CN109280389B - Preparation method of silver nanoparticle composite organic silicon resin - Google Patents
Preparation method of silver nanoparticle composite organic silicon resin Download PDFInfo
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Abstract
The invention relates to the technical field of metal nano composite materials, in particular to a preparation method of silver nano particle composite organic silicon resin. The preparation method comprises the steps of firstly preparing silver nanoparticles and organic silicon resin prepolymer coated by a silicon dioxide shell layer, then preparing a uniformly dispersed and stable dispersion system of the silver nanoparticles in the organic silicon resin prepolymer, and finally curing to obtain the solid sol material of the silver nanoparticle composite organic silicon resin. The silver nanoparticle composite organic silicon resin material prepared by the invention has the advantages of high light transmittance, high weather resistance, high temperature resistance and the like, has antistatic capability, antibacterial capability and special optical properties, and has wide application prospect when being used as a nonlinear optical material or an optical coating material and the like.
Description
Technical Field
The invention relates to the technical field of metal nano composite materials, in particular to a preparation method of silver nano particle composite organic silicon resin.
Background
The silver nano-particles are nano-crystals with the size from several nanometers to hundreds of nanometers, and the currently reported silver nano-particles comprise silver nanospheres, silver nanorods, silver nanocubes, silver nanosheets, silver nanocopologues and the like. The silver nano-particles show local surface plasmon resonance characteristics under the action of an external electromagnetic field, and the surface plasmon resonance signals of the silver nano-particles are influenced by the size, the shape, the composition, the aggregation degree and the surrounding dielectric environment of the nano-particles. Generally, the surface plasmon resonance absorption peak of the spherical silver nanoparticles is near 420 nm, and the red shift occurs along with the increase of the particle size; anisotropic silver nanoparticles such as silver nanorods and silver nanosheets have two or more surface plasmon resonance absorption peaks. The silver nanoparticles have good application prospect as an optical active material due to the optical characteristics generated by the surface plasmon resonance phenomenon. In addition, silver nanoparticles have been widely used in heterogeneous catalysis, surface enhanced raman spectroscopy, energy conversion, and antimicrobial applications.
In the prior art, research on silver nanoparticle composite materials has advancedFor example, silver nanoparticle composite polyvinylpyrrolidone films, organic glass (polymethyl methacrylate), alkyd resins, and other composite materials are used. However, since the thermal decomposition temperature of these polymers based on carbon alkanes is generally not more than 300oC, which makes these silver nanoparticle composites unsuitable for use in high temperature environments, especially when they are easily ablated by laser irradiation.
The organic silicon resin is a highly crosslinked semi-inorganic high polymer which takes Si-O-Si bonds as a main chemical structure and part of silicon atoms have organic groups, is an inert, non-toxic and non-flammable material, has the characteristics of high light transmittance, high weather resistance, high temperature resistance and the like, and is widely applied to the aspects of aerospace, electronic and electrical products, buildings, machinery and the like. The silver nano particles are compounded with the organic silicon resin to obtain the silver nano particle composite material with high temperature resistance, the laser ablation resistance is improved, and the silver nano particle composite material has main application advantages.
On the other hand, in the prior art, the preparation of silver nanoparticles usually adopts an in-situ generation method, the obtained silver nanoparticles have wide size distribution (from less than 1 nanometer to hundreds of nanometers), and the obtained composite material has poor uniformity, so that the application range of the material is limited.
Disclosure of Invention
The invention aims to find a method which meets the requirements of low cost, simple equipment, environmental protection and the like, and prepare novel composite materials and coating materials formed by silver nanoparticles and organic silicon resin. The silver nanoparticles prepared by the method have narrow size distribution, can form a uniform dispersion system in the organic silicon resin matrix, and the obtained composite material has good uniformity.
In order to achieve the purpose, the silver nano particles coated by the silicon dioxide shell layer and the organic silicon resin prepolymer are firstly prepared, and then the silver nano particle composite organic silicon resin material is prepared through a solvent-assisted compounding process.
