethane synthetic leather - Google Patents
Preparation method of antibacterial antistatic anti-ultraviolet polyurethane synthetic leather Download PDFInfo
- Publication number
- CN115283227A CN115283227A CN202111526317.5A CN202111526317A CN115283227A CN 115283227 A CN115283227 A CN 115283227A CN 202111526317 A CN202111526317 A CN 202111526317A CN 115283227 A CN115283227 A CN 115283227A
- Authority
- CN
- China
- Prior art keywords
- synthetic leather
- polyurethane synthetic
- graphene oxide
- ultraviolet
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
- B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
-
- 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
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
-
- 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
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
Abstract
The invention provides a preparation method of antibacterial antistatic anti-ultraviolet polyurethane synthetic leather, which comprises the following steps: dissolving dopamine hydrochloride in a Tris solution to prepare a dopamine solution; adding polyurethane synthetic leather into the dopamine solution, and stirring for reaction to obtain polydopamine-coated polyurethane synthetic leather; soaking the polydopamine-coated polyurethane synthetic leather into a graphene oxide aqueous solution, and obtaining graphene oxide-coated polyurethane synthetic leather after soaking; and (3) immersing the graphene oxide coating polyurethane synthetic leather into a copper ion aqueous solution, sequentially adding an alkali liquor and a reducing agent, carrying out reduction reaction, and finishing the reaction to obtain the antibacterial antistatic ultraviolet-proof polyurethane synthetic leather. The preparation method has simple process, no pollution to the environment and low cost; the prepared polyurethane synthetic leather has high-efficiency and lasting antibacterial property, and the antibacterial property has good washing fastness; and simultaneously has uvioresistant performance and antistatic performance.
Description
Technical Field
The invention belongs to the technical field of synthetic leather, and particularly relates to a preparation method of antibacterial, antistatic and ultraviolet-proof polyurethane synthetic leather.
Background
Because of soft hand feeling, strong mechanical property and low price, the polyurethane synthetic leather has gradually increased use amount and gradually replaces natural leather. With the improvement of living standard, the requirements of people on synthetic leather do not meet single functionality, and gradually develop towards two or more special functionalities, such as antistatic, antibacterial, flame retardant and ultraviolet resistant properties.
The method for preparing the functional polyurethane synthetic leather generally comprises the steps of adding various functional additives into polyurethane slurry, and coating the slurry on base cloth, but various additives are required to be used in the processing process, so that the use performances of the synthetic leather, such as hand feeling, luster and the like, are influenced to a certain extent. Inspired by the adhesion mechanism of mussels, dopamine has been widely used as an excellent candidate material for surface modification due to its advantages of simple composition, mild reaction conditions, and general applicability to various matrix materials. The dopamine is self-polymerized on the surface of the synthetic leather to form an adhesion layer, and various functional nano materials are firmly fixed on the surface of the adhesion layer, so that the synthetic leather can be endowed with various functionalities.
The cuprous oxide nano particles have good physical and chemical properties and wide application prospect, and the polyurethane synthetic leather treated by the cuprous oxide has the characteristics of conductivity, antibiosis, ultraviolet resistance and the like. Especially, the cuprous oxide nano particles have the biological killing property on bacteria and viruses, and have important significance on the application of the cuprous oxide nano particles in the medical fields of home textiles, medical treatment, protective clothing and the like. Although cuprous oxide has excellent antibacterial performance, the development of cuprous oxide is limited by the problems of rapid recombination of photogenerated electrons and holes and easy agglomeration of nano particles.
The graphene has extremely high specific surface area, good conductivity and carrier mobility, and is an ideal carrier for preparing the metal oxide nano composite material. Meanwhile, the graphene serving as a functional nano material can endow the high polymer material with functions of static resistance, heat conduction, electric conduction, far infrared emission and the like.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of antibacterial antistatic ultraviolet-proof polyurethane synthetic leather, the synthetic leather loaded with graphene/cuprous oxide polyurethane prepared by the method has high-efficiency and lasting antibacterial property and good washing fastness, and the sterilization rate can still reach more than 98% after 30 times of washing; simultaneously has uvioresistant performance and antistatic performance; and the preparation process is simple, does not cause pollution to the environment and has low cost.
A preparation method of antibacterial antistatic anti-ultraviolet polyurethane synthetic leather comprises the following steps:
(1) Dissolving dopamine hydrochloride in a Tris solution to prepare a dopamine solution;
(2) Adding polyurethane synthetic leather into the dopamine solution, and stirring for reaction to obtain polydopamine-coated polyurethane synthetic leather;
(3) Soaking the polydopamine-coated polyurethane synthetic leather into a graphene oxide aqueous solution, and obtaining graphene oxide-coated polyurethane synthetic leather after soaking;
(4) Immersing the graphene oxide coating polyurethane synthetic leather into copper ions (Cu) 2+ ) And (3) sequentially adding alkali liquor and a reducing agent into the aqueous solution, carrying out reduction reaction, and finishing the reaction to obtain the antibacterial antistatic anti-ultraviolet polyurethane synthetic leather.
