A polystyrene microsphere / chitosan composite film loaded with hydrophobic substances and its electrodeposition preparation method
By co-depositing polystyrene microspheres with chitosan, the problem of the difficulty in co-depositing hydrophobic substances was solved, and a stable composite membrane was prepared. This membrane can be applied in the fields of coating and catalysis, and it has color development and catalytic properties. Moreover, the preparation method is simple and environmentally friendly.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WUHAN UNIV OF TECH
- Filing Date
- 2023-01-03
- Publication Date
- 2026-05-26
AI Technical Summary
Existing technologies make it difficult to achieve the co-deposition of hydrophobic substances with chitosan, which limits the development of chitosan electrodeposition technology.
Polystyrene microspheres were used as carriers for hydrophobic substances and co-deposited with chitosan to form a composite film. The hydrophobic substances were stably maintained on the electrode by electrodeposition. The co-deposition of hydrophobic substances was achieved by utilizing the stability of the surfactant in polystyrene microspheres and the pH responsiveness of chitosan.
The hydrophobic substances in the prepared composite membrane are stable for a long time, maintaining color development and catalytic performance. It can be applied in the fields of coating and catalysis. Moreover, the preparation method is simple and environmentally friendly, and the membrane thickness and hydrophobic substance content can be controlled.
Smart Images
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of materials technology, specifically relating to a polystyrene microsphere / chitosan composite film loaded with hydrophobic substances and its electrodeposition preparation method. Background Technology
[0002] Electrodeposition technology primarily involves assembling stimulus-responsive biomolecules, such as chitosan, sodium alginate, carboxymethyl chitosan, and hyaluronic acid, by applying specific electrical stimulation signals. Chitosan, in particular, exhibits pH responsiveness and excellent film-forming properties, making it suitable for cathodic electrodeposition. Furthermore, the numerous amino and hydroxyl groups on the chitosan molecule allow it to coordinate with metal ions to form hydrogels, thus enabling anodic coordination electrodeposition. Currently, chitosan is co-deposited with other nanomaterials to prepare biosensors, supercapacitors, biomembrane materials, catalysts, and more. For example, chitosan can be electrodeposited with graphene to prepare hydrogen peroxide sensors [Talanta, 2018, 190: 70-77]; chitosan and hydroxyapatite can be co-deposited to prepare tubular hydrogels, which have good biocompatibility and can be applied in the regeneration or replacement of tubular tissues and organs [Materials, 2021, 14(5): 1288]; chitosan can be co-deposited with hydrophilic carbon quantum dots to prepare electrodeposited films with fluorescent properties [Journal of Materials Chemistry B, 2015, 3: 7511-7517]; chitosan and hydrophilic silver nanoparticles can be co-deposited to prepare biofilm materials with antibacterial properties [Materials Science and Engineering C, 2015, 53: 222-228], etc.
[0003] Current research focuses on co-deposition of hydrophilic materials with chitosan; however, there are no reports on the co-deposition of hydrophobic materials. Since chitosan electrolytes are water-soluble, while hydrophobic materials are insoluble in water, they cannot dissolve in the chitosan electrolyte, making co-deposition with chitosan difficult. Therefore, exploring the co-deposition of hydrophobic materials with chitosan is of great significance to the development of chitosan electrodeposition technology. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to address the shortcomings of the existing technology by providing a polystyrene microsphere / chitosan composite film loaded with hydrophobic substances and its electrodeposition preparation method. Polystyrene microspheres are used as a carrier for hydrophobic substances (hydrophobic dyes and hydrophobic metal nanoparticles) and are co-deposited with chitosan onto an electrode to form a composite film. The hydrophobic substances in the composite film can exist stably for a long time and still retain their original color development, catalytic and other properties, thus showing good application prospects in coating, catalysis and other fields.
[0005] To address the technical problem proposed in this invention, this invention provides a method for electrodepositing a polystyrene microsphere / chitosan composite film loaded with hydrophobic substances, comprising the following steps:
[0006] 1) Mix the compound emulsifier, styrene, water and hydrophobic substance to form a homogeneous mixed solution. Under nitrogen atmosphere and stirring conditions, heat the mixed solution to the polymerization temperature, add azobisisobutyronitrile to carry out the polymerization reaction, centrifuge to take the lower solid layer, dilute with water to obtain polystyrene microsphere emulsion loaded with hydrophobic substance.
