CN109096766B - Preparation method of gold nanoparticle composite organic silicon resin - Google Patents

Preparation method of gold nanoparticle composite organic silicon resin Download PDF

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CN109096766B
CN109096766B CN201810886458.XA CN201810886458A CN109096766B CN 109096766 B CN109096766 B CN 109096766B CN 201810886458 A CN201810886458 A CN 201810886458A CN 109096766 B CN109096766 B CN 109096766B
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李东祥
林伟鸿
高媛媛
李春芳
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Qingdao University of Science and Technology
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Abstract

The invention relates to the technical field of metal nano composite materials, in particular to a preparation method of gold nanoparticle composite organic silicon resin. The gold nanoparticle composite organic silicon resin solid sol material is prepared by firstly preparing gold nanoparticles coated with silicon dioxide, then mixing the gold nanoparticles with an organic silicon resin prepolymer through the dispersion effect of a solvent, fully stirring and uniformly mixing to obtain a uniform dispersion system of the gold nanoparticles and the organic silicon resin prepolymer, then adding a curing agent and evaporating the solvent, and curing at room temperature or by heating. The gold nanoparticle composite organic silicon resin material prepared by the invention has the characteristics of excellent oxidation resistance, chemical resistance and the like, has very high temperature resistance and ageing resistance, can keep long-term stability, and has wide application prospect when being used as a color development material, a nonlinear optical material, a laser protection material and the like.

Description

Preparation method of gold nanoparticle composite organic silicon resin
Technical Field
The invention relates to the technical field of metal nano composite materials, in particular to a preparation method of gold nanoparticle composite organic silicon resin.
Background
The gold nanoparticles belong to metal nanomaterials and are nanoscale spherical and rod-shaped crystal particles composed of gold atoms and having different sizes and shapes. The interaction between the gold nanoparticles and an external electromagnetic field (such as light) generates a local surface plasmon resonance phenomenon, and the gold nanoparticles have strong resonance absorption in a visible light region to a near infrared region. Wherein, the surface plasma resonance absorption peak of the spherical gold nano-particles can be increased from 515 nm to 600 nm according to the difference of the sizes, and the spherical gold nano-particles show different colors such as red, pink, purple and the like; the surface plasma resonance of the gold nanorods has two absorption peaks in the radial direction and the axial direction, wherein the radial absorption peak is near 510 nm, the axial absorption peak is gradually increased from 550 nm to a near infrared region along with the increase of the length-diameter ratio of the gold nanorods, and the color of a dispersion system of the gold nanorods respectively shows red, purple, blue, scarlet, khaki and the like along with the increase of the length-diameter ratio.
The gold nanoparticles are not decomposed by ultraviolet irradiation, and compared with organic dye molecules, the color of the gold nanoparticles does not fade and change with time, and the gold nanoparticles have nearly permanent optical stability. The gold nanoparticles have potential application in the fields of optical sensing, biological imaging, biological detection, disease detection, cancer treatment and the like due to the characteristics of absorption, surface-enhanced scattering, surface-enhanced fluorescence, photothermal conversion, luminescence and the like caused by surface plasmon resonance.
The organic silicon resin is a highly cross-linked polysiloxane network structure taking silicon-oxygen-silicon bonds as a main component, and part of silicon atoms are connected with organic groups, so that the organic silicon resin has the characteristics of organic materials and inorganic materials, has a plurality of unique performances such as excellent thermal oxidation stability, cold resistance, weather resistance, electric insulation linearity, hydrophobicity, anti-adhesion and demolding performance and the like, is widely used for high and low temperature resistant insulating paint, special coating, molding compound and the like, and is widely applied to the aspects of aerospace, electronic and electric appliances, building, machinery and the like.
In the prior art, people prepare the composite film embedded in a silicon dioxide matrix by a mixed deposition technology of plasma enhanced chemical vapor deposition silicon dioxide and co-sputtered gold nanoparticles, but the technology has high requirements on equipment conditions, high technical difficulty and cost and is not suitable for practical production.
