A temperature-sensitive and environmentally friendly antifouling agent microsphere coating material, its preparation method and application
By preparing an O/W/O type emulsion and crosslinking it through the mixing of sodium β-glycerophosphate and chitosan solution, the problems of insufficient temperature responsiveness and emulsification performance of microsphere coating materials in the prior art are solved, and microsphere coating materials with uniform particle size and good chemical stability are realized, which are suitable for marine antifouling.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- INST OF CHEM CHINESE ACAD OF SCI
- Filing Date
- 2024-03-07
- Publication Date
- 2026-05-26
AI Technical Summary
The microsphere coating materials prepared in the prior art cannot meet the requirements of drug release in the ocean as the release amount changes with temperature, and have poor emulsification properties and insufficient mechanical properties.
An O/W/O type emulsion was formed by mixing sodium β-glycerophosphate solution, chitosan solution, isothiazolinone and emulsifier, and microsphere coating material was prepared by crosslinking with glutaraldehyde, with the particle size controlled within 500 μm. A thermosensitive material was added to achieve temperature responsiveness.
The prepared microspheres have uniform particle size, good morphology, good chemical stability, temperature-sensitive responsiveness, drug release characteristics that change with temperature, and are environmentally friendly.
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Figure CN118271890B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of marine antifouling technology, specifically relating to a temperature-sensitive and environmentally friendly antifouling agent microsphere coating material, its preparation method, and its application. Background Technology
[0002] Marine fouling is a major and unavoidable problem during ship navigation. Statistics show that over 4,000 microorganisms from more than 1,700 species can adhere to the hull surface, causing biofouling. Microbial fouling directly increases drag, reduces speed, significantly increases fuel consumption, and can even damage hull coatings and hull structure. Therefore, protection against marine fouling is imperative. Antifouling coatings that prevent marine biofouling primarily rely on the stable release of antifouling agents from the coating to achieve the desired antifouling effect.
[0003] Existing technologies often employ O / W / O double emulsion or ionic crosslinking methods to prepare microsphere-coated materials.
[0004] I. Preparation of chitosan microspheres encapsulating seanine211 using the O / W / O double emulsion method. The preparation process is as follows:
[0005] A chitosan-acetic acid solution prepared from chitosan and a 2% acetic acid aqueous solution was mixed with a xylene solution of seanine211 and sonicated until homogeneous. Liquid paraffin was used as the external oil phase. It was added to a three-necked flask at a specific oil-to-water ratio, along with the water-in-oil surfactant Span-80 and the oil-in-water surfactant Tween-80. While stirring, a chitosan oil-in-water O / W emulsion was slowly added to form an O / W / O emulsion. The mixture was thoroughly stirred magnetically until the xylene in the internal oil phase completely evaporated. Glutaraldehyde solution was added as a crosslinking agent, and the mixture was first stirred at low temperature and then heated for crosslinking. Finally, the product was cooled to room temperature and filtered under reduced pressure to obtain yellow spherical particles. These particles were washed three times each with alternating petroleum ether and anhydrous ethanol. The final sample was spread evenly in a petri dish, pre-frozen, and then freeze-dried to obtain chitosan microspheres coated with the antifouling agent seanine211.
[0006] II. Preparation of chitosan microspheres encapsulating the antifouling agent paeonol by ionic crosslinking method. The preparation process is as follows:
[0007] 200 mg of chitosan with a degree of deacetylation of 95% was dissolved in 50 mL of 0.1 mol / L acetic acid solution. 50 mL of acetone solution containing Tween 80 and 4 mg / mL antifouling agent paeonol was added. The mixture was stirred at 1500 rpm and sonicated for 10 minutes. 10 mL of isopropanol was added as a co-solvent. The final solution was emulsified but not turbid. 100 g of sodium tripolyphosphate was then added dropwise to the above solution to solidify the microspheres. The mixture was stirred for 30 minutes. The resulting solution was filtered off. The solid was washed with acetone and deionized water to remove residual solvent. The solid was then freeze-dried under vacuum to obtain a product of solid chitosan carrying antifouling agent microparticles.
