A method for preparing organic polymer-coated inorganic nanoparticles

Abstract

This invention discloses a method for preparing inorganic nanoparticles coated with organic polymers, belonging to the field of nanomaterials technology. The method involves mixing organic polymers and metal nanoparticles in the same solvent in a container (such as a culture medium), and then spraying the mixture through microdroplets at the edges of oil droplets to achieve organic polymer coating of inorganic nanoparticles. This organic polymer coating effectively prevents large-area aggregation and oxidation of the inorganic nanoparticles. The proposed method for preparing inorganic nanoparticles coated with organic polymers is simple, fast, efficient, controllable, and low-cost, solving the problems of complex, long-cycle, and costly traditional methods for coating gold nanoparticles.

Description

Technical Field

[0001] This invention belongs to the field of nanomaterials technology, specifically relating to a method for preparing inorganic nanoparticles coated with organic polymers. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Nanomaterials possess unique properties distinct from bulk materials due to their size effect, making them crucial for applications in energetic materials. Nanoparticles exhibit unique physicochemical properties, allowing for wide applicability in chemical, biological, and pharmaceutical fields. While many methods for preparing metallic nanomaterials have matured in recent years, they haven't effectively addressed the problem of large-area aggregation caused by strong surface interactions of metallic nanoparticles. More importantly, the enormous specific surface area and surface energy of metallic nanoparticles make them more susceptible to oxidation by oxygen. Nanometals possess unique physical and chemical properties, particularly their unique optical properties; many metallic structures (such as gold or silver) exhibit strong absorption of visible light at the nanoscale. However, traditional methods for encapsulating metallic nanoparticles typically involve complex procedures, are time-consuming, and costly, sometimes leading to the degradation of some physicochemical properties. Furthermore, they cannot prevent large-area aggregation of metallic nanoparticles or guarantee precise and efficient encapsulation. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing inorganic nanoparticles coated with organic polymers. This invention utilizes organic polymers to coat inorganic nanoparticles, thereby effectively coating the inorganic nanoparticles and demonstrating high practical applicability.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows:

[0006] In a first aspect, the present invention provides a method for preparing inorganic nanoparticles coated with organic polymers, comprising the following steps:

[0007] The organic polymer is dissolved in an organic solvent to obtain solution A;

[0008] The metal nanoparticle solution is mixed with solution A to obtain solution B; the solvent of the metal nanoparticle solution is the same as the organic solvent in solution A.

[0009] A polar solvent is added to water, mixed well, and then solution B is dropped into it. The solution is sprayed through the edge of the oil droplet, and the organic polymer is coated on the surface of the metal nanoparticles to obtain organic polymer coated inorganic nanoparticles.

[0010] This invention involves mixing organic polymers and metal nanoparticles in the same solvent in a container (such as a culture medium), and then spraying the mixture through microdroplets at the edges of oil droplets to achieve organic polymer coating of inorganic nanoparticles. This organic polymer coating effectively prevents large-scale aggregation and oxidation of the inorganic nanoparticles. The proposed method for preparing organic polymer-coated inorganic nanoparticles is characterized by its simplicity, speed, high efficiency, controllable process, and low cost.

[0011] In some embodiments of the present invention, the organic polymer is selected from polylactic acid, polymethyl methacrylate, polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyurethane, urea-formaldehyde resin, polyethylene terephthalate, phenolic resin and polyethylene glycol.

[0012] In some embodiments of the present invention, the organic solvent is selected from at least one of carbon tetrachloride, chloroform, dichloromethane, trichloroethylene, chloropropane, 1-chloro-n-pentane, toluene, benzene, and diethyl ether.

[0013] Accordingly, the organic solvent of the metal nanoparticle solution is also selected from at least one of carbon tetrachloride, chloroform, dichloromethane, trichloroethylene, chloropropane, 1-chloro-n-pentane, toluene, benzene, and diethyl ether.

[0014] In some embodiments of the present invention, the concentration of solution A is 0.005 to 0.1 mg / mL.

[0015] The present invention does not limit the concentration of the metal nanoparticle solution, which can be 0.03-0.08 mg / mL, such as 0.05 mg / mL.

[0016] The present invention does not limit the type of metal nanoparticles, and can be gold nanoparticles with a particle size of 3.5 to 4.5 nm, or other types or sizes of metal nanoparticles.

[0017] In some embodiments of the present invention, the volume ratio of the metal nanoparticle solution to solution A is 3 to 10:100, mL:mL.