Disclosure of Invention
The invention aims to find a technology and a method for realizing uniform dispersion of gold nanoparticles and an organic silicon resin matrix material, and meets the requirements of low cost, simple equipment, environmental friendliness and the like.
According to the invention, the gold nanoparticles are protected by silicon dioxide, so that the problem of nanoparticle agglomeration in the process of preparing the composite material is solved, and the prepared nanoparticle composite material has good uniformity; the gold nanoparticles adopted by the invention have the advantages of uniform size and shape; the organic silicon resin adopted by the invention is used as a matrix material, not only has high transparency, but also has high temperature resistance, so that the organic silicon resin has obvious advantages when being used as an optical material, in particular a laser and strong light protection material.
In order to achieve the purpose, the gold nanoparticles coated with silicon dioxide are firstly prepared, then are mixed with the organic silicon resin prepolymer through the solvent dispersion effect, the mixture is fully stirred and uniformly mixed to obtain a uniform dispersion system of the gold nanoparticles and the organic silicon resin prepolymer, then a curing agent is added, the solvent is evaporated, and the gold nanoparticle composite organic silicon resin solid sol material is prepared after room temperature or heating curing.
In addition, the gold 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 gold nanoparticle composite organic silicon resin comprises the following steps:
(1) preparing gold nanoparticles by adopting a seed-mediated growth method under the protection of a surfactant;
(2) preparing gold nanoparticles coated with silicon dioxide by using the gold nanoparticles obtained in the step (1) through a Stoeber hydrolysis method;
(3) preparing an organic silicon resin prepolymer;
(4) and (3) taking the gold nanoparticles coated by the silicon dioxide shell layer prepared in the step (2) and the organic silicon resin prepolymer prepared in the step (3), and preparing the gold nanoparticle composite organic silicon resin material through a solvent-assisted compounding process.
Preferably, the step (1) is:
gold chloride acid is used as a raw material, and sodium borohydride is used for reduction to prepare a gold nano seed solution under the protection of cetyl trimethyl ammonium bromide serving as a surfactant;
adding the gold nano-seed solution into the growth solution, and stirring for reaction;
and after the reaction is finished, centrifuging, washing and precipitating the reaction product to obtain gold nanoparticles, and dispersing the gold nanoparticles in water for storage.
Preferably, the step (2) is:
adding mercaptopropyl trimethoxy silane solution into the gold nanoparticles obtained in the step (1) to enable the surfaces of the gold nanoparticles to be connected with a layer of mercaptopropyl trimethoxy silane molecules through gold-sulfur bonds;
adding ethyl orthosilicate into the system, uniformly mixing, adding ammonia water to form an alkaline environment, hydrolyzing silicon-alkoxy bonds into silicon-oxygen-silicon bonds, and forming a silicon dioxide protective layer on the surface of the gold nanoparticles; the thickness of the silicon dioxide layer is controlled by the using amount and hydrolysis time of the ethyl orthosilicate, the concentration of the sodium hydroxide and other conditions. The thickness of the silicon dioxide layer is typically adjusted between 2-50 nm.
After the reaction is finished, the gold nanoparticles coated with the silicon dioxide are dispersed in tetrahydrofuran after being centrifuged and washed.
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 as an organic silicon resin precursor, stirring for reaction, and carrying out hydrolysis and polycondensation reaction on the organic silicon resin precursor;
after the reaction is finished, the solvent and water are removed by rotary evaporation to be viscous, and the organic silicon resin prepolymer with an organic group of R' is obtained, the prepolymer contains a certain amount of Si-OH structures, and tetrahydrofuran is added into the organic silicon resin prepolymer for dilution and preservation.
Preferably, the step (4) is:
dispersing the gold nanoparticles coated with 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 gold nanoparticles and the organic silicon resin prepolymer to form a uniform dispersion system;
and then removing the solvent to be viscous, adding aminopropyltriethoxysilane as a cross-linking agent, uniformly stirring, pouring the dispersion system into a mould, removing gas and residual solvent in vacuum, and curing to obtain the gold nanoparticle composite organic silicon resin material.