In the above preparation method, in step (1):
preferably, the mass volume concentration of the dopamine in the dopamine solution is 0.5-5 g/L. More preferably 1 to 3g/L.
Preferably, the pH value of the dopamine solution is 8-8.5. Further preferably 8.5.
Preferably, the Tris (Tris hydroxymethyl aminomethane) solution has a Tris concentration of 0.5 to 4g/L by mass volume. More preferably 1 to 3g/L.
In the above preparation method, in the step (2):
preferably, the polyurethane synthetic leather is one or more of solvent type polyurethane synthetic leather, water-based polyurethane synthetic leather and solvent-free polyurethane synthetic leather.
Preferably, the temperature of the stirring reaction is 25-35 ℃, and the time is 12-48 h. More preferably, the stirring reaction time is 12 to 28 hours.
Preferably, the polyurethane synthetic leather is washed before being added into the dopamine solution.
Preferably, in the step (2), the obtained polydopamine-coated polyurethane synthetic leather is washed and dried, and then is soaked in the graphene oxide aqueous solution in the step (3).
In the above preparation method, in the step (3):
preferably, the graphene oxide aqueous solution has a mass volume concentration of 0.5 to 5g/L. More preferably 0.5 to 2g/L. More preferably 2g/L.
Preferably, the graphene oxide sheets are single or multi-sheets.
Preferably, the graphene oxide sheets have a size of 5 to 30 μm and a thickness of 0.4 to 20nm.
Preferably, the soaking time of the polydopamine coated polyurethane synthetic leather is 0.5-24 h. More preferably, the soaking time of the polydopamine coated polyurethane synthetic leather is 0.5 to 3 hours. More preferably 0.5 to 2 hours.
Preferably, in the step (3), the obtained graphene oxide coating polyurethane synthetic leather is washed, dried in vacuum at 70-90 ℃, and then soaked in the copper ion aqueous solution in the step (4).
In the above preparation method, in the step (4):
preferably, the copper ion aqueous solution is one or more of copper sulfate aqueous solution, copper nitrate aqueous solution and copper chloride aqueous solution.
Preferably, the molar volume concentration of copper ions in the aqueous solution of copper ions is 0.01 to 1mol/L. More preferably 0.1 to 1mol/L.
To make Cu 2+ The aqueous solution is dispersed more uniformly, and preferably, before the graphene oxide coating polyurethane synthetic leather is immersed, a surfactant is added into the copper ion aqueous solution.
Further preferably, the surfactant is one or more of polyvinylpyrrolidone, polyethylene glycol, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
Preferably, the reducing agent is sodium sulfite (Na) 2 S 2 O 4 ) L-ascorbic acid, glucose, sodium borohydride (NaBH) 4 ) One or more of (a).
Preferably, the amount of the reducing agent added is 0.01 to 1.5mol/L.
Preferably, the alkali liquor is one or a mixture of a sodium hydroxide (NaOH) aqueous solution and a potassium hydroxide (KOH) aqueous solution. More preferably an aqueous sodium hydroxide solution.
More preferably, the molar volume concentration of the alkali liquor is 0.5-3 mol/L. More preferably 1 to 2mol/L.
Preferably, the reaction temperature of the reduction reaction is 50-80 ℃, and the reaction time is 0.5-2 h. More preferably, the reaction temperature of the reduction reaction is 70 to 80 ℃ and the reaction time is 1 to 2 hours.
In order to ensure that the graphene oxide is completely reduced into reduced graphene oxide, preferably, after the reduction reaction is finished, the product is stirred in a water bath at 50-150 ℃ for 0.5-3 h, and after the stirring is finished, the antibacterial antistatic anti-ultraviolet polyurethane synthetic leather is obtained by drying.
More preferably, the temperature of the water bath is 80 to 100 ℃ and the time is 2 to 3 hours.
As specific optimization, the preparation method of the antibacterial antistatic ultraviolet-proof polyurethane synthetic leather comprises the following steps:
(1) Dissolving Tris in water to prepare a Tris solution (Tris buffer solution), adjusting the pH value to 8-8.5, dissolving dopamine hydrochloride in the Tris solution to prepare a dopamine solution with the mass volume concentration of 0.5-5 g/L;
(2) Adding the cleaned polyurethane synthetic leather into the prepared dopamine solution, controlling the reaction temperature at 25-35 ℃, stirring for reacting for 24-48 h, taking out, washing and drying to obtain the polyurethane synthetic leather coated with polydopamine (polydopamine-coated polyurethane synthetic leather);
(3) Soaking the polyurethane synthetic leather coated with the polydopamine prepared in the step (2) into a graphene oxide aqueous solution with the mass volume concentration of 0.5-5 g/L, taking out after soaking, washing, drying, and repeating the steps for multiple times to obtain the graphene oxide coating-loaded polyurethane synthetic leather (graphene oxide coating polyurethane synthetic leather);
(4) Immersing the graphene oxide-loaded coating polyurethane synthetic leather prepared in the step (3) into Cu with the molar volume concentration of 0.01-1 mol/L 2+ Adding surfactant to the solution to make Cu 2+ Dispersing the aqueous solution more uniformly, adding NaOH (aqueous solution) to make Cu 2+ Formation of Cu (OH) 2 Precipitating, finally adding a reducing agent for reduction at 50-80 ℃, and after the reaction is finished, taking out the product from the solution, washing and drying;
(5) And (5) stirring the product dried in the step (4) in a water bath at 50-150 ℃ for 0.5-3 h to ensure that the graphene oxide is completely reduced into reduced graphene oxide, and drying to obtain the reduced graphene oxide/cuprous oxide coating-loaded polyurethane synthetic leather (antibacterial antistatic anti-ultraviolet polyurethane synthetic leather).