[0018] In some embodiments of the present invention, the polar solvent is selected from one of ethanol, N,N-dimethylformamide, propylene glycol, glycerol, methanol, tetrahydrofuran, isopropanol, acetonitrile, dimethyl sulfoxide, and hexamethylphosphoric triamine.

[0019] In some embodiments of the present invention, the volume ratio of the polar solvent to water is 1 to 3:100, mL:mL.

[0020] In some embodiments of the present invention, water is added to a petri dish, followed by the addition of a polar solvent and stirring. After thorough mixing, solution B is then added dropwise. The petri dish is 10cm x 10cm in size. Solution B can be added to the water-polar solvent mixture using a pipette.

[0021] In some embodiments of the present invention, a polar solvent is added to water, mixed well, and then solution B is added dropwise, with the amount of solution B added being 500 μL to 2 mL.

[0022] In a second aspect, the present invention provides an organic polymer-coated inorganic nanoparticle, wherein the organic polymer-coated inorganic nanoparticle is prepared by the above-described preparation method.

[0023] The beneficial effects of this invention are as follows:

[0024] This invention involves mixing organic polymers and metal nanoparticles in the same solvent in a container (such as a culture medium), and then spraying the mixture through microdroplets at the edges of oil droplets to achieve organic polymer coating of inorganic nanoparticles. This organic polymer coating effectively prevents large-scale aggregation and oxidation of the inorganic nanoparticles. The proposed method for preparing organic polymer-coated inorganic nanoparticles is simple, rapid, efficient, controllable, and low-cost, solving the problems of complex, time-consuming, and costly traditional gold nanoparticle coating processes.

[0025] Furthermore, the organic polymer-coated metal nanoparticles obtained in this invention provide excellent protection for the physicochemical properties of metal nanoparticles and can achieve the coating of nanoscale gold particles. In subsequent use, the organic polymer coating on the surface of the metal nanoparticles dissolves in the organic solvent, and the metal nanoparticles are released again, thus avoiding any impact of the organic polymer coating layer on the performance of the metal nanoparticles. Attached Figure Description

[0026] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0027] Figure 1 This is a TEM image of 4nm gold nanoparticles using chloroform as the solvent in an embodiment of the present invention.

[0028] Figure 2 This is a schematic diagram of the edge microdroplet ejection of oil droplets from polystyrene with added gold nanoparticles in Embodiment 1 of the present invention, wherein the light-colored part is the oil droplet;

[0029] Figure 3 This is a TEM image of gold nanoparticles coated with polystyrene obtained in Example 1 of the present invention.

[0030] Figure 4 This is a schematic diagram of the oil droplet edge microdroplet ejection of polylactic acid with gold nanoparticles in Embodiment 3 of the present invention, wherein the light-colored part is the oil droplet;

[0031] Figure 5 This is a schematic diagram of the actual experiment.

[0032] Figure 6 This is a schematic diagram illustrating the principle. Detailed Implementation

[0033] Glossary:

[0034] Oil droplet edge micro-droplet ejection: An oil droplet composed of two miscible organic liquids forms an edge along its circumference representing the less volatile component. The solution in contact with this edge contains a polar solvent. Due to Rayleigh-plateau instability, monodisperse droplets are periodically ejected, forming oil droplet edge micro-droplet ejection. In this invention, after solution B is dropped into a water-polar solvent mixture, surface tension causes the contact edge between the oil droplet and the water-polar solvent mixture to periodically eject small droplets, namely, organic polymer-coated metal nanoparticles.

[0035] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0036] The reagents used in the following examples are all commercially available products that can be purchased.

[0037] The concentration of the gold nanoparticle solution used in the following examples is 0.05 mg / mL, the solvent is chloroform, and the diameter of the gold nanoparticles is 4 nm. Figure 1 This is a TEM image of 4 nm gold nanoparticles in chloroform as solvent.

[0038] Example 1

[0039] A method for preparing inorganic nanoparticles coated with organic polymers includes the following steps:

[0040] (1) Prepare a polystyrene solution with a concentration of 0.01 mg / mL using chloroform as the organic solvent to obtain solution A.

[0041] (2) Prepare a mixed solution B of gold nanoparticle solution and solution A. The volume ratio of gold nanoparticle solution with organic phase of trichloromethane to solution A is 3:100, mL:mL, to obtain solution B.