In the step (1) of the present invention, the size and shape of the gold nanoparticles can be adjusted by changing the concentration of each reactant in the growth liquid. The concentration of hexadecyl trimethyl ammonium bromide in a growth solution is 0.02-0.05mol/L when the gold nanospheres are prepared, silver nitrate is not contained, the size of the obtained gold nanospheres is uniform and can be adjusted between 10 nm and 200 nm; when the gold nanorods are prepared, the concentration of hexadecyl trimethyl ammonium bromide in the growth solution is 0.08-0.15mol/L, the concentration of silver nitrate is 0.3-1.5mmol/L, the length-diameter ratio of the obtained gold nanorods is controlled by the concentration of silver nitrate, and the length-diameter ratio range is 1.5-10.
The alkylalkoxysilane [ (RO) used in the step (3) of the present invention4-nSiR’n]Wherein R includes methyl, ethyl, etc., R' includes methyl, ethyl, phenyl, etc., and n is 1-2. The volume ratio of the alkyl alkoxy silane to the ethyl orthosilicate used in the step can be adjusted to be 3-0.3, and the volume ratio of the mercaptopropyl trimethoxy silane to the ethyl orthosilicate can be adjusted to be 0.01-0.2.
Preferably, the gold nanoparticles in the step (1) are gold nanospheres or gold nanorods;
the specific preparation method of the gold nanospheres comprises the following steps:
preparation of seed solution: mixing cetyl trimethyl ammonium bromide solution and chloroauric acid water solution, adding sodium borohydride solution, 25-28%oUniformly stirring for 1-2h under C to obtain brown gold nano seed solution;
the concentrations of hexadecyl trimethyl ammonium bromide, chloroauric acid and sodium borohydride in the whole reaction solution are respectively 0.08-0.15mol/L, 0.2-0.3mmol/L and 0.5-0.8 mmol/L;
preparing gold nanospheres: adding gold nanometer seed solution into the growth solution at 25-28 deg.CoC, slowly stirring for reaction for 6-12 hours, centrifuging and washing the solution after reaction, collecting gold nanosphere precipitate, and dispersing the gold nanosphere precipitate in water for later use;
in the growth solution, the concentrations of cetyl trimethyl ammonium bromide, chloroauric acid and ascorbic acid in the growth solution are 0.02-0.05mol/L, 0.05-0.10mmol/L and 2.0-2.5mmol/L respectively;
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 gold nanorods comprises the following steps:
preparation of seed solution: mixing cetyl trimethyl ammonium bromide solution and chloroauric acid solution uniformly, and adding into a mixing tank at 25-28 deg.CoAdding a sodium borohydride solution under C, and stirring at high speed for 2-6h to obtain a brownish yellow gold nanoparticle solution;
the concentrations of hexadecyl trimethyl ammonium bromide, chloroauric acid and sodium borohydride in the whole reaction solution are respectively 0.08-0.15mol/L, 0.2-0.3mmol/L and 0.5-0.8 mmol/L;
preparing gold nanorods: in the range of 25-28oAdding the seed solution into the growth solution, uniformly stirring, standing for reacting for 6-12 hours, centrifuging and washing a reaction product, collecting gold nanorod precipitates, and dispersing the gold nanorod precipitates in water for later use;
in the growth solution, the concentrations of cetyl trimethyl ammonium bromide, chloroauric acid, silver nitrate and ascorbic acid in the growth solution are respectively 0.08-0.15mol/L, 0.4-0.7mmol/L, 0.3-1.5mmol/L and 0.5-0.8 mmol/L;
the volume of the seed solution added into the growth solution accounts for 0.1-0.5% of the volume of the growth solution;
preferably, the step (2) is specifically:
taking the gold nanoparticle dispersion solution prepared in the step (1), dropwise adding an ethanol solution of mercaptopropyl trimethoxy silane under the stirring condition, adjusting the pH of the solution to 10-11 by using ammonia water, and then dropwise adding the solution with the volume ratio of 10% of ethyl orthosilicate in ethanol in a concentration of 25-28oStirring and reacting for 5-12h under C; then, centrifuging, washing and precipitating to obtain gold nanospheres coated with silicon dioxide, and dispersing in tetrahydrofuran;
the added gold nano particles are 0.1-2mg, and the amounts of the added mercaptopropyltrimethoxysilane and the added ethyl orthosilicate are 1-5mmol and 20-100mmol respectively.