In addition, the silver nanoparticle composite organic silicon resin prepared by the method is also within the protection scope of the invention.
The specific technical scheme of the invention is as follows:
a preparation method of silver nanoparticle composite organic silicon resin comprises the following steps:
(1) preparing silver nanoparticles by adopting a seed growth method under the protection of a surfactant;
(2) preparing silver nanoparticles coated by a silicon dioxide shell layer by using the silver nanoparticles obtained in the step (1) through a Stoeber hydrolysis method;
(3) preparing an organic silicon resin prepolymer;
(4) and (3) preparing the silver nanoparticle composite organic silicon resin material through a solvent-assisted compounding process by taking the silver nanoparticles coated by the silicon dioxide shell layer prepared in the step (2) and the organic silicon resin prepolymer prepared in the step (3).
Preferably, the step (1) is:
reducing silver nitrate by using sodium borohydride under the protection of sodium citrate to prepare a silver nano seed solution;
adding the silver nano seed solution into a growth solution containing hexadecyl trimethyl ammonium bromide (0.01-0.2 mol/L), silver nitrate (0.1-0.5 mmol/L), ascorbic acid (0.5-5 mmol/L) and sodium hydroxide (5-20 mmol/L), and stirring for reaction;
and after the reaction is finished, centrifuging, washing and precipitating the reaction product to obtain silver nanoparticles, and dispersing the silver nanoparticles in water for storage.
Preferably, in the step (1), the shape of the silver nanoparticles is adjusted by changing the concentration of cetyl trimethyl ammonium bromide in the growth solution; when preparing the silver nanospheres, the concentration of hexadecyl trimethyl ammonium bromide is 0.04-0.05mol/L, the sizes of the obtained silver nanospheres are uniform, and the average diameter of the silver nanospheres is adjusted to be 10-100 nm by controlling reaction conditions; when the silver nano-sheet is prepared, the concentration of hexadecyl trimethyl ammonium bromide is 0.09-0.15mol/L, the obtained silver nano-sheet is a triangular sheet, a hexagonal sheet or a nearly circular sheet, the diameter can be adjusted between 50-200 nm, and the thickness is 10-50 nm.
Preferably, the step (2) is:
adding a mercaptopropyl trimethoxy silane solution into the silver nanoparticles obtained in the step (1), and fixing mercaptopropyl trimethoxy silane on the surfaces of the silver nanoparticles through the action between silver atoms and sulfydryl;
adding tetraethoxysilane into the system, uniformly mixing, adding sodium hydroxide to hydrolyze siloxy bonds into silicon hydroxyl under the alkalescent condition, and then forming silicon-oxygen-silicon bonds through condensation polymerization among the silicon hydroxyl groups to form a layer of silicon dioxide on the surface of the silver nano particles;
and centrifuging and washing the product to obtain silver nanoparticles coated by a silicon dioxide shell, and dispersing the silver nanoparticles coated by the silicon dioxide shell in tetrahydrofuran for later use.
In the step (2), the silver nanoparticles are coated by using silicon dioxide, wherein the thickness of the silicon dioxide layer is controlled by the conditions of the using amount of tetraethoxysilane, hydrolysis time, the using amount of sodium hydroxide and the like, and is generally adjusted between 2 and 50 nm. The purpose of using silicon dioxide to coat the silver nanoparticles is to reduce the interface energy between the silver nanoparticles and the organic silicon resin matrix, prevent the silver nanoparticles from agglomerating in the process of preparing the composite material and improve the dispersibility of the silver nanoparticles and the organic silicon resin prepolymer when the silver nanoparticles and the organic silicon resin prepolymer are subjected to solvent-assisted mixing.
Preferably, the step (3) is:
adjusting pH of water to weak acidity, adding ethyl orthosilicate and alkyl alkoxy silane (formula (RO)4- nSiR’n]And mercaptopropyl trimethoxy silane and the like as organic silicon resin precursors, stirring for reaction, and carrying out hydrolysis and polycondensation reaction on the organic silicon resin precursors;
after the reaction is finished, the solvent and the water are removed by rotary evaporation to be viscous, so that the organic silicon resin prepolymer with the organic group R' is obtained, and tetrahydrofuran is added into the organic silicon resin prepolymer for dilution and storage.