In the step (4), adding NaOH aqueous solution and then adding Cu 2+ React with hydroxide ions to form Cu (OH) 2 Precipitating; cu (OH) after addition of reducing agent 2 The precipitate is reduced into cuprous oxide in situ, the generated cuprous oxide is combined with graphene oxide on the surface of the polyurethane synthetic leather through physical adsorption, electrostatic adsorption and charge transfer, and the cuprous oxide is fixed on the surface of the polyurethane synthetic leather. Reducing agent Cu (OH) 2 And reducing the precipitate into cuprous oxide, and simultaneously reducing the graphene oxide into reduced graphene oxide.
Wherein the generated cuprous oxide is nano-scale, and the average particle size is 200 nm-1 μm.
The invention provides a preparation method of antibacterial antistatic anti-ultraviolet polyurethane synthetic leather, which comprises the following steps: firstly, coating a layer of polydopamine on the surface of the polyurethane synthetic leather by a mild method, wherein the polydopamine can play a role of an adhesive; and then putting the polydopamine-finished polyurethane synthetic leather into a graphene oxide aqueous solution, soaking, washing, drying, and circulating for multiple times to obtain the graphene oxide-loaded polyurethane synthetic leather. And finally, under the action of a reducing agent, copper ions grow cuprous oxide nanoparticles in situ on the surface of the polyurethane synthetic leather through a one-step impregnation process, and graphene oxide is reduced to reduced graphene oxide.
According to the invention, the surface of the polyurethane synthetic leather is modified, a polydopamine layer is adhered to a graphene oxide nanosheet, cuprous oxide nanoparticles are further synthesized in situ, and graphene oxide is reduced in one step at the same time, so that the multifunctional polyurethane synthetic leather with antibacterial, antistatic and ultraviolet-proof functions is prepared. Reduced graphene oxide as a loading layer has proven to be an effective alternative to improve the dispersibility, stability and antibacterial activity of cuprous oxide nanoparticles.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the multifunctional coating polyurethane synthetic leather (antibacterial antistatic anti-ultraviolet polyurethane synthetic leather) loaded with the reduced graphene oxide/cuprous oxide, firstly, the polyurethane synthetic leather is placed in an alkaline buffer solution (dopamine solution), and dopamine hydrochloride is subjected to polymerization reaction on the surface of the polyurethane synthetic leather to form a polydopamine film; the poly-dopamine adheres the graphene oxide to the surface of the synthetic leather through the in-situ reduction effect and coordination effect of a catechol group in the molecule of the poly-dopamine; the graphene oxide and the nano cuprous oxide are combined through physical adsorption, electrostatic adsorption or charge transfer, and the nano cuprous oxide is fixed on the surface of the synthetic leather. The prepared polyurethane synthetic leather (antibacterial antistatic anti-ultraviolet polyurethane synthetic leather) carrying the reduced graphene oxide/cuprous oxide coating has good washing fastness and high-efficiency durable antibacterial property, and the sterilization rate can still reach more than 98% after 30 times of washing; meanwhile, the coating has good ultraviolet resistance and antistatic property; and the preparation method has simple process and is green and environment-friendly.
Drawings
In fig. 1: a is a scanning electron microscope picture of polyurethane synthetic leather; b is a scanning electron microscope image of the graphene oxide-loaded polyurethane synthetic leather prepared in example 1; c is a scanning electron microscope image of the reduced graphene oxide/cuprous oxide-loaded polyurethane synthetic leather prepared in example 1; d is a scanning electron microscope picture of the cross section of the polyurethane synthetic leather;
fig. 2 is a comparison diagram of the antibacterial properties of the reduced graphene oxide/cuprous oxide-loaded polyurethane synthetic leather and the polyurethane synthetic leather in example 1 of the present invention;
wherein 1a is an antibacterial property test result of the polyurethane synthetic leather on staphylococcus aureus; 1b is the antibacterial property test result of the polyurethane synthetic leather on escherichia coli; 2a is an antibacterial property test result of the load reduced graphene oxide/cuprous oxide polyurethane synthetic leather on staphylococcus aureus; 2b is an antibacterial property test result of the load reduced graphene oxide/cuprous oxide polyurethane synthetic leather on escherichia coli; 3a is an antibacterial property test result of the load reduced graphene oxide/cuprous oxide polyurethane synthetic leather to staphylococcus aureus after being washed for 30 times; and 3b is an antibacterial property test result of the loaded reduced graphene oxide/cuprous oxide polyurethane synthetic leather to escherichia coli after being washed for 30 times. .