[0007] 2) Dissolve chitosan in an aqueous acetic acid solution to obtain a chitosan solution;
[0008] 3) Mix the polystyrene microsphere emulsion loaded with hydrophobic substances with chitosan solution until homogeneous, then add sodium chloride solution and hydrogen peroxide in sequence and mix until homogeneous to obtain electrodeposition solution;
[0009] 4) Using platinum (Pt) as the anode material and indium tin oxide (ITO) as the cathode material, the anode and cathode are simultaneously immersed in the electrodeposition solution, and a voltage is applied to perform electrodeposition. A thin film is deposited on the cathode, which is then rinsed with water and dried to obtain a polystyrene microsphere / chitosan composite film loaded with hydrophobic substances.
[0010] In the above scheme, the compound emulsifier is composed of dodecylphenol polyoxyethylene ether and sodium dodecyl sulfate, and the mass ratio of dodecylphenol polyoxyethylene ether to sodium dodecyl sulfate is (18-20):1.
[0011] In the above scheme, the hydrophobic material is a hydrophobic dye or hydrophobic metal nanoparticles.
[0012] In the above scheme, the mass ratio of the compound emulsifier, styrene, water, hydrophobic substance and initiator is 0.2:(4-6.5):(50-90):(0.01-0.1):(0.05-0.08).
[0013] In the above scheme, the polymerization temperature is 60-85℃ and the polymerization reaction time is 6-24h.
[0014] In the above scheme, the mass concentration of the polystyrene microsphere emulsion loaded with hydrophobic substances is 0.1-0.2%.
[0015] In the above scheme, the concentration of the acetic acid aqueous solution is 0.1-0.2 mol / L.
[0016] In the above scheme, the mass concentration of the chitosan solution is 0.9-2%.
[0017] In the above scheme, the concentration of sodium chloride in the electrodeposition solution is 0.15-0.2 mol / L.
[0018] In the above scheme, the concentration of hydrogen peroxide in the electrodeposition solution is 100-300 mmol / L.
[0019] In the above scheme, the mass concentration of polystyrene microspheres loaded with hydrophobic substances in the electrodeposition solution is 0.03-0.06%.
[0020] In the above scheme, the anode and cathode are ultrasonically cleaned with acetone, anhydrous ethanol and distilled water for 20-30 minutes in sequence before electrodeposition.
[0021] In the above scheme, the anode and cathode are placed perpendicular to the surface of the electrodeposition solution, and the anode and cathode are parallel and maintained at a distance of 2-3 cm.
[0022] In the above scheme, the electrodeposition voltage is 2-4V and the electrodeposition time is 7-12min.
[0023] In the above scheme, the number of times the water is rinsed is 3-5 times to remove excess electrodeposition solution from the membrane surface.
[0024] In the above scheme, the drying temperature is 40-45℃ and the drying time is 90-100min.
[0025] The present invention also provides a polystyrene microsphere / chitosan composite membrane loaded with hydrophobic substances, which is prepared by the above method.
[0026] In the above scheme, the thickness of the composite film is 20-128 μm.
[0027] In the above scheme, the polystyrene microspheres loaded with hydrophobic substances in the composite membrane have a particle size of 50-900 nm.
[0028] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0029] 1) This invention utilizes polystyrene microspheres as a carrier for hydrophobic substances. The surface of the polystyrene microspheres is stabilized by surfactant molecules, exhibiting a hydrophobic interior and a hydrophilic exterior, thus enabling uniform dispersion in a hydrophilic environment. A mixed solution of polystyrene microspheres and chitosan is used as the electrolyte, with Pt metal as the anode material and ITO as the cathode material for electrodeposition. During electrolysis, a pH gradient is generated near the cathode, causing the chitosan to undergo a dissolution-insolubility transition, simultaneously dragging the polystyrene microspheres to co-deposit onto the electrode plate. This also achieves co-deposition of the hydrophobic substances, resulting in a polystyrene microsphere / chitosan composite membrane encapsulating hydrophobic substances. This composite membrane possesses certain mechanical strength and can be completely removed from the electrode for independent use. The hydrophobic substances in the composite membrane can remain stable for a long time while retaining their original color development and catalytic properties, thus showing promising application prospects in coatings, catalysis, and other fields.
[0030] 2) The method for preparing the composite membrane of the present invention has the advantages of simple operation, controllable conditions, and green environmental protection. During the electrodeposition process, by adjusting the deposition conditions such as electrodeposition voltage, electrodeposition time, and cathode electrode shape, the thickness, shape, and content of hydrophobic substances deposited in the composite membrane can be controlled to meet different application requirements. Attached Figure Description
[0031] Figure 1 This refers to the polystyrene microsphere / chitosan composite membrane loaded with hydrophobic silver nanoparticles prepared in Example 1 of the present invention.