The alkylalkoxysilane [ (RO) used in the step (3)4-nSiR’n]Wherein the R group includes methyl, ethyl, etc., the R' group includes methyl, ethyl, phenyl, etc., and n is 1-2.
Preferably, the step (4) is:
dispersing the silver nanoparticles coated by the silicon dioxide shell layer prepared in the step (2) in a tetrahydrofuran solvent, adding the organic silicon resin prepolymer prepared in the step (3), and fully stirring to mix the silver nanoparticles and the organic silicon resin prepolymer to form a uniform dispersion system;
and then removing the solvent by rotary evaporation to a viscous state, adding aminopropyltriethoxysilane, uniformly stirring, pouring into a mould, removing gas and residual solvent in vacuum, and curing and forming to obtain the silver nanoparticle composite organic silicon resin material.
Preferably, the silver nanoparticles in the step (1) are silver nanospheres or silver nanosheets;
the specific preparation method of the silver nanospheres comprises the following steps:
preparation of seed solution: adding the sodium citrate solution into the silver nitrate solution, stirring and mixing, adding the sodium borohydride solution, and stirring and reacting for 10-20min to obtain a silver nano seed solution;
the concentrations of sodium citrate, silver nitrate and sodium borohydride in the whole reaction solution are respectively 1-1.5mmol/L, 0.2-0.25mmol/L and 0.25-0.3 mmol/L;
the preparation of silver nanosphere comprises adding silver nanometer seed solution into growth liquid 25-28 timesoStirring and reacting for 10-30min under C, centrifuging the reaction system, washing and precipitating to obtain silver nanospheres, and dispersing the silver nanospheres in water for later use;
in the growth solution, the concentrations of cetyl trimethyl ammonium bromide, silver nitrate, ascorbic acid and sodium hydroxide in the growth solution are respectively 0.04-0.05mol/L, 0.20-0.25mmol/L, 4-5mmol/L and 6-6.5 mmol/L;
the volume of the seed solution added into the growth solution accounts for 1-10% of the volume of the growth solution;
the specific preparation method of the silver nanosheet comprises the following steps:
preparation of seed solution: adding the sodium citrate solution into the silver nitrate solution, stirring and mixing, adding the sodium borohydride solution, and stirring and reacting for 10-20min to obtain a silver nano seed solution;
the concentrations of sodium citrate, silver nitrate and sodium borohydride in the whole reaction solution are respectively 1-1.5mmol/L, 0.2-0.25mmol/L and 0.25-0.3 mmol/L;
preparing silver nanosheets: adding silver nano seed solution into the growth liquid, 25-28%oStanding and reacting for 10-30min at the temperature of C, centrifuging, washing and precipitating a reaction system to obtain silver nano-sheets, and dispersing the silver nano-sheets in water for storage;
in the growth solution, the concentrations of cetyl trimethyl ammonium bromide, silver nitrate, ascorbic acid and sodium hydroxide in the growth solution are respectively 0.09-0.15mol/L, 0.25-0.3mmol/L, 6-7mmol/L and 10-15 mmol/L;
wherein the volume of the seed solution added into the growth solution accounts for 1-2% of the volume of the growth solution.
Preferably, the step (2) is specifically:
adding mercaptopropyl trimethoxy silane into the silver nanoparticles prepared in the step (1) at a temperature of between 25 and 30 percentoStirring for 4-5h under C; then regulating the pH value to 9-10 by using a NaOH solution, dropwise adding an ethyl orthosilicate ethanol solution, stirring to react for 10-15h, centrifuging, washing and precipitating by using water to obtain silver nanoparticles coated with a silicon dioxide shell, wherein the thickness of the silicon dioxide layer is 2-50nm, and dispersing the silver nanoparticles coated with the silicon dioxide shell in Tetrahydrofuran (THF) for storage for later use;
the amount of silver nano particles added is 1-2mg, and the amount of the substance of mercaptopropyltrimethoxysilane and ethyl orthosilicate added is 1-5mmol and 30-100mmol respectively.