Detailed Description
The present invention will be further illustrated by the following examples, but the present invention is not limited to the following examples.
Example 1
(1) Preparing a Tris buffer solution (Tris solution) with the concentration of 2g/L, adjusting the pH value to 8.5 by using NaOH, and dissolving dopamine hydrochloride into the Tris buffer solution to prepare the dopamine solution with the concentration of 2g/L.
(2) And (3) soaking the cleaned polyurethane synthetic leather in the prepared dopamine solution, controlling the reaction temperature to be 25 ℃, stirring for reaction for 24 hours, taking out, cleaning and drying to obtain the polyurethane synthetic leather coated with polydopamine.
(3) And (3) putting the polydopamine-coated polyurethane synthetic leather prepared in the step (2) into a graphene oxide aqueous solution with the concentration of 2g/L, soaking for 1h, taking out, washing with distilled water, drying in vacuum at 80 ℃, and repeating the steps for 5 times to obtain the graphene oxide-loaded polyurethane synthetic leather.
(4) Immersing the graphene oxide-loaded polyurethane synthetic leather prepared in the step (3) into CuSO with the concentration of 0.1mol/L 4 And (3) adding 2mol/L NaOH aqueous solution and 1 mol/L-ascorbic acid into the solution at the same time to perform reduction reaction for 1.5h at 80 ℃, taking the product out of the solution after the reaction is finished, washing the product with distilled water, and then drying the product in vacuum at 80 ℃.
(5) And (4) stirring the dried product prepared in the step (4) in a water bath at 100 ℃ for 2h to ensure that the graphene oxide is completely reduced into reduced graphene oxide, and drying to obtain the polyurethane synthetic leather loaded with the reduced graphene oxide/cuprous oxide coating.
Example 2
(1) Preparing a Tris buffer solution (Tris solution) with the concentration of 1g/L, adjusting the pH value to 8.5 by using NaOH, and then dissolving dopamine hydrochloride into the Tris buffer solution to prepare the dopamine solution with the concentration of 1 g/L.
(2) And (3) soaking the cleaned polyurethane synthetic leather in the prepared dopamine solution, controlling the reaction temperature to be 30 ℃, stirring for reacting for 16 hours, taking out, and cleaning to obtain the polyurethane synthetic leather coated with the polydopamine film.
(3) And (3) putting the polyurethane synthetic leather coated with the polydopamine film prepared in the step (2) into a graphene oxide aqueous solution with the concentration of 2g/L, soaking for 1.5h, taking out, washing with distilled water, drying in vacuum at 80 ℃, and repeating the steps for 4 times to obtain the graphene oxide-loaded polyurethane synthetic leather.
(4) Immersing the graphene oxide-loaded polyurethane synthetic leather prepared in the step (3) into CuCl with the concentration of 0.1mol/L 2 Adding 2mol/L NaOH aqueous solution and 0.1mol/L sodium sulfite into the solution at the same time, performing reduction reaction at 80 deg.C for 1.5h, taking out the product from the solution, and adding distilled waterAnd after washing, drying in vacuum at 80 ℃.
(5) And (4) stirring the dried product prepared in the step (4) in a water bath at 80 ℃ for 3 hours to ensure that the graphene oxide is completely reduced into reduced graphene oxide, and drying to obtain the polyurethane synthetic leather loaded with the reduced graphene oxide/cuprous oxide coating.
Example 3
(1) Preparing a Tris buffer solution (Tris solution) with the concentration of 3g/L, adjusting the pH value to 8.5 by using NaOH, and dissolving dopamine hydrochloride into the Tris buffer solution to prepare the dopamine solution with the concentration of 3g/L.
(2) And (3) soaking the cleaned polyurethane synthetic leather in the prepared dopamine solution, controlling the reaction temperature to be 35 ℃, stirring for reaction for 12 hours, taking out the polyurethane synthetic leather, and cleaning to obtain the polyurethane synthetic leather coated with the polydopamine film.
(3) And (3) putting the polyurethane synthetic leather coated with the polydopamine film prepared in the step (2) into a graphene oxide aqueous solution with the concentration of 2g/L, soaking for 0.5h, taking out, washing with distilled water, drying in vacuum at 80 ℃, and repeating the steps for 6 times to obtain the graphene oxide-loaded polyurethane synthetic leather.
(4) Immersing the polyurethane synthetic leather loaded with graphene oxide prepared in the step (3) into Cu (NO) with the concentration of 1mol/L 3 ) 2 And (3) adding 1mol/L NaOH solution and 0.2mol/L glucose into the solution at the same time to perform reduction reaction for 1.5h at 80 ℃, taking the product out of the solution after the reaction is finished, washing the product with distilled water, and drying the product in vacuum at 60 ℃.