[0042] (3) Prepare a polar solution in a petri dish. The polar solvent is ethanol, and the volume ratio of the polar solvent to water is 2:100 (mL:mL). Then, add 2 mL of solution B to the petri dish and spray it through the edge of the oil droplet to obtain gold nanoparticles coated with polystyrene.

[0043] Figure 2 This is a schematic diagram of the edge droplet ejection of gold nanoparticles into polystyrene in Example 1. Figure 2 The image, captured by a high-speed camera, vividly illustrates the micro-droplet ejection behavior at the edge of an oil droplet, demonstrating how gold nanoparticles are encapsulated by the tip during micro-droplet ejection in polystyrene.

[0044] Figure 3 The image shown is a TEM image of the gold nanoparticles encapsulated in polystyrene obtained in Example 1. It demonstrates that polystyrene has good encapsulation properties for gold nanoparticles, and the spherical structure of polystyrene can encapsulate more gold nanoparticles.

[0045] Example 2

[0046] A method for preparing inorganic nanoparticles coated with organic polymers includes the following steps:

[0047] (1) Prepare a solution with a polystyrene concentration of 0.001 mg / mL using chloroform as the organic solvent to obtain solution A.

[0048] (2) Prepare a mixed solution B of gold nanoparticle solution and solution A. The volume ratio of gold nanoparticle solution with trichloromethane organic phase to solution A is 5:100, mL:mL, to obtain solution B.

[0049] (3) Prepare a polar solution in a petri dish. The polar solvent is ethanol, and the volume ratio of the polar solvent to water is 1:100 (mL:mL). Then, add 2 mL of solution B to the petri dish and spray it through the edge of the oil droplet to obtain gold nanoparticles coated with polystyrene.

[0050] Example 3

[0051] A method for preparing inorganic nanoparticles coated with organic polymers includes the following steps:

[0052] (1) Prepare a solution of polylactic acid with a concentration of 0.01 mg / mL using chloroform as the organic solvent to obtain solution A.

[0053] (2) Prepare a mixed solution B of gold nanoparticle solution and solution A. The organic phase is chloroform. The volume ratio of gold nanoparticle solution to solution A is 3:100, mL:mL, to obtain solution B.

[0054] (3) Prepare a polar solution in a petri dish. The polar solvent is ethanol, and the volume ratio of the polar solvent to water is 1:100 (mL:mL). Then, add 2 mL of solution B to the petri dish and spray it through the edge of the oil droplet to obtain gold nanoparticles coated with polylactic acid.

[0055] Figure 4 This is a schematic diagram of the edge microdroplet spraying of polylactic acid with gold nanoparticles in Example 3. Figure 4 Also captured by a high-speed camera, it vividly demonstrates the micro-droplet ejection behavior at the edge of the oil droplet, illustrating that when polylactic acid undergoes micro-droplet ejection, gold nanoparticles are encapsulated by the tip. It also shows that different organic polymers can encapsulate gold nanoparticles under suitable conditions. Figure 4 The light-colored particles in the middle are the ejected tips. Due to the instability of the evaporation stage caused by factors such as evaporability, the linear droplets will split into discrete smaller sub-droplets.

[0056] Example 4

[0057] A method for preparing inorganic nanoparticles coated with organic polymers includes the following steps:

[0058] (1) Prepare a solution of polymethyl methacrylate with a concentration of 0.05 mg / mL using chloroform as the organic solvent to obtain solution A.

[0059] (2) Prepare a mixed solution B of gold nanoparticle solution and solution A. The volume ratio of gold nanoparticle solution with trichloromethane organic phase to solution A is 10:100, mL:mL, to obtain solution B.

[0060] (3) Prepare a polar solution in a petri dish. The polar solvent is ethanol, and the volume ratio of the polar solvent to water is 3:100 (mL:mL). Then, add 2 mL of solution B to the petri dish and obtain gold nanoparticles coated with polymethyl methacrylate by micro-droplet spraying through the edge of the oil droplet.

[0061] Example 5

[0062] A method for preparing inorganic nanoparticles coated with organic polymers includes the following steps:

[0063] (1) Prepare a polystyrene solution with a concentration of 0.01 mg / mL using tetrachloromethane as the organic solvent to obtain solution A.

[0064] (2) Prepare a mixed solution B of gold nanoparticle solution and solution A. The volume ratio of the gold nanoparticle solution with organic phase tetrachloromethane to solution A is 3:100, mL:mL, to obtain solution B.