[0032] Figure 2 This is a transmission electron microscope (TEM) image of the polystyrene microsphere / chitosan composite membrane loaded with hydrophobic silver nanoparticles prepared in Example 1 of the present invention.
[0033] Figure 3 This refers to the polystyrene microsphere / chitosan composite membrane loaded with the hydrophobic dye Sudan III prepared in Example 2 of the present invention.
[0034] Figure 4 This refers to the polystyrene microsphere / chitosan composite membrane loaded with the hydrophobic dye curcumin prepared in Example 3 of the present invention. Detailed Implementation
[0035] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.
[0036] Example 1
[0037] An electrodeposition method for preparing a polystyrene microsphere / chitosan composite film loaded with hydrophobic silver nanoparticles includes the following steps:
[0038] 1) A compound emulsifier was prepared by mixing dodecylphenol polyoxyethylene ether and sodium dodecyl sulfate at a mass ratio of 18:1. The compound emulsifier, styrene, water and hydrophobic silver nanoparticles were mixed at a mass ratio of 0.2:4:60:0.05 to form a homogeneous mixed solution. Under nitrogen atmosphere and stirring conditions, the mixed solution was heated to 65°C, and azobisisobutyronitrile was added. The mass ratio of azobisisobutyronitrile to styrene was 0.05:4. The reaction was carried out for 9 hours. The lower solid layer was collected by centrifugation and diluted with water to obtain a polystyrene microsphere emulsion with a mass concentration of 0.1% loaded with hydrophobic silver nanoparticles.
[0039] 2) Dissolve chitosan in a 0.1 mol / L aqueous acetic acid solution to prepare a chitosan solution with a mass concentration of 1%;
[0040] 3) The polystyrene microsphere emulsion loaded with hydrophobic silver nanoparticles was mixed evenly with the chitosan solution, and then sodium chloride solution and hydrogen peroxide were added in sequence and mixed evenly to obtain the electrodeposition solution. The mass concentration of polystyrene microspheres loaded with hydrophobic silver nanoparticles in the electrodeposition solution was 0.04%, the concentration of sodium chloride in the electrodeposition solution was 0.15 mol / L, and the concentration of hydrogen peroxide in the electrodeposition solution was 300 mmol / L.
[0041] 4) Using Pt metal as the anode material and ITO as the cathode material, the anode and cathode were ultrasonically cleaned sequentially with acetone, anhydrous ethanol, and distilled water for 20 minutes. The anode and cathode were then immersed in the electrodeposition solution perpendicular to the surface of the electrodeposition solution, with the anode and cathode parallel and 2 cm apart. A voltage of 2V was applied for deposition for 9 minutes, and a thin film was deposited on the cathode. After rinsing with water three times, the film was dried at 45°C for 90 minutes to obtain a polystyrene microsphere / chitosan composite film loaded with hydrophobic silver nanoparticles.
[0042] Figure 1 The polystyrene microsphere / chitosan composite membrane loaded with hydrophobic silver nanoparticles prepared in this embodiment has an area of 2 cm². 2 The thickness is 72μm.
[0043] Figure 2 The image shows a transmission electron microscope (TEM) image of the polystyrene microsphere / chitosan composite film loaded with hydrophobic silver nanoparticles prepared in this embodiment. As can be seen from the image, polystyrene microspheres with a particle size of approximately 110 nm are uniformly distributed in the composite film. Monodisperse silver nanoparticles with a particle size of approximately 10 nm are present on the surface and inside the polystyrene microspheres, without obvious aggregation. This proves that polystyrene microspheres can serve as a carrier for hydrophobic silver nanoparticles and can be co-deposited with chitosan.
[0044] Example 2
[0045] A method for electrodepositing a polystyrene microsphere / chitosan composite film loaded with the hydrophobic dye Sudan III, comprising the following steps:
[0046] 1) A compound emulsifier was prepared by mixing dodecylphenol polyoxyethylene ether and sodium dodecyl sulfate at a mass ratio of 19:1. The compound emulsifier, styrene, water and hydrophobic dye Sudan III were mixed at a mass ratio of 0.2:5:60:0.08 to form a homogeneous mixed solution. Under nitrogen atmosphere and stirring, the mixed solution was heated to 70°C, and azobisisobutyronitrile was added. The mass ratio of azobisisobutyronitrile to styrene was 0.06:5. The reaction was carried out for 8 hours. The lower solid layer was centrifuged and diluted with water to obtain a polystyrene microsphere emulsion with a mass concentration of 0.15% loaded with hydrophobic dye Sudan III.