Preferably, the step (3) is specifically:
adding dilute hydrochloric acid into pure water to adjust pH to 3-4, adding ethyl orthosilicate, alkylalkoxysilane and mercaptopropyltrimethoxysilane, and heating to 40-70oC, stirring at a high speed for reacting for 4-6 h; then, removing the solvent and water by rotary evaporation until the residual substrate is viscous to obtain an organic silicon resin prepolymer, adding THF (tetrahydrofuran) for dilution and storing;
the volume ratio of pure water, tetraethoxysilane, alkyl alkoxy silane and mercaptopropyl trimethoxy silane is 1: 0.1-0.5: 0.1-0.5: 0.003-0.02;
the molecular formula of the alkylalkoxysilane is (RO)4-nSiR’nWherein R is methyl, ethyl, etc., and R' is methyl, ethyl, phenyl, etc.
Preferably, in the step (4), the mass of the silver nanoparticles coated by the silica shell, the mass of the silicone resin prepolymer and the mass of the aminopropyltriethoxysilane are 0.02-2mg, 0.3-1.0g and 2-20mg, respectively.
Advantageous effects
The invention discloses a preparation method of silver nanoparticle composite organic silicon resin, which has the advantages of low cost, simple equipment and environmental friendliness. The preparation method comprises the steps of firstly preparing silver nanoparticles and organic silicon resin prepolymer coated by a silicon dioxide shell layer, then preparing a uniformly dispersed and stable dispersion system of the silver nanoparticles in the organic silicon resin prepolymer, and finally curing to obtain the solid sol material of the silver nanoparticle composite organic silicon resin.
The silver nanoparticles prepared by the method have narrow size distribution, can form a uniform dispersion system in an organic silicon resin matrix, and the obtained solid sol composite material has good uniformity.
In the preparation method, the silicon dioxide is used for coating the silver nanoparticles, so that the interface energy between the silver nanoparticles and the organic silicon resin matrix can be reduced, the aggregation of the silver nanoparticles in the process of preparing the composite material is prevented, and the dispersibility of the silver nanoparticles and the organic silicon resin prepolymer in solvent-assisted mixing is improved.
The optical property of the silver nanoparticle composite organic silicon resin material prepared by the invention is mainly determined by the optical property of the used silver nanoparticles, and the absorbance and the light transmittance of the absorption spectrum of the silver nanoparticle composite organic silicon resin material are controlled by the amount of the added silver nanoparticles. The composite material has wide application prospect in the field of optical materials, such as plasma materials, nonlinear optical materials, laser protection materials and the like. Moreover, the composite material combines the high weather resistance of the silicone resin and the high stability of the metal nanoparticles, and the color thereof has long-term stability in a normal environment, and has antibacterial and antistatic capabilities.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) photograph of silver nanospheres;
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of silica-coated silver nanospheres;
FIG. 3 is a Fourier transform infrared (FT-IR) spectrum of a silicone resin prepolymer;
FIG. 4 is a photograph of a silver nanosphere composite silicone resin material;
FIG. 5 is a UV-vis spectrum of the silver nanosphere composite silicone resin material;
FIG. 6 shows thermogravimetric spectrum of silver nanosphere composite organic silicon resin material
FIG. 7 Transmission Electron Microscopy (TEM) photograph of silver nanoplates;
FIG. 8 Transmission Electron Microscope (TEM) photograph of silica-coated silver nanoplates
FIG. 9 is a photograph of a silver nanoplate composite silicone resin material;
FIG. 10 is a UV-vis spectrum of the silver nanosheet composite organic silicon resin material.
Detailed Description
For better understanding of the present invention, the technical solution of the present invention will be described in detail with specific examples, but the present invention is not limited thereto.