[0008] The microspheres prepared by the above method cannot meet the requirements of varying drug release with temperature in the ocean, and the above method has poor emulsification performance, making it difficult to achieve the expected encapsulation effect by relying solely on the emulsification ability of chitosan itself.
[0009] The product obtained by the ion crosslinking method of method two is in powder form. Since no chemical reaction occurs and it relies entirely on physical ion adsorption, its mechanical properties are poor. Summary of the Invention
[0010] To address the aforementioned technical problems, this invention provides a method for preparing microsphere-coated materials, the method comprising:
[0011] (1) Prepare an intermediate product by mixing sodium β-glycerophosphate solution, chitosan solution, xylene solution of isothiazolinone (seanine211), emulsifier and cosolvent;
[0012] (2) Mix dimethyl silicone oil, water, water-in-oil surfactant, oil-in-water surfactant and the intermediate product from step (1);
[0013] (3) Add a crosslinking agent to step (2), heat and crosslink to prepare the microsphere coated material.
[0014] According to an embodiment of the present invention, in step (1), the sodium β-glycerophosphate solution is an aqueous solution of sodium β-glycerophosphate, and the concentration of the sodium β-glycerophosphate solution is 0.5 g / ml-5 g / ml, preferably 1 g / ml-3 g / ml, and for example 1.25 g / ml.
[0015] According to an embodiment of the present invention, in step (1), the chitosan solution is a chitosan acetate solution, and the concentration of the chitosan solution is 0.5g / ml-5g / ml, preferably 1g / ml-3g / ml, and for example 1.25g / ml.
[0016] According to an embodiment of the present invention, in step (1), the emulsifier is selected from at least one of Tween-80, Span-80, etc., preferably Tween-80.
[0017] According to an embodiment of the present invention, in step (1), the co-solvent is selected from at least one of isopropanol, isooctanol, etc., preferably isopropanol.
[0018] According to an embodiment of the present invention, in step (1), the mixing temperature is 15-35°C; the mixing time is 5-60 minutes; for example, the mixing temperature is room temperature; and the mixing time is 10 minutes.
[0019] According to an embodiment of the present invention, in step (1), the mass ratio of sodium β-glycerophosphate, chitosan, seanine211, emulsifier and cosolvent is 50-100:50-100:50-100:1:1, for example 100:100:100:1:1.
[0020] According to an embodiment of the present invention, in step (2), the water-in-oil surfactant is selected from at least one of Span-80, sodium alkylbenzene sulfonate, polyethylene glycol (e.g., polyethylene glycol 400, 600, 800).
[0021] According to an embodiment of the present invention, in step (2), the water-in-oil surfactant is selected from at least one of Tween-80, sodium dodecyl sulfate, etc.
[0022] According to an embodiment of the present invention, in step (2), the mass ratio of dimethyl silicone oil, water, water-in-oil surfactant, oil-in-water surfactant and intermediate product in step (1) is 150-300:50-150:2-8:1-3:60-150, for example 250:100:6:2:125.
[0023] According to an embodiment of the present invention, in step (2), the mixing temperature is 15-35°C; the mixing time is 1-6 hours; for example, the mixing temperature is room temperature; the mixing time is 3 hours.
[0024] According to an embodiment of the present invention, in step (3), after the xylene in the reaction system has completely evaporated, a crosslinking agent is added.
[0025] According to an embodiment of the present invention, in step (3), the crosslinking agent is selected from at least one of glutaraldehyde, sodium tripolyphosphate, etc., preferably glutaraldehyde.
[0026] According to an embodiment of the present invention, in step (3), the mass ratio of the crosslinking agent to dimethyl silicone oil is 1:5-20, for example, 1:10.
[0027] According to an embodiment of the present invention, in step (3), the heating crosslinking process is as follows: first stirring at 15-35°C, then crosslinking at 50-90°C; for example, stirring at room temperature first and then heating to 70°C for crosslinking.
[0028] According to an embodiment of the present invention, the product of step (3) can also be post-processed: the prepared product is cooled, filtered, washed, dried, etc.; for example, it is washed with petroleum ether, ethanol, etc.
[0029] The present invention also provides microsphere-coated materials prepared by the above method.