Preferably, the step (3) is specifically:
adding dilute hydrochloric acid into water, adjusting pH of water to 3-4, adding ethyl orthosilicate and alkyl alkoxy silicon [ molecular formula (RO)4-nSiR’nWherein R is methyl, ethyl, etc., and R' is methyl, ethyl, phenyl, etc]And mercaptopropyltrimethoxysilane, heated to 40-70oStirring and reacting for 4-6h under the condition of C; after the reaction is finished, carrying out rotary evaporation on the solution, removing the solvent and water until the residual substrate is viscous, obtaining a viscous and transparent liquid, namely the organic silicon resin prepolymer, and adding Tetrahydrofuran (THF) to dilute and store the liquid;
the volume ratio of water, ethyl orthosilicate, alkylalkoxysilane and mercaptopropyltrimethoxysilane is 1: 0.1-0.5: 0.1-0.5: 0.003-0.05.
Preferably, in the step (4), the mass ratio of the silver nanoparticles coated with the silica shell layer, the silicone resin prepolymer and the aminopropyltriethoxysilane is 0.02-2mg, 0.3-1.0g and 2-20mg, respectively.
The solid sol formed by the gold nanoparticles and the organic silicon resin prepared by the invention is an optically active material and has good application value.
Advantageous effects
The invention discloses a preparation method of gold nanoparticle composite organic silicon resin, which is low in cost, simple in equipment and environment-friendly.
In the preparation process, the gold nanoparticles coated with the silicon dioxide are prepared, and on one hand, the silicon dioxide shell layer on the surface of the gold nanoparticles prevents the gold nanoparticles from agglomerating in the process of preparing the composite material; on the other hand, the shell layer has the same main chemical structure (Si-O-Si bond) with the organic silicon resin, so that the interface energy between the metal nano particles and the organic silicon resin matrix can be reduced, and the composite dispersion system has better compatibility when being prepared.
According to the invention, the organic silicon resin and the gold nanoparticles are combined to prepare a uniform solid sol material of the metal nanoparticles in the silicon resin, so that the combination of the characteristics of the gold nanoparticles and the excellent performances of the silicon resin, such as temperature resistance, coatability and the like, is realized, and the gold nanoparticle composite organic silicon resin material with uniform dispersion, high transparency and unique performance is obtained and can be used as a coating material. The gold nanoparticle composite organic silicon resin material prepared by the invention has the characteristics of excellent oxidation resistance, chemical resistance and the like, has high temperature resistance and ageing resistance, and can keep long-term stability.
The optical characteristics of the gold nanoparticle composite organic silicon resin material prepared by the invention are mainly determined by the optical characteristics of the used gold nanoparticles, and the absorbance and the light transmittance of the absorption spectrum are controlled by the properties and the dosage of the added gold nanoparticles.