Example 1
The preparation method of the silver nanosphere composite organic silicon resin comprises the following steps:
(1) the silver nanospheres are prepared by adopting a seed growth method.
(1-1) preparation of seed solution: and (3) taking 20 mL of sodium citrate solution (1.25 mmol/L), adding 0.1 mL of silver nitrate solution (50 mmol/L), stirring and mixing, adding 1.2 mL of sodium borohydride solution (5 mmol/L), and stirring and reacting for 10 min to obtain the silver nano seed solution.
(1-2) preparation of silver nanosphere by taking 20 mL of cetyltrimethylammonium bromide solution (0.05 mol/L), adding 0.1 mL of silver nitrate (50 mmol/L), 1 mL of ascorbic acid (0.1 mol/L) and 1.5 mL of the silver nanophase seed solution obtained in the above step (1-1), and then adding 0.14 mL of sodium hydroxide solution (1 mol/L), 27oAnd C, stirring and reacting for 15 min, centrifuging the reaction system, washing the precipitate, and re-dispersing the silver nanosphere precipitate into water.
(2) Silica coating of silver nanospheres. Taking 20 mL (containing 0.5 mg silver) of the silver nanosphere solution prepared in the step (1-2), adding 0.2 mL mercaptopropyltrimethoxysilane (10.8 mmol/L) in 27oC, stirring for 5 hours under heating in a water bath. Then adjusting the pH value to 9-10 by using 0.1 mol/L NaOH solution, dropwise adding 0.16 mL ethyl orthosilicate ethanol solution (0.9 mol/L), stirring and reacting for 12 h, centrifuging, washing the precipitate by using water, washing the precipitate by using THF, and dispersing into THF.
(3) And (3) preparing an organic silicon resin prepolymer. Adding 33.75 mL of ultrapure water into a 50 mL single-neck flask, adding 0.04 mL of dilute hydrochloric acid (0.1 mol/L) to adjust the diluted hydrochloric acid to be weakly acidic, adding 5 mL of ethyl orthosilicate, 10 mL of methyltriethoxysilane and 0.2 mL of mercaptopropyltrimethoxysilane, and adding 60 mL of pure wateroC, stirring and reacting for 5 hours under the heating of water bath. And then, removing ethanol and water by rotary evaporation until the residual substrate is viscous, thus obtaining the organic silicon resin prepolymer, and adding THF for dilution and then storing.
(4) And (3) preparing the silver nanosphere composite organic silicon resin. Taking a certain amount of silicon dioxide-coated silver nanosphere THF dispersion system (containing 0.27 mg and 0.45 mg of silver respectively and corresponding to samples a and b), centrifugally concentrating to 1 mL, adding the THF solution containing 1 g of the organic silicon resin prepolymer prepared in the step (3), stirring and mixing uniformly, evaporating most of the solvent in vacuum to enable the system to be viscous, adding 10 mg of aminopropyl trimethoxysilane, stirring fully, taking 0.3 g of the solution to be transferred into a polytetrafluoroethylene mold, removing gas and residual solvent in vacuum, and curing at room temperature to obtain the silver nanoparticle composite organic silicon resin material.
The transmission electron microscope photograph of the silver nanospheres obtained in step (1-2) of this example is shown in fig. 1. As can be seen from the figure, the size of the obtained silver nanoparticles is between 15-40 nm, and the average size is 30 nm.
The transmission electron microscope photograph of the silica-coated silver nanospheres obtained in step (2) of this example is shown in fig. 2. It can be seen from the figure that the average thickness of the silica shell layer is 15 nm.
The FT-IR spectrum of the silicone resin prepolymer obtained in step (3) of this example is shown in FIG. 3. As can be seen from the figure, 3443 cm-1In the corresponding absorption of hydroxyl groups, 2970, 2934 and 1273 cm-1Corresponds to the absorption of methyl, 1000-1124 cm-1The broad peak between corresponds to the absorption of this Si-O-Si bond.