[0065] (3) Prepare a polar solution in a petri dish. The polar solvent is N,N-dimethylformamide, and the volume ratio of the polar solvent to water is 1:100 (mL:mL). Then, add 2 mL of solution B to the petri dish and spray it through the edge of the oil droplet to obtain gold nanoparticles coated with polystyrene.

[0066] Example 6

[0067] A method for preparing inorganic nanoparticles coated with organic polymers includes the following steps:

[0068] (1) Prepare a solution of polymethyl methacrylate with a concentration of 0.03 mg / mL using tetrachloromethane as the organic solvent to obtain solution A.

[0069] (2) Prepare a mixed solution B of gold nanoparticle solution and solution A. The volume ratio of the gold nanoparticle solution with organic phase tetrachloromethane to solution A is 5:100, mL:mL, to obtain solution B.

[0070] (3) Prepare a polar solution in a petri dish. The polar solvent is ethanol, and the volume ratio of the polar solvent to water is 1:100 (mL:mL). Then, add 2 mL of solution B to the petri dish and obtain gold nanoparticles coated with polymethyl methacrylate by micro-droplet spraying through the edge of the oil droplet.

[0071] Example 7

[0072] A method for preparing inorganic nanoparticles coated with organic polymers includes the following steps:

[0073] (1) Prepare a solution of polylactic acid with a concentration of 0.1 mg / mL using tetrachloromethane as the organic solvent to obtain solution A.

[0074] (2) Prepare a mixed solution B of gold nanoparticle solution and solution A. The volume ratio of the gold nanoparticle solution with organic phase tetrachloromethane to solution A is 10:100, mL:mL, to obtain solution B.

[0075] (3) Prepare a polar solution in a petri dish. The polar solvent is ethanol, and the volume ratio of the polar solvent to water is 2:100 (mL:mL). Then, add 2 mL of solution B to the petri dish and spray it through the edge of the oil droplet to obtain gold nanoparticles coated with polylactic acid.

[0076] Figure 5 This is a schematic diagram of the actual experiment in the above embodiment. By adding suitable water and polar solvent to a petri dish and spraying the coated gold nanoparticles through the edge of the oil droplet, it is shown that the invention can achieve the coating of gold nanoparticles more simply and effectively.

[0077] Figure 6This is a schematic diagram of the principle of the present invention. The micro-droplet ejection behavior at the edge of the oil droplet in the present invention illustrates that the oil droplet can carry gold particles and obtain encapsulated gold nanoparticles through the micro-droplet ejection behavior at the edge of the oil droplet.

[0078] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made 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 inorganic nanoparticles coated with organic polymers, characterized in that, Includes the following steps: The organic polymer is dissolved in an organic solvent to obtain solution A; The metal nanoparticle solution is mixed with solution A to obtain solution B; the solvent of the metal nanoparticle solution is the same as the organic solvent in solution A. Add a polar solvent to water, mix well, and then drop it into solution B. Spray the solution through the edge of the oil droplet. The organic polymer coats the surface of the metal nanoparticles, resulting in organic polymer-coated inorganic nanoparticles. The organic polymer is selected from one of polylactic acid, polymethyl methacrylate, polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyurethane, urea-formaldehyde resin, polyethylene terephthalate, phenolic resin and polyethylene glycol; The concentration of the metal nanoparticle solution is 0.03-0.08 mg / mL; The volume ratio of the metal nanoparticle solution to solution A is 3~10:100, mL:mL; The volume ratio of the polar solvent to water is 1~3:100, mL:mL; Add a polar solvent to the water, mix well, and then add solution B dropwise. The amount of solution B added is 500 μL to 2 mL.

2. The method for preparing organic polymer-coated inorganic nanoparticles as described in claim 1, characterized in that, The organic solvent is selected from at least one of carbon tetrachloride, chloroform, dichloromethane, trichloroethylene, chloropropane, 1-chloro-n-pentane, toluene, benzene, and diethyl ether.

3. The method for preparing organic polymer-coated inorganic nanoparticles as described in claim 1, characterized in that, The concentration of solution A is 0.005~0.1 mg / mL.

4. The method for preparing organic polymer-coated inorganic nanoparticles as described in claim 1, characterized in that, The polar solvent is selected from one of ethanol, N,N-dimethylformamide, propylene glycol, glycerol, methanol, tetrahydrofuran, isopropanol, acetonitrile, dimethyl sulfoxide, and hexamethylphosphoric triamine.

5. An organic polymer-coated inorganic nanoparticle, characterized in that, The organic polymer-coated inorganic nanoparticles are prepared by the preparation method described in any one of claims 1-4.

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