[0047] 2) Chitosan was dissolved in a 0.15 mol / L aqueous acetic acid solution to prepare a chitosan solution with a mass concentration of 1.2%;
[0048] 3) The polystyrene microsphere emulsion loaded with the hydrophobic dye Sudan III was mixed evenly with the chitosan solution, and then sodium chloride solution and hydrogen peroxide were added in sequence and mixed evenly to obtain the electrodeposition solution. The mass concentration of the polystyrene microspheres loaded with the hydrophobic dye Sudan III in the electrodeposition solution was 0.05%, the concentration of sodium chloride in the electrodeposition solution was 0.18 mol / L, and the concentration of hydrogen peroxide in the electrodeposition solution was 200 mmol / L.
[0049] 4) Using Pt metal as the anode material and ITO as the cathode material, the anode and cathode were ultrasonically cleaned for 25 minutes in sequence with acetone, anhydrous ethanol and distilled water. The anode and cathode were then immersed in the electrodeposition solution perpendicular to the surface of the electrodeposition solution, with the anode and cathode parallel and kept at a distance of 2.5 cm. A voltage of 3V was applied for deposition for 8 minutes, and a thin film was deposited on the cathode. After rinsing with water 4 times, the film was dried at 40℃ for 95 minutes to obtain a polystyrene microsphere / chitosan composite film loaded with the hydrophobic dye Sudan III.
[0050] Figure 3 The polystyrene microsphere / chitosan composite membrane loaded with the hydrophobic dye Sudan III prepared in this embodiment has an area of 3 cm². 2 The composite membrane, with a thickness of 84 μm and a brownish-red color, demonstrates that polystyrene microspheres can serve as a carrier for the hydrophobic dye Sudan III and can be co-deposited with chitosan. The composite membrane contains uniformly distributed polystyrene microspheres with a particle size of approximately 200 nm.
[0051] Example 3
[0052] A method for electrodepositing a polystyrene microsphere / chitosan composite film loaded with the hydrophobic dye curcumin, comprising the following steps:
[0053] 1) A compound emulsifier was prepared by mixing dodecylphenol polyoxyethylene ether and sodium dodecyl sulfate at a mass ratio of 20:1. The compound emulsifier, styrene, water and hydrophobic dye curcumin were mixed at a mass ratio of 0.2:6:70:0.1 to form a homogeneous mixed solution. Under nitrogen atmosphere and stirring conditions, the mixed solution was heated to 80°C, and azobisisobutyronitrile was added. The mass ratio of azobisisobutyronitrile to styrene was 0.07:6. The reaction was carried out for 7 hours. The lower solid layer was collected by centrifugation and diluted with water to obtain a polystyrene microsphere emulsion with a mass concentration of 0.2% loaded with hydrophobic dye curcumin.
[0054] 2) Chitosan was dissolved in a 0.2 mol / L aqueous acetic acid solution to prepare a chitosan solution with a mass concentration of 1.5%;
[0055] 3) The polystyrene microsphere emulsion loaded with the hydrophobic dye curcumin was mixed evenly with the chitosan solution, and then sodium chloride solution and hydrogen peroxide were added in sequence and mixed evenly to obtain the electrodeposition solution. The mass concentration of polystyrene microspheres loaded with the hydrophobic dye curcumin in the electrodeposition solution was 0.06%, the concentration of sodium chloride in the electrodeposition solution was 0.1 mol / L, and the concentration of hydrogen peroxide in the electrodeposition solution was 300 mmol / L.
[0056] 4) Using Pt metal as the anode material and ITO as the cathode material, the anode and cathode were ultrasonically cleaned for 30 minutes in sequence with acetone, anhydrous ethanol and distilled water. The anode and cathode were then immersed in the electrodeposition solution perpendicular to the surface of the electrodeposition solution, with the anode and cathode parallel and 3 cm apart. A voltage of 4V was applied for deposition for 7 minutes, and a thin film was deposited on the cathode. After rinsing with water 5 times, the film was dried at 40℃ for 100 minutes to obtain a polystyrene microsphere / chitosan composite film loaded with the hydrophobic dye curcumin.
[0057] Figure 4 The polystyrene microsphere / chitosan composite membrane loaded with the hydrophobic dye curcumin prepared in this embodiment has an area of 3.5 cm². 2 The composite membrane, with a thickness of 90 μm and an orange-yellow color, demonstrates that polystyrene microspheres can serve as a carrier for the hydrophobic dye curcumin and can be co-deposited with chitosan. The composite membrane contains uniformly distributed polystyrene microspheres with a particle size of approximately 350 nm.
[0058] The above embodiments are merely examples for clear illustration and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations, and any obvious variations or modifications derived therefrom are still within the scope of protection of this invention.
Claims
1. A method for the electrodeposition of polystyrene microspheres / cyclodextrin composite films entrapping hydrophobic substances, characterized in that, Includes the following steps: 1) A compound emulsifier, styrene, water, and a hydrophobic substance are mixed to form a homogeneous mixed solution. Under a nitrogen atmosphere and stirring conditions, the mixed solution is heated to the polymerization temperature, and azobisisobutyronitrile is added to initiate a polymerization reaction. The lower solid layer is collected by centrifugation and diluted with water to obtain a polystyrene microsphere emulsion loaded with a hydrophobic substance. The hydrophobic substance is a hydrophobic dye or hydrophobic metal nanoparticles. 2) Dissolve chitosan in an aqueous acetic acid solution to obtain a chitosan solution; 3) Mix the polystyrene microsphere emulsion loaded with hydrophobic substances with chitosan solution until homogeneous, then add sodium chloride solution and hydrogen peroxide in sequence and mix until homogeneous to obtain electrodeposition solution; 4) Using Pt metal as the anode material and ITO as the cathode material, the anode and cathode are simultaneously immersed in the electrodeposition solution, and a voltage is applied to perform electrodeposition. A thin film is deposited on the cathode, which is then rinsed with water and dried to obtain a polystyrene microsphere / chitosan composite film loaded with hydrophobic substances.
2. The method for the electrodeposition of polystyrene microspheres / chitosan composite films entrapping hydrophobic substances according to claim 1, characterized in that, The compound emulsifier is composed of dodecylphenol polyoxyethylene ether and sodium dodecyl sulfate in a mass ratio of (18-20):
1. The mass ratio of the compound emulsifier, styrene, water, hydrophobic substance and azobisisobutyronitrile is 0.2:(4-6.5):(50-90):(0.01-0.1):(0.05-0.08).
3. The electrodeposition preparation method of the polystyrene microsphere / chitosan composite film loaded with hydrophobic substances according to claim 1, characterized in that, The polymerization temperature is 60-85℃, and the polymerization reaction time is 6-24h; the mass concentration of the polystyrene microsphere emulsion loaded with hydrophobic substances is 0.1-0.2%.
4. The method for electrodepositing a polystyrene microsphere / chitosan composite film loaded with hydrophobic substances according to claim 1, characterized in that, The concentration of the acetic acid aqueous solution is 0.1-0.2 mol / L; the mass concentration of the chitosan solution is 0.9-2%.
5. The electrodeposition preparation method of the polystyrene microsphere / chitosan composite film loaded with hydrophobic substances according to claim 1, characterized in that, In the electrodeposition solution, the concentration of sodium chloride is 0.15-0.2 mol / L, the concentration of hydrogen peroxide is 100-300 mmol / L, and the mass concentration of polystyrene microspheres loaded with hydrophobic substances is 0.03-0.06%.
6. The electrodeposition preparation method of the polystyrene microsphere / chitosan composite film loaded with hydrophobic substances according to claim 1, characterized in that, The anode and cathode are placed perpendicular to the surface of the electrodeposition solution, and are parallel to each other with a distance of 2-3 cm; the electrodeposition voltage is 2-4 V, and the electrodeposition time is 7-12 min.
7. The electrodeposition preparation method of the polystyrene microsphere / chitosan composite film loaded with hydrophobic substances according to claim 1, characterized in that, The drying temperature is 40-45℃, and the drying time is 90-100 min.
8. A polystyrene microsphere / chitosan composite membrane loaded with hydrophobic substances, prepared by the method according to any one of claims 1-7.
9. The polystyrene microsphere / chitosan composite membrane loaded with hydrophobic substances according to claim 8, characterized in that, The thickness of the composite membrane is 20-128 μm, and the particle size of the polystyrene microspheres loaded with hydrophobic substances in the composite membrane is 50-900 nm.