The gold nanoparticle composite organic silicon resin prepared by the invention has good high temperature resistance, and 700 is proved by thermal weight loss analysisoThe weight loss rate at C is only 5%. The gold nanoparticle composite organic silicon resin prepared by the method combines the high weather resistance of the organic silicon resin and the high stability of the metal nanoparticles, and the color of the gold nanoparticle composite organic silicon resin has long-term stability in common environment. The gold nanoparticle composite organic silicon resin prepared by the invention has wide application prospects as a color developing material, a nonlinear optical material, a strong light protection material and the like, such as a high-stability red material, a laser protection material and the like.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of gold nanospheres;
FIG. 2 is a Transmission Electron Microscope (TEM) image of silica-coated gold nanospheres;
FIG. 3 is a Transmission Electron Microscope (TEM) image of gold nanorods;
FIG. 4 is a Transmission Electron Microscope (TEM) image of silica-coated gold nanorods;
FIG. 5 is a Fourier transform infrared (FT-IR) spectrum of a silicone resin prepolymer;
FIG. 6 is a photograph of a gold nanosphere composite silicone resin material;
FIG. 7 is a UV-vis spectrum of gold nanosphere composite silicone resin material;
FIG. 8 is a photograph of a gold nanorod composite silicone resin material;
FIG. 9 is a UV-vis spectrum of the gold nanorod composite organic silicon resin material;
FIG. 10 shows the thermogravimetric spectrum of the gold nanorod 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 gold nanosphere composite organic silicon resin material comprises the following specific steps:
(1) and preparing the gold nanospheres by adopting a surfactant-assisted seed growth method. 2 mL of hexadecyltrimethylammonium bromide (0.2 mol/L) and 2 mL of chloroauric acid aqueous solution (0.5 mmol/L) are mixed uniformly, and 0.48 mL of sodium borohydride solution (5 mmol/L) and 27oAnd C, uniformly stirring for 2 hours to obtain a gold nano seed solution. Then, 0.7 mL of the nanophase seed solution was added to a mixture (growth solution) of 10mL of cetyltrimethyl ammonium bromide (0.04 mol/L), 10mL of chloroauric acid solution (1.0 mmol/L) and 0.2 mL of ascorbic acid solution (0.2 mol/L) at 27oThe reaction was stirred slowly for 6 hours under C. And centrifuging the red solution obtained by the reaction, collecting gold nanosphere precipitate, and dispersing in water for later use.
(2) Silicon dioxideAnd preparing the coated gold nanospheres. Taking 10mL of the above gold nanosphere dispersion solution, dropwise adding 0.2 mL of mercaptopropyltrimethoxysilane ethanol solution (10.8 mmol/L) while stirring, adjusting pH of the solution to 10-11 with ammonia water, then dropwise adding 3.2 mL of ethyl orthosilicate ethanol solution (volume ratio of 10%) in 27oThe reaction was stirred for 12 hours at C. Then, the precipitate was centrifuged and washed to obtain silica-coated gold nanospheres, which were dispersed in Tetrahydrofuran (THF).
(3) And (3) preparing an organic silicon resin prepolymer. To 33.75 mL of water was added 0.040 mL of dilute hydrochloric acid (0.10 mol/L), followed by 5mL of ethyl orthosilicate (4.65 g, 0.022 mol), 10mL of methyltriethoxysilane (8.96 g, 0.050 mol), 0.9 mL of mercaptopropyltrimethoxysilane (0.95 g, 0.005 mol), and the mixture was mixed at 60 mLoReflux with stirring at C for 5 hours. And (3) performing rotary evaporation on the solution after the reaction to remove ethanol and most of water to obtain viscous and transparent liquid, namely the organic silicon resin prepolymer, and adding a THF (tetrahydrofuran) solvent for dilution and then storing.
(4) Preparing the gold nanosphere composite organic silicon resin material. And (3) respectively taking three parts of THF solution containing 1.0g of organic silicon resin prepolymer and dispersed in the step (3), adding THF dispersing liquid (containing gold nanospheres, namely 0.3 mg, 0.8 mg and 1.4 mg respectively, and corresponding samples, namely a, b and c) of the silicon dioxide-coated gold nanospheres in the step (2) with different volumes, and fully stirring and uniformly mixing at room temperature to form a uniform and transparent dispersing system. Then, evaporating the solvent under vacuum until the system is viscous, adding 20mg aminopropyltriethoxysilane, stirring, pouring 0.3 g into a mold, removing gas and residual solvent, storing at room temperature for 5 hr, and adding 45%oAnd C, preserving the mixture in an oven for 3 hours to obtain the cured gold nanosphere composite organic silicon resin material.