[0030] According to an embodiment of the present invention, the particle size of the microsphere coating material is within 500 μm, preferably 1-500 μm, and even more preferably 20-500 μm.
[0031] The present invention also provides the application of the above-mentioned microsphere coating material in marine antifouling.
[0032] The beneficial effects of this invention are:
[0033] 1. Since the precipitation and coagulation method involves manual injection, the morphology cannot be controlled and the particle size is very large. Compared with the precipitation and coagulation method, the microspheres prepared by the method of the present invention have uniform particle size, small particle size and good morphology.
[0034] 2. Compared with the ionic crosslinking method, the microspheres prepared by the method of the present invention have better chemical stability.
[0035] 3. The raw materials used in this invention are environmentally friendly, safe, and pollution-free. After the addition of temperature-sensitive materials, they have a certain degree of temperature responsiveness.
[0036] The microsphere-coated material prepared by the method of this invention consists of spherical particles with a uniform particle size controlled below 500 μm. The addition of the thermosensitive material sodium β-glycerophosphate gives the microsphere-coated material temperature-sensitive responsiveness. The method of this invention can stably produce O / W / O emulsions with good reproducibility. Specifically:
[0037] 1. The microsphere coating material of the present invention has temperature responsiveness, and the addition of the temperature-sensitive material sodium β-glycerophosphate makes the microsphere material have different release characteristics at low temperature and room temperature.
[0038] 2. The microsphere coating material prepared by the method of the present invention has a uniform morphology, a complete spherical shape, and a particle size that can be controlled below 500 μm. Attached Figure Description
[0039] Figure 1 This is an SEM image of the microsphere-coated material in Example 1.
[0040] Figure 2These are curves showing the changes in UV absorbance values of the microsphere-coated material in Example 1 over time at 4°C and 15°C. Detailed Implementation
[0041] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.
[0042] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.
[0043] Example 1
[0044] 1. Dissolve sodium β-glycerophosphate in distilled water to obtain a sodium β-glycerophosphate solution with a concentration of 1.25 g / ml. Add the prepared sodium β-glycerophosphate solution dropwise to a chitosan-acetic acid solution prepared with chitosan and 2% acetic acid aqueous solution under stirring in an ice-water bath. The concentration of the chitosan-acetic acid solution is 1.25 g / ml. Mix the chitosan-acetic acid solution with sodium β-glycerophosphate and a xylene solution of seanine211. Add the emulsifier Tween-80 and the cosolvent isopropanol. Stir at room temperature until the solution is homogeneous for 10 min to obtain a chitosan oil-in-water O / W emulsion. The mass ratio of sodium β-glycerophosphate, chitosan, seanine211, emulsifier and cosolvent is 100:100:100:1:1.
[0045] 2. Dimethyl silicone oil was selected as the external oil phase. It was added to a three-necked flask at a specific oil-to-water ratio, along with the water-in-oil surfactant Span-80 and the oil-in-water surfactant Tween-80. The mass ratio of dimethyl silicone oil, water, water-in-oil surfactant, oil-in-water surfactant, and the intermediate product from step (1) was 250:100:6:2:125. While stirring, chitosan oil-in-water O / W emulsion was slowly added to form an O / W / O emulsion. The mixture was stirred thoroughly with magnetic stirring for 1 hour until the xylene in the internal oil phase had completely evaporated.
[0046] Glutaraldehyde solution was added as a crosslinking agent, with a mass ratio of crosslinking agent to dimethyl silicone oil of 1:10. The mixture was first stirred at low temperature and then heated to 70°C for crosslinking. Finally, the product was cooled to room temperature and filtered under reduced pressure to obtain yellow spherical particles. These particles were washed three times each with alternating petroleum ether and anhydrous ethanol. The final sample was spread evenly in a petri dish, pre-frozen, and then freeze-dried to obtain chitosan microspheres coated with the antifouling agent seanine211.