(5) And (4) stirring the dried product prepared in the step (4) in a water bath at 90 ℃ for 2.5 hours to ensure that the graphene oxide is completely reduced into reduced graphene oxide, and drying to obtain the polyurethane synthetic leather loaded with the reduced graphene oxide/cuprous oxide coating.
Comparative example 1
The method is the same as example 1, except that no graphene loading layer is provided, and cuprous oxide is prepared in situ, and the specific preparation process is as follows:
(1) Preparing a Tris buffer solution (Tris solution) with the concentration of 2g/L, adjusting the pH value to 8.5 by using NaOH, and dissolving dopamine hydrochloride into the Tris buffer solution to prepare a dopamine solution with the concentration of 1 g/L.
(2) And (3) soaking the cleaned polyurethane synthetic leather in the prepared dopamine solution, controlling the reaction temperature to be 35 ℃, stirring for reaction for 24 hours, taking out, cleaning and drying to obtain the polyurethane synthetic leather coated with polydopamine.
Comparative example 2
The difference from example 1 is that no nano cuprous oxide is prepared in situ, and the specific preparation process is as follows:
(1) Preparing a Tris buffer solution (Tris solution) with the concentration of 2g/L, adjusting the pH value to 8.5 by using NaOH, and dissolving dopamine hydrochloride into the Tris buffer solution to prepare a dopamine solution with the concentration of 1 g/L.
(2) And (3) soaking the cleaned polyurethane synthetic leather in the prepared dopamine solution, controlling the reaction temperature to be 35 ℃, stirring for reaction for 24 hours, taking out, cleaning and drying to obtain the polyurethane synthetic leather coated with polydopamine.
(3) And (3) putting the polyurethane synthetic leather coated with the polydopamine prepared in the step (2) into a graphene oxide aqueous solution with the concentration of 2g/L, soaking for 1h, taking out, washing with distilled water, drying in vacuum at the temperature of 80 ℃, and repeating the steps for 5 times to obtain the graphene oxide-loaded polyurethane synthetic leather.
(4) And (4) immersing the graphene oxide-loaded polyurethane synthetic leather prepared in the step (3) into a NaOH aqueous solution with the concentration of 2mol/L (wherein the NaOH aqueous solution contains 1mol/L of L-ascorbic acid), carrying out reduction reaction for 1.5h at the temperature of 80 ℃, taking out the polyurethane synthetic leather from the solution after the reaction is finished, washing the polyurethane synthetic leather with distilled water, and then drying the polyurethane synthetic leather in vacuum at the temperature of 80 ℃.
(5) And (4) stirring the polyurethane synthetic leather loaded with the graphene oxide prepared in the step (4) in a water bath at 100 ℃ for 2 hours to ensure that the graphene oxide is completely reduced into reduced graphene oxide, and drying to obtain the polyurethane synthetic leather loaded with the reduced graphene oxide/cuprous oxide coating.
Comparative example 3
The difference from example 1 is that there is no poly-dopamine adhesion layer, and the specific preparation process is as follows:
(1) And (3) putting the cleaned polyurethane synthetic leather into a graphene oxide aqueous solution with the concentration of 2g/L, soaking for 1h, taking out, washing with distilled water, drying in vacuum at the temperature of 80 ℃, and repeating the steps for 5 times to obtain the graphene oxide-loaded polyurethane synthetic leather.
(2) Immersing the graphene oxide-loaded polyurethane synthetic leather prepared in the step (3) into CuSO with the concentration of 0.1mol/L 4 And (2) adding a 2mol/L NaOH solution and 1 mol/L-ascorbic acid into the solution at the same time, performing reduction reaction for 1.5 hours at 80 ℃, taking the product out of the solution after the reaction is finished, washing the product with distilled water, and drying the product in vacuum at 80 ℃.
(3) And (5) stirring the dried product prepared in the step (4) in a water bath at 100 ℃ for 2 hours to ensure that the graphene oxide is completely reduced into reduced graphene oxide, and drying to obtain the polyurethane synthetic leather loaded with the reduced graphene oxide/cuprous oxide coating.
Fig. 1 is a scanning electron microscope image of polyurethane synthetic leather (a), graphene oxide-loaded polyurethane synthetic leather (B) prepared in example 1, reduced graphene oxide/cuprous oxide coated polyurethane synthetic leather (C) prepared in example 1, and a cross section of polyurethane synthetic leather (D). The polyurethane leather is prepared by coating a layer of polyurethane on the surface of the superfine fiber, and it can be seen from A in FIG. 1 that the polyurethane leather on the surface is partially coated by the polyurethane, and the shape of the exposed fiber is relatively smooth. The polydopamine nanoparticles are formed by self polymerization of dopamine under an alkaline condition, the surface of the polyurethane synthetic leather is rough after polydopamine finishing, and the surface (B) of the polyurethane synthetic leather impregnated with graphene oxide is frequently grooved and rough, which is the lamellar particles of graphene oxide. As is apparent from C in FIG. 1, cuprous oxide nanoparticles are uniformly deposited on the surface of the polyurethane synthetic leather, and the particle size is 800-950nm. In FIG. 1, D is a cross-sectional electron microscope image of the polyurethane synthetic leather, which is formed by compounding superfine fibers and a polyurethane coating.