The photo of the silver nanosphere composite silicone resin material obtained in step (4) of this embodiment is shown in fig. 4, and a sample is placed on a base plate with letters, so that the sample is better in transparency, and the samples a and b are yellow transparent solids, and the color deepens as the content of the silver nanospheres increases; the corresponding UV-vis spectrum is shown in FIG. 5, and the central position of the absorption peak is 450nm, wherein the absorbance of the sample a is 0.38, and the absorbance of the sample b is 0.66.
Fig. 6 shows a thermal weight loss curve of the silver nanosphere composite silicone resin obtained in step (4) of this example under a nitrogen atmosphere. From the plot, it can be seen that the sample is at 200oThe weight loss rate of C or less is about 2.5% to 700%oThe weight loss at C was about 7%.
Example 2
The preparation method of the silver nanosheet composite organic silicon resin comprises the following steps:
(1) and preparing the silver nanosheet by adopting a seed growth method.
(1-1) preparation of seed solution: and (3) taking 20 mL of sodium citrate solution (1.25 mmol/L), adding 0.1 mL of silver nitrate solution (50 mmol/L), stirring and mixing, adding 1.2 mL of sodium borohydride solution (5 mmol/L), and stirring and reacting for 10-20min to obtain the silver nano seed solution.
(1-2) preparation of silver nanoplates: 30 mL of a cetyltrimethylammonium bromide solution (0.1 mol/L) was added0.2 mL of silver nitrate solution (50 mmol/L), 2 mL of ascorbic acid solution (0.1 mol/L), 0.5 mL of the silver nanophase solution obtained in the above step (1-1), and then 0.44 mL of sodium hydroxide (1 mol/L), 27 mLoAnd C, standing for reaction for 10-30min, centrifuging the reaction system, washing and precipitating to obtain silver nano sheets, and re-dispersing the silver nano sheets into water.
(2) Silica coating of silver nanoplates. 20 mL of the silver nanoparticles prepared in step (1-3) above was added with 0.2 mL of mercaptopropyltrimethoxysilane (10.8 mmol/L) at 27oC, stirring for 5 hours under heating in a water bath. Then, the pH value is adjusted to 9-10 by 0.1 mol/L NaOH solution, 0.16 mL ethyl orthosilicate ethanol solution (0.9 mol/L) is dripped, the mixture is stirred and reacted for 12 hours, and then the mixture is centrifuged, washed and precipitated by water, washed and precipitated by THF and dispersed into THF.
(3) And (3) preparing an organic silicon resin prepolymer. Adding 33.75 mL of ultrapure water into a 50 mL single-neck flask, adding 0.04 mL of dilute hydrochloric acid (0.1 mol/L) to adjust the diluted hydrochloric acid to be weakly acidic, adding 8 mL of tetraethoxysilane, 7 mL of methyltriethoxysilane and 0.3 mL of mercaptopropyltrimethoxysilane, and adding the mixture into the flask at 60 mLoC, stirring and reacting for 5 hours under the heating of water bath. And then, removing ethanol and water by rotary evaporation until the residual substrate is viscous, thus obtaining the organic silicon resin prepolymer, and adding THF for dilution and then storing.
(4) And (3) preparing the silver nanosheet composite organic silicon resin. Taking a certain volume of silicon dioxide-coated silver nanosheet THF dispersion system (containing 0.18 mg and 0.36 mg of silver respectively, corresponding to samples c and d), centrifugally concentrating to a volume of 1 mL, then adding the THF solution containing 1 g of the organic silicon resin prepolymer prepared in the step (3), stirring and mixing uniformly, evaporating the solvent in vacuum to enable the system to become viscous, then adding aminopropyl trimethoxysilane, fully stirring, removing 0.3 g of the solution, transferring the solution to a polytetrafluoroethylene mold, removing gas and residual solvent in vacuum, and curing at room temperature to obtain the silver nanoparticle composite organic silicon resin material.
The transmission electron micrograph of the silver nanosheets obtained in step (1-2) of this example is shown in fig. 7. As can be seen from the figure, the size of the obtained silver nanoplates ranges from 80 to 110 nm.