The TEM photograph of the gold nanospheres obtained in step (1) of this example is shown in FIG. 1, and it can be seen that the size of the gold nanospheres is between 10 and 20 nm, and the average size is 15 nm; the transmission electron microscope photograph of the silica-coated gold nanospheres obtained in step (2) is shown in fig. 2, and it can be seen that the thickness of the coated silica layer is 10 nm on average;
the Fourier transform infrared spectrum (FT-IR) of the silicone resin prepolymer obtained in step (3) of this example is shown in FIG. 5, in which 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.
Optical photographs and UV-vis spectra of the gold nanosphere composite silicone resin material with different contents obtained in step (4) of this example are shown in fig. 6 and 7. In fig. 6, the sample is placed on the bottom plate with letters, so that the transparency of the sample is better, the samples a, b and c are red transparent solids, the color is deepened along with the increase of the amount of the added gold nanospheres, and the plasma resonance absorption peak position of the sample is 540 nm.
Example 2
The embodiment prepares the gold nanorod composite organic silicon resin material, and the preparation process comprises the following specific steps:
(1) and preparing gold nanorods. 2 mL of a cetyltrimethyl ammonium bromide solution (0.20 mol/L) was mixed with 2 mL of HAUCL4The solution (0.5 mmol/L) was mixed well and then at 27oAdd 0.48 mL NaBH under C4The solution (5 mmol/L) was stirred at high speed for 2 hours to give a brownish yellow seed solution. Then, at 27oUnder C, 0.024 mL of the above seed solution was added to 10mL of a cetyltrimethyl ammonium bromide solution (0.20 mol/L) and 10mL of HAuCl4Solution (1.0 mmol/L), 0.12 mL ascorbic acid solution (0.1 mol/L) and 0.6 mL AgNO3The solution (4 mmol/L) was stirred uniformly and allowed to stand for 12 hours. The reaction product is centrifugally washed and then is dispersed into water again for storage.
(2) And the gold nanorods are coated with silicon dioxide. 20 mL of gold nanorod dispersion solution is added with 0.2 mL of mercaptopropyl trimethoxy silane ethanol solution (10.8 mmol/L) and the mixture is stirred at 27oStirring at high speed for 5h, adding 0.04 mL ammonia water (0.4 mol/L), slowly adding 0.08 mL ethyl orthosilicate ethanol solution (0.9 mol/L), reacting for 12h under stirring, finishing centrifugation, washing precipitate with water, and dispersing into THF.
(3) And (3) preparing an organic silicon resin prepolymer. Adding 0.040 mL of dilute hydrochloric acid (0.1 mol/L) into 33.75 mL of water, and sequentially adding 7 mL of tetraethoxysilane, 8 mL of methyltriethoxysilane and 0.15 mL of mercaptopropyltrimethoxysilane, and 60 mL ofoThe reaction was stirred for 5h under C. And then removing most of water and ethanol by rotary evaporation to obtain an organic silicon resin prepolymer, adding THF for dilution, and storing.
(4) And (3) respectively taking three parts of THF (tetrahydrofuran) dispersion liquid containing gold nanorods with different amounts obtained in the step (2) (the gold-containing nanorods are 0.032 mg, 0.16 mg and 0.32 mg respectively, and correspond to sample numbers d, e and f), respectively adding THF solution containing 1.0g of organic silicon resin prepolymer prepared in the step (3), fully stirring to form a uniform dispersion system, removing most of solvent in vacuum until the solvent is sticky, adding 20mg of aminopropyltrimethoxysilane, stirring and mixing uniformly, then taking 0.3 g of solution to transfer into a mold, removing gas and residual solvent in vacuum, and standing and curing at room temperature to obtain the gold nanorod composite organic silicon resin material.