Fig. 2 is a comparative antibacterial property diagram of the reduced graphene oxide/cuprous oxide-loaded polyurethane synthetic leather and the polyurethane synthetic leather prepared in example 1. Wherein, 1 represents polyurethane synthetic leather, 2 represents polyurethane synthetic leather loaded with reduced graphene oxide/cuprous oxide, and 3 represents polyurethane synthetic leather loaded with reduced graphene oxide/cuprous oxide after washing for 30 times; a represents Staphylococcus aureus, and b represents Escherichia coli.
As can be seen from fig. 2, 1a and 1b, the polyurethane synthetic leather has substantially no antibacterial effect against staphylococcus aureus and escherichia coli. As can be seen from fig. 2a and 2b, the reduced graphene oxide/cuprous oxide-loaded polyurethane synthetic leather prepared in example 1 has excellent antibacterial effects against staphylococcus aureus and escherichia coli. The reason is that the reduced graphene oxide nanosheet on the polyurethane synthetic leather has higher specific surface area and hydrophobicity, so that the barrier property is enhanced, the adhesion and proliferation of bacteria on the polyurethane synthetic leather are reduced, and the cuprous oxide nanoparticles have good antibacterial activity on various microorganisms, so that the antibacterial property is improved.
Considering the washing fastness of the polyurethane synthetic leather loaded with the reduced graphene oxide/cuprous oxide, it can be known from experimental results that even after 30 times of washing, the polyurethane synthetic leather loaded with the reduced graphene oxide/cuprous oxide prepared in example 1 still has a good antibacterial effect on staphylococcus aureus and escherichia coli (see 3a and 3b in fig. 2), which indicates that the polyurethane synthetic leather loaded with the reduced graphene oxide/cuprous oxide prepared in example 1 has excellent antibacterial performance and washing durability with excellent antibacterial performance. Probably due to Cu 2 Strong hydrogen bonds are generated between the L-ascorbic acid and polyurethane around the O nano-particles, or hydrophobic rGO (reduced graphene oxide) nano-sheets and Cu on the synthetic leather 2 The O nano particles are wound together, so that the Cu content of the polyurethane synthetic leather after the water washing resistance treatment is improved 2 The adhesion capability of the O nano particles ensures that the polyurethane synthetic leather can keep good antibacterial performance after being washed for 30 times.
The antibacterial properties of the surface-treated polyurethane synthetic leathers obtained in examples 1 to 3 and comparative examples 1 to 3 are compared in Table 1.
TABLE 1 results of the tests of antibacterial properties of examples 1 to 3 and comparative examples 1 to 3
As can be seen from Table 1, the polyurethane synthetic leathers prepared in examples 1 to 3 and comparative example 3 both pass the tests of Escherichia coli and Staphylococcus aureus, and the bacteriostatic rate reaches over 99.99%. The surface of the comparative example 1 only has a polydopamine coating layer, and the polyurethane synthetic leather has no antibacterial effect; in comparative example 2, cuprous oxide is not prepared in situ, and only reduced graphene oxide is on the surface, but the load of graphene oxide is less, so that the polyurethane synthetic leather prepared in comparative example 2 has a poor antibacterial effect on escherichia coli and staphylococcus aureus, and the antibacterial requirement is not met.
Examples 1 to 3 and comparative examples 2 and 3 were tested for their antibacterial performance after washing according to the method in GB/T12490-2014, and it can be seen from table 1 that even after 30 washes, the fabric of comparative example 3 without the polydopamine adhesion layer is poor in water washing resistance and the antibacterial effect has not reached the standard; the polyurethane synthetic leathers prepared in examples 1-3 exhibited good wash durability, probably due to the hydrophobic reduced graphene oxide nanosheets and the Cu on the polyurethane synthetic leather 2 The O nano particles are wound together, so that the Cu of the polyurethane synthetic leather after the water washing resistant treatment is improved 2 The adhesion capability of the O nano particles ensures that the polyurethane synthetic leather can also keep good antibacterial performance. The reduced graphene oxide/cuprous oxide loaded multifunctional coating polyurethane synthetic leather prepared by the preparation method disclosed by the invention is proved to have high-efficiency and lasting antibacterial performance.
The antistatic properties of the surface-treated polyurethane synthetic leathers obtained in examples 1 to 3 and comparative examples 1 to 3 are compared in Table 2.