A transmission electron micrograph of the silica-coated silver nanosheet obtained in step (2) of this example is shown in fig. 8. As can be seen, the thickness of the silica shell is about 5 nm.
The photo of the silver nanosheet composite organic silicon resin material obtained in step (4) of the embodiment is shown in fig. 9, and when a sample is placed on a bottom plate with letters, it can be seen that the transparency of the sample is better, and the obtained samples c and d are blue transparent solids, so that the color deepens along with the increase of the content of the silver nanosheets. The corresponding UV-vis spectrum is shown in FIG. 10. As can be seen from the figure, the sample has strong absorption between 350 nm and 700 nm, the maximum absorption peak position is 620 nm, the absorbance of the sample corresponding to c is 0.21, and the absorbance of the sample corresponding to d is 0.32.
Claims (5)
1. The preparation method of the silver nanoparticle composite organic silicon resin is characterized by comprising the following steps of:
(1) preparing silver nanoparticles by adopting a seed growth method under the protection of a surfactant;
(2) preparing silver nanoparticles coated by a silicon dioxide shell layer by using the silver nanoparticles obtained in the step (1) through a Stoeber hydrolysis method;
(3) preparing an organic silicon resin prepolymer;
(4) preparing silver nano particles coated by the silicon dioxide shell layer prepared in the step (2) and the organic silicon resin prepolymer prepared in the step (3) into a silver nano particle composite organic silicon resin material through a solvent-assisted compounding process;
the step (1) is as follows:
reducing silver nitrate by using sodium borohydride under the protection of sodium citrate to prepare a silver nano seed solution;
adding the silver nano seed solution into a growth solution containing hexadecyl trimethyl ammonium bromide, silver nitrate, ascorbic acid and sodium hydroxide, and stirring for reaction;
after the reaction is finished, centrifuging, washing and precipitating the reaction product to obtain silver nanoparticles, and dispersing the silver nanoparticles in water for storage;
the silver nano particles in the step (1) are silver nanospheres and silver nano sheets;
the specific preparation method of the silver nanospheres comprises the following steps:
preparation of seed solution: adding the sodium citrate solution into the silver nitrate solution, stirring and mixing, adding the sodium borohydride solution, and stirring and reacting for 10-20min to obtain a silver nano seed solution;
the concentrations of sodium citrate, silver nitrate and sodium borohydride in the whole reaction solution are respectively 1-1.5mmol/L, 0.2-0.25mmol/L and 0.25-0.3 mmol/L;
preparing silver nanospheres: adding the silver nano seed solution into the growth solution, stirring and reacting for 10-30min at 25-28 ℃, centrifuging a reaction system, washing and precipitating to obtain silver nanospheres, and dispersing the silver nanospheres in water for later use; in the growth solution, the concentrations of cetyl trimethyl ammonium bromide, silver nitrate, ascorbic acid and sodium hydroxide in the growth solution are respectively 0.04-0.05mol/L, 0.20-0.25mmol/L, 4-5mmol/L and 6-6.5 mmol/L;
the volume of the seed solution added into the growth solution accounts for 1-10% of the volume of the growth solution;
the specific preparation method of the silver nanosheet comprises the following steps:
preparation of seed solution: adding the sodium citrate solution into the silver nitrate solution, stirring and mixing, adding the sodium borohydride solution, and stirring and reacting for 10-20min to obtain a silver nano seed solution;
the concentrations of sodium citrate, silver nitrate and sodium borohydride in the whole reaction solution are respectively 1-1.5mmol/L, 0.2-0.25mmol/L and 0.25-0.3 mmol/L;
preparing silver nanosheets: adding the silver nano seed solution into the growth solution, standing and reacting for 10-30min at 25-28 ℃, centrifuging, washing and precipitating a reaction system to obtain silver nano sheets, and dispersing the silver nano sheets in water for storage;
in the growth solution, the concentrations of cetyl trimethyl ammonium bromide, silver nitrate, ascorbic acid and sodium hydroxide in the growth solution are respectively 0.09-0.15mol/L, 0.25-0.3mmol/L, 6-7mmol/L and 10-15 mmol/L;
wherein the volume of the seed solution added into the growth solution accounts for 1-2% of the volume of the growth solution;
the step (2) is as follows:
adding mercaptopropyl trimethoxy silane solution into the silver nanoparticles obtained in the step (1), then adding ethyl orthosilicate, uniformly mixing, adding sodium hydroxide to enable a system to be in a weak alkaline condition, and stirring for reaction;
after the reaction is finished, centrifuging and washing the product to obtain silver nanoparticles coated by a silicon dioxide shell layer, and dispersing the silver nanoparticles coated by the silicon dioxide shell layer in tetrahydrofuran for storage;
the step (3) is as follows:
adjusting the pH value of water to weak acidity, adding ethyl orthosilicate, alkylalkoxysilane and mercaptopropyl trimethoxysilane serving as an organic silicon resin precursor, stirring for reaction, and carrying out hydrolysis and polycondensation on the organic silicon resin precursor;
after the reaction is finished, removing the solvent and water by rotary evaporation to be viscous to obtain an organic silicon resin prepolymer, and adding tetrahydrofuran into the organic silicon resin prepolymer for dilution and storage;
the step (4) is as follows:
taking the silver nanoparticles coated by the silicon dioxide shell layer prepared in the step (2), adding the organic silicon resin prepolymer prepared in the step (3), and fully stirring to mix the silver nanoparticles coated by the silicon dioxide shell layer with the organic silicon resin prepolymer to form a uniform dispersion system;
and then removing the solvent by rotary evaporation to a viscous state, adding aminopropyltriethoxysilane, uniformly stirring, pouring into a mould, removing gas and residual solvent in vacuum, and curing and forming to obtain the silver nanoparticle composite organic silicon resin material.
2. The method for preparing the silver nanoparticle composite silicone resin according to claim 1, wherein the step (2) is specifically:
adding mercaptopropyl trimethoxy silane into the silver nanoparticles prepared in the step (1), and stirring for 4-5h at the temperature of 25-30 ℃; then regulating the pH value to 9-10 by using a NaOH solution, dropwise adding an ethyl orthosilicate ethanol solution, stirring for reacting for 10-15h, centrifuging, washing and precipitating by using water to obtain silver nanoparticles coated by a silicon dioxide shell, wherein the thickness of the silicon dioxide shell is 2-50nm, and dispersing the silver nanoparticles coated by the silicon dioxide shell in tetrahydrofuran for later use;
the amount of silver nanoparticles added was 1-2mg, and the amount of the added substances of mercaptopropyltrimethoxysilane and ethyl orthosilicate was 1-5mmol and 30-100mmol, respectively.
3. The method for preparing the silver nanoparticle composite silicone resin according to claim 1, wherein the step (3) is specifically:
adding dilute hydrochloric acid into pure water to adjust pH to 3-4, adding tetraethoxysilane, alkylalkoxysilane and mercaptopropyltrimethoxysilane, heating to 40-70 ℃, and reacting for 4-6h under high-speed stirring; then, removing the solvent and water by rotary evaporation until the residual substrate is viscous to obtain an organic silicon resin prepolymer, adding tetrahydrofuran for dilution, and storing;
the volume ratio of pure water, tetraethoxysilane, alkyl alkoxy silane and mercaptopropyl trimethoxy silane is 1: 0.1-0.5: 0.1-0.5: 0.003-0.02.
4. The method for preparing silver nanoparticle composite silicone resin according to claim 1, wherein in step (4), the mass of the silver nanoparticles coated with the silica shell, the mass of the silicone resin prepolymer and the mass of the aminopropyltriethoxysilane are 0.02-2mg, 0.3-1.0g and 2-20mg, respectively.
5. A silver nanoparticle composite silicone resin, characterized by being produced by the method according to any one of claims 1 to 4.
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