In this example, a TEM photograph of the gold nanorods obtained in step (1) is shown in fig. 3, and a TEM photograph of the silica-coated gold nanorods obtained in step (2) is shown in fig. 4. As can be seen from the figure, the average length of the gold nanorods is 50 nm, the diameter of the gold nanorods is 20 nm, and the thickness of the wrapping silica shell layer is 10 nm.
An optical photograph of the gold nanorod composite silicone resin material obtained in step (4) of this example is shown in fig. 8, and a UV-vis spectrum is shown in fig. 9. In fig. 8, the sample is placed on the bottom plate with letters, it can be seen that the transparency of the sample is better, the samples d, e and f are blue transparent solids, the color deepens with the increase of the concentration of the gold nanorods, the major axis plasma resonance absorption peak position is 670 nm, and the minor axis absorption peak position is 525 nm.
The thermal weight loss change of the gold nanorod composite organic silicon resin material obtained in the step (4) of the embodiment under the nitrogen environment is shown in fig. 10, and 700 can be seen from the figureoThe thermal weight loss at C was about 5%.

Claims (8)

1. A preparation method of gold nanoparticle composite organic silicon resin is characterized by comprising the following steps:
(1) preparing gold nanoparticles by adopting a seed-mediated growth method under the protection of a surfactant;
(2) preparing gold nanoparticles coated with silicon dioxide by a Stoeber hydrolysis method by using the gold nanoparticles prepared in the step (1);
(3) preparing an organic silicon resin prepolymer;
(4) preparing the gold nanoparticle-coated gold nanoparticles prepared in the step (2) and the organic silicon resin prepolymer prepared in the step (3) through a solvent-assisted compounding process to prepare a gold nanoparticle composite organic silicon resin material;
the gold nanoparticles in the step (1) are gold nanospheres or gold nanorods;
the specific preparation method of the gold nanospheres comprises the following steps:
preparation of seed solution: taking a cetyl trimethyl ammonium bromide solution and a chloroauric acid aqueous solution, uniformly mixing, adding a sodium borohydride solution, and uniformly stirring at 25-28 ℃ for 1-2 hours to obtain a brown gold nano seed solution;
the concentrations of hexadecyl trimethyl ammonium bromide, chloroauric acid and sodium borohydride in the whole reaction solution are respectively 0.08-0.15mol/L, 0.2-0.3mmol/L and 0.5-0.8 mmol/L;
preparing gold nanospheres: adding the gold nano-seed solution into the growth solution, slowly stirring and reacting for 6-12 hours at 25-28 ℃, centrifuging and washing the reacted solution, collecting gold nano-sphere precipitate, and dispersing the gold nano-sphere precipitate in water for later use;
in the growth solution, the concentrations of cetyl trimethyl ammonium bromide, chloroauric acid and ascorbic acid in the growth solution are 0.02-0.05mol/L, 0.05-0.10mmol/L and 2.0-2.5mmol/L respectively;
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 gold nanorods comprises the following steps:
preparation of seed solution: uniformly mixing a hexadecyl trimethyl ammonium bromide solution and a chloroauric acid solution, adding a sodium borohydride solution at 25-28 ℃, and stirring at a high speed for 2-6 hours to obtain a brownish yellow gold nano seed solution;
the concentrations of hexadecyl trimethyl ammonium bromide, chloroauric acid and sodium borohydride in the whole reaction solution are respectively 0.08-0.15mol/L, 0.2-0.3mmol/L and 0.5-0.8 mmol/L;
preparing gold nanorods, namely adding the seed solution into a growth solution at the temperature of 25-28 ℃, uniformly stirring, standing for reacting for 6-12 hours, centrifuging and washing a reaction product, collecting gold nanorod precipitates, and dispersing the gold nanorod precipitates in water for later use;
in the growth solution, the concentrations of cetyl trimethyl ammonium bromide, chloroauric acid, silver nitrate and ascorbic acid in the growth solution are respectively 0.08-0.15mol/L, 0.4-0.7mmol/L, 0.3-1.5mmol/L and 0.5-0.8 mmol/L;
the volume of the seed solution added into the growth solution accounts for 0.1-0.5% of the volume of the growth solution;
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;
and after the reaction is finished, removing the solvent and the water by rotary evaporation to be viscous to obtain the organic silicon resin prepolymer, and adding tetrahydrofuran into the organic silicon resin prepolymer for dilution and storage.