TABLE 2 results of testing antistatic Properties of examples 1 to 3 and comparative examples 1 to 3
The volume resistance of each example and each comparative example is tested by measuring the charge surface density of the polyurethane synthetic leather according to GB/T12703.4-2010 evaluation on electrostatic performance of textiles, and three points are randomly selected for each measurement. As can be seen from Table 2, the polyurethane synthetic leathers prepared in examples 1 to 3 and comparative example 3 all had good antistatic effects and volume resistances of 10 5 And the standard A level is reached. The main reason is related to the strong electron transmission capability of the reduced graphene oxide, and when the reduced graphene oxide and cuprous oxide are prepared by reduction, the volume resistance of the polyurethane synthetic leather is reduced, so that the range of static dissipative materials is reached, and the requirement of antistatic performance of common materials is met. Besides the large specific surface area and good conductivity of the reduced graphene oxide reduced from graphene oxide, the finally obtained polyurethane synthetic leather achieves a high-efficiency antistatic effect, and the good antistatic performance of the polyurethane synthetic leather is related to the conductivity of cuprous oxide metal nanoparticles.
The ultraviolet resistance properties of the surface-treated polyurethane synthetic leathers obtained in examples 1 to 3 and comparative examples 1 to 3 are compared in Table 3.
TABLE 3 test results of UV resistance of examples 1 to 3 and comparative examples 1 to 3
According to GB/T18830-2009 evaluation on ultraviolet resistance of textiles, polyurethane synthetic leather is flatly laid in a single layer during testing, different positions are respectively selected on the front side and the back side to be measured for 3 times, and an average value is calculated through 6 times of measurement to serve as a final testing result. As can be seen from Table 3, the polyurethane synthetic leathers prepared in examples 1 to 3 and comparative example 3 have good anti-ultraviolet effect, the UPF values reach more than 600, and the UVA and UVB transmissivity values are respectively less than 3%. These results exceed the standard excellent protection UPF rating (50). The reduced graphene oxide sheets have strong absorptivity in an ultraviolet region, so that the polyurethane synthetic leather loaded with the reduced graphene oxide has extremely high ultraviolet absorption capability. In addition, the existence of the reduced graphene oxide increases the thickness, and a large number of gaps among synthetic leather fibers are filled, so that the transmittance of ultraviolet light is greatly reduced.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the invention, and the invention is intended to cover all the modifications, equivalents and modifications of the above embodiments without departing from the spirit of the invention.
Claims (10)
1. A preparation method of antibacterial antistatic anti-ultraviolet polyurethane synthetic leather is characterized by comprising the following steps:
(1) Dissolving dopamine hydrochloride in a Tris solution to prepare a dopamine solution;
(2) Adding polyurethane synthetic leather into the dopamine solution, and stirring for reaction to obtain polydopamine-coated polyurethane synthetic leather;
(3) Soaking the polydopamine-coated polyurethane synthetic leather into a graphene oxide aqueous solution, and obtaining graphene oxide-coated polyurethane synthetic leather after soaking;
(4) And (3) immersing the graphene oxide coating polyurethane synthetic leather into a copper ion aqueous solution, sequentially adding an alkali liquor and a reducing agent, carrying out reduction reaction, and finishing the reaction to obtain the antibacterial antistatic anti-ultraviolet polyurethane synthetic leather.
2. The preparation method of the antibacterial antistatic anti-ultraviolet polyurethane synthetic leather according to claim 1, wherein the mass volume concentration of dopamine in the dopamine solution is 0.5-5 g/L;
the pH value of the dopamine solution is 8-8.5.
3. The preparation method of the antibacterial antistatic anti-ultraviolet polyurethane synthetic leather according to claim 1, wherein in the step (2), the stirring reaction is carried out at the temperature of 25-35 ℃ for 12-48 h.
4. The preparation method of the antibacterial antistatic anti-ultraviolet polyurethane synthetic leather according to claim 1, wherein the mass volume concentration of the graphene oxide aqueous solution is 0.5-5 g/L;
the soaking time of the polydopamine coating polyurethane synthetic leather is 0.5-24 h.
5. The method for preparing the antibacterial antistatic ultraviolet-proof polyurethane synthetic leather as claimed in claim 1, wherein the aqueous solution of copper ions is one or more of aqueous solution of copper sulfate, aqueous solution of copper nitrate and aqueous solution of copper chloride.
6. The preparation method of the antibacterial antistatic anti-ultraviolet polyurethane synthetic leather according to claim 1, wherein the molar volume concentration of copper ions in the copper ion aqueous solution is 0.01-1 mol/L.
7. The preparation method of the antibacterial antistatic anti-ultraviolet polyurethane synthetic leather according to claim 1, wherein a surfactant is added into the copper ion aqueous solution before the graphene oxide coated polyurethane synthetic leather is immersed.
8. The preparation method of the antibacterial antistatic anti-ultraviolet polyurethane synthetic leather according to claim 1, wherein the reducing agent is one or more of sodium sulfite, L-ascorbic acid, glucose and sodium borohydride;
the alkali liquor is one or the mixture of sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
9. The method for preparing the antibacterial antistatic anti-ultraviolet polyurethane synthetic leather according to claim 1, wherein the reaction temperature of the reduction reaction is 50-80 ℃ and the reaction time is 0.5-2 h.