[0047] In this invention, a chitosan solution reacts with a xylene solution of the inner oil phase (seane-211) to form an O / W emulsion. Under the combined action of the composite emulsifiers Span-80 and Tween-80, an O / W / O emulsion is formed. Glutaraldehyde reacts with the amino groups on the chitosan to form Schiff base bonds, resulting in the cross-linking and precipitation of microspheres. These Schiff base bonds (amines) undergo electrophilic addition reactions with carbonyl compounds to form semiamine aldehydes, which, upon dehydration, form imines, thus preparing the microsphere coating material. Sodium β-glycerophosphate exhibits thermosensitive properties, allowing the microspheres of this invention to maintain different properties at room temperature and low temperature. At low temperatures, the molecular chains shrink, resulting in a slow drug release rate; at room temperature, they remain in a gel state with a slightly faster drug release rate.
[0048] Figure 1 This is a SEM image of the microsphere-coated material in Example 1. From... Figure 1 It can be seen that the material is spherical with good morphology and the particle size distribution is in the range of 1um-500um.
[0049] Figure 2 The curves showing the change of UV absorbance values of the microspheres at 4℃ and 15℃ over time in Example 1 are shown. Figure 2 Test procedure: 20 mg of microsphere-coated material was placed in 100 ml of artificial seawater. At intervals of 1 h, 3 h, 7 h, 12 h, 24 h, and 48 h, 5 ml of the solution was drawn into a cuvette using a syringe at 4℃ and 15℃. The absorbance was measured using a UV spectrophotometer. The results are shown in the figure. Figure 2 As can be seen, the material exhibits good temperature sensitivity. The figure above shows the release curves of the material placed in seawater at 4℃ and 15℃, respectively, with a significant difference in release rate (the absorbance in the figure is directly proportional to the drug release concentration).
[0050] The embodiments of the present invention have been described above by way of example. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A method for preparing a microsphere-coated material, characterized in that, The method includes: (1) Prepare an intermediate product by mixing sodium β-glycerophosphate solution, chitosan solution, xylene solution of isothiazolinone, emulsifier and cosolvent; (2) Mix dimethyl silicone oil, water, water-in-oil surfactant, oil-in-water surfactant and intermediate product from step (1); (3) Add a crosslinking agent to step (2), heat to crosslink, and prepare the microsphere-coated material; The concentration of the β-glycerophosphate sodium solution is 0.5 g / ml to 5 g / ml; In step (1), the mass ratio of sodium β-glycerophosphate, chitosan, isothiazolinone, emulsifier and cosolvent is 50-100:50-100:50-100:1:
1.
2. The method according to claim 1, characterized in that, The β-glycerophosphate sodium solution is an aqueous solution of β-glycerophosphate sodium.
3. The method according to claim 1, characterized in that, In step (1), the chitosan solution is a chitosan acetate solution, and the concentration of the chitosan solution is 0.5g / ml-5g / ml.
4. The method according to claim 1, characterized in that, In step (1), the emulsifier is selected from at least one of Tween-80 and Span-80; In step (1), the co-solvent is selected from at least one of isopropanol and isooctanol.
5. The method according to claim 1, characterized in that, In step (2), the water-in-oil surfactant is selected from Span-80; In step (2), the water-in-oil surfactant is selected from at least one of Tween-80 and sodium dodecyl sulfate.
6. The method according to claim 1, characterized in that, In step (2), the mass ratio of dimethyl silicone oil, water, water-in-oil surfactant, oil-in-water surfactant and intermediate product in step (1) is 150-300: 50-150: 2-8: 1-3: 60-150.
7. The method according to claim 1, characterized in that, In step (3), after the xylene in the reaction system has completely evaporated, a crosslinking agent is added; In step (3), the crosslinking agent is selected from at least one of glutaraldehyde and sodium tripolyphosphate.
8. The method according to claim 1, characterized in that, In step (3), the mass ratio of the crosslinking agent to dimethyl silicone oil is 1:5-20; In step (3), the heating crosslinking process is as follows: first stir at 15-35℃, then crosslink at 50-90℃.
9. The microsphere coating material prepared by the method according to any one of claims 1-7.
10. The microsphere coating material according to claim 9, characterized in that, The particle size of the microsphere coating material is less than 500 μm.
11. The application of the microsphere coating material according to claim 10 in marine antifouling.