2. The method for preparing gold nanoparticle composite silicone resin according to claim 1, wherein the step (1) is:
gold chloride acid is used as a raw material, and sodium borohydride is used for reduction to prepare a gold nano seed solution under the protection of cetyl trimethyl ammonium bromide serving as a surfactant;
adding the gold nano-seed solution into the growth solution, and stirring for reaction;
and after the reaction is finished, centrifuging, washing and precipitating the reaction product to obtain gold nanoparticles, and dispersing the gold nanoparticles in water for storage.
3. The method for preparing gold nanoparticle composite silicone resin according to claim 1, wherein the step (2) is:
adding mercaptopropyl trimethoxy silane solution into the gold nanoparticles obtained in the step (1), then adding ethyl orthosilicate into the system, uniformly mixing, adding ammonia water to form an alkaline environment, and stirring for reaction;
after the reaction is finished, centrifuging and washing the product to obtain gold nanoparticles coated with silicon dioxide, and dispersing the gold nanoparticles in tetrahydrofuran for storage.
4. The method for preparing gold nanoparticle composite silicone resin according to claim 1, wherein the step (4) is:
dispersing the gold nanoparticles coated with 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 gold nanoparticles and the organic silicon resin prepolymer to form a uniform dispersion system;
and then removing the solvent by rotary evaporation to be viscous, adding aminopropyltriethoxysilane, uniformly stirring, pouring the dispersion system into a mould, removing gas and residual solvent in vacuum, and curing to obtain the gold nanoparticle composite organic silicon resin material.
5. The method for preparing gold nanoparticle composite silicone resin according to claim 1, wherein the step (2) is specifically:
dropwise adding the ethanol solution of mercaptopropyl trimethoxy silane into the gold nanoparticle dispersion solution prepared in the step (1) under the stirring condition, adjusting the pH of the solution to 10-11 by using ammonia water, then dropwise adding the ethanol solution of ethyl orthosilicate, and stirring and reacting for 5-12h at the temperature of 25-28 ℃; then, centrifuging, washing and precipitating to obtain gold nanospheres coated with silicon dioxide, and dispersing in tetrahydrofuran;
the added gold nano particles are 0.1-2mg, and the amounts of the added mercaptopropyltrimethoxysilane and the added ethyl orthosilicate are 1-5mmol and 20-100mmol respectively.
6. The method for preparing gold nanoparticle composite silicone resin according to claim 1, wherein the step (3) is specifically:
adding dilute hydrochloric acid into water, adjusting the pH value of the water to 3-4, then adding tetraethoxysilane, alkyl alkoxy silicon and mercaptopropyl trimethoxy silane, heating to 40-70 ℃, and stirring for reaction for 4-6 h; after the reaction is finished, carrying out rotary evaporation on the solution, removing the solvent and water until the residual substrate is viscous, obtaining a viscous and transparent liquid, namely the organic silicon resin prepolymer, and adding a tetrahydrofuran solvent for dilution and then storing;
the volume ratio of water, ethyl orthosilicate, alkylalkoxysilane and mercaptopropyltrimethoxysilane is 1: 0.1-0.5: 0.1-0.5: 0.003-0.05.
7. The method for preparing gold nanoparticle composite silicone resin according to claim 1, wherein in the step (4), the mass ratio of the gold nanoparticles coated with the silica shell, the silicone resin prepolymer and the aminopropyltriethoxysilane is 0.02-2mg, 0.3-1.0g and 2-20mg, respectively.
8. A gold nanoparticle composite silicone resin, characterized by being prepared by the method according to any one of claims 1 to 7.
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