10. The preparation method of the antibacterial antistatic anti-ultraviolet polyurethane synthetic leather according to claim 1, wherein after the reduction reaction is finished, the product is stirred in a water bath at 50-150 ℃ for 0.5-3 h, and after the stirring is finished, the antibacterial antistatic anti-ultraviolet polyurethane synthetic leather is obtained by drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111526317.5A CN115283227A (en) | 2021-12-14 | 2021-12-14 | Preparation method of antibacterial antistatic anti-ultraviolet polyurethane synthetic leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111526317.5A CN115283227A (en) | 2021-12-14 | 2021-12-14 | Preparation method of antibacterial antistatic anti-ultraviolet polyurethane synthetic leather |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115283227A true CN115283227A (en) | 2022-11-04 |
Family
ID=83819003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111526317.5A Pending CN115283227A (en) | 2021-12-14 | 2021-12-14 | Preparation method of antibacterial antistatic anti-ultraviolet polyurethane synthetic leather |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115283227A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117822310A (en) * | 2024-03-05 | 2024-04-05 | 苏州金泉新材料股份有限公司 | Non-stimulated polylactic acid non-woven fabric with natural weak acid and antibacterial effect |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107446401A (en) * | 2017-04-01 | 2017-12-08 | 华南理工大学 | Using dopamine as high hydrophobicity anti-bacterial attachment surface of anchor molecule and preparation method thereof |
| CN108625158A (en) * | 2017-03-21 | 2018-10-09 | 上海大学 | A kind of antistatic graphene coated fabric and preparation method thereof |
-
2021
- 2021-12-14 CN CN202111526317.5A patent/CN115283227A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108625158A (en) * | 2017-03-21 | 2018-10-09 | 上海大学 | A kind of antistatic graphene coated fabric and preparation method thereof |
| CN107446401A (en) * | 2017-04-01 | 2017-12-08 | 华南理工大学 | Using dopamine as high hydrophobicity anti-bacterial attachment surface of anchor molecule and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 秦益民: "《海洋源生物活性纤维》", vol. 1, 中国纺织出版社有限公司, pages: 19 * |
| 肖凤等: "纳米氧化亚铜/还原氧化石墨烯负载棉织物的制备及性能研究", vol. 35, no. 35, pages 13 - 16 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117822310A (en) * | 2024-03-05 | 2024-04-05 | 苏州金泉新材料股份有限公司 | Non-stimulated polylactic acid non-woven fabric with natural weak acid and antibacterial effect |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ali et al. | Copper electroless plating of cotton fabrics after surface activation with deposition of silver and copper nanoparticles | |
| Yan et al. | A superhydrophobic bionic coating on silk fabric with flame retardancy and UV shielding ability | |
| Simončič et al. | Multifunctional water and oil repellent and antimicrobial properties of finished cotton: influence of sol–gel finishing procedure | |
| CN105463854B (en) | A kind of electromagnetic shield cloth and preparation method thereof | |
| DE102006055763B4 (en) | Process for metallizing polyester, metallized polyester and its use | |
| CN106854833B (en) | A kind of antistatic ultra high molecular weight polyethylene fiber of lightweight and preparation method thereof | |
| CN105544222A (en) | Chitosan and polyester-polyether copolymer hydrophilic finishing method of dacron fabric | |
| CN103981719B (en) | A kind of preparation method of polyaniline titanium dioxide UV resistance conductive fabric | |
| CN1432084A (en) | Yarns and fabrics having wash-durable non-electrically conductive topically applied metal-based finish | |
| CN112323490B (en) | Method for carrying out super-hydrophobic modification on waste cotton fabric by polyphenol | |
| CN115283227A (en) | Preparation method of antibacterial antistatic anti-ultraviolet polyurethane synthetic leather | |
| CN106758148A (en) | A kind of preparation method of antimicrobial conductive acrylic fibre/copper sulfide composite fibre | |
| CN108893990B (en) | Preparation method of multifunctional silk-containing fabric | |
| CN108103771B (en) | Reduced graphene oxide assembled polyacrylonitrile fiber and preparation method thereof | |
| CN104404763A (en) | Method for preparing antistatic anti-felting wool fabric with good dyeing property | |
| CN111335026A (en) | Super-hydrophobic antibacterial conductive fabric and preparation method thereof | |
| US20150233049A1 (en) | Wash-durable antimicrobial textiles and methods of manufacture | |
| CN109440443B (en) | Preparation method of super-hydrophobic fabric | |
| Jiang et al. | Application of chemical silver plating on polyester and cotton blended fabric | |
| El-Sayed et al. | Synergistic combination of reduction and polymerization reactions to prepare silver/waterborne polyurethane nanocomposite for coating applications | |
| CN108588942A (en) | A kind of acrylic fibers copper facing-boron alloy electrically conductive filament and preparation method thereof | |
| CN115216958A (en) | Antibacterial breathable polyester fabric and preparation method thereof | |
| CN104894842B (en) | Ultraviolet resistant finishing application and method of baffeta of ionic liquid metal complex and ultraviolet resistant baffeta | |
| Kale et al. | Simultaneous dyeing and anti-bacterial finishing of textile by sol-gel technique | |
| CN102477689A (en) | Multi-ion electromagnetic wave radiation resistance fabric and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |