CN111423874A - Preparation method of organic polymer grafted nano-silica coated quantum dot - Google Patents
Preparation method of organic polymer grafted nano-silica coated quantum dot Download PDFInfo
- Publication number
- CN111423874A CN111423874A CN202010341735.6A CN202010341735A CN111423874A CN 111423874 A CN111423874 A CN 111423874A CN 202010341735 A CN202010341735 A CN 202010341735A CN 111423874 A CN111423874 A CN 111423874A
- Authority
- CN
- China
- Prior art keywords
- solution
- quantum dot
- core
- nano
- low molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a preparation method of quantum dots coated by organic polymer grafted nano silicon dioxide. Firstly, SiO is firstly2The modified nano-silica composite particles are uniformly coated on silanized quantum dots, then the surface of nano-silica is modified, short soft polyalcohol chain segments are grafted on the surface, and relatively long linear polyester low molecular chains with certain rigidity are introduced, so that the modified nano-silica composite particles with surface grafting rigid-flexible combination, appropriate polymer molecular chains with different properties and chemical structures, and greatly improved amphipathy, chemical activity, dispersibility and organic compatibility are obtained. Such nanoparticles have good compatibility with most resin matrices, which areThe middle polyester chain segment can nucleate and crystallize, and the quantum dot has excellent luminescence property, so that the luminescent nucleating agent is stable.
Description
Technical Field
The invention relates to the field of nanoparticle preparation and quantum dot luminescence, in particular to a luminescent quantum dot material of a graft polymer and a preparation method thereof.
Background
Many modern luminescent materials and devices are composed of semiconductor quantum structures, and the quantum dots formed by the materials have the size close to that of dye molecules commonly used in the past, so that the materials have great application as fluorescent dyes. Quantum dots have a significant size effect due to the wonderful rules of quantum mechanics, light above a certain threshold can be absorbed substantially, while an organic dye molecule can rise from the ground state to a higher excited state only after absorption of photons of appropriate energy, the light used must be of a precise wavelength or color, which is clearly different from that of the semiconductor bulk material, while quantum dots absorb all photons above their band gap energy, but the wavelength (i.e., color) of the emitted light is very size dependent.
Silica is a widely used inorganic material that is widely found in nature. The nano silicon dioxide has stable property and very excellent acid and alkali resistance, fire resistance and other properties. The nano silicon dioxide is coated on the surface of the quantum dot, so that the surface of the quantum dot can be modified while the property of the quantum dot is stable, and the compatibility of the quantum dot in various matrixes is improved.
Disclosure of Invention
The invention aims to provide a preparation method of a polymer grafted on the surface of a quantum dot coated with nano silicon dioxide, which can promote PET crystallization and realize high-efficiency and stable luminescence performance.
The invention is realized by the following steps of the technical scheme:
a preparation method of quantum dots coated by organic polymer grafted nano silicon dioxide comprises the following steps:
step (1), synthesis and silanization of core-shell structure quantum dots: adding a certain amount of cadmium oxide and octadecylphosphonic acid into trioctylamine, and heating to 300 ℃ until the cadmium oxide and the octadecylphosphonic acid are dissolved; then adding a certain amount of tri-n-octylphosphine solution of selenium, reacting for two minutes at 300 ℃, and then cooling to room temperature to obtain CdSe quantum dot core solution; cadmium acetate dihydrate and anhydrous zinc acetate are placed in trioctylamine and heated to 300 ℃, and a quantum dot solution and a sulfur tri-n-octylphosphine solution are sequentially injected. Keeping the temperature at 300 ℃ for 1.5h, and then cooling to room temperature to obtain a quantum dot solution with a core-shell structure; adding a certain amount of tetraethoxysilane and stirring for a period of time to silanize the tetraethoxysilane;
step (2), coating of nano silicon dioxide on the surface of the quantum dot: dispersing a certain amount of lgepal co-520 into cyclohexane, then sequentially adding the redispersed silanized core-shell structure quantum dot solution, ammonia water and ethyl orthosilicate to obtain a reverse microemulsion system, and stirring and reacting for a period of time to complete the coating of the nano silicon dioxide layer;
step (3), the preparation method of the low molecular weight polyethylene terephthalate comprises the following steps: dimethyl terephthalate, ethylene glycol and zinc acetate are added into a flask for reaction, and mechanical stirring is carried out; adding antimony trioxide and triphenyl phosphite for reaction, distilling under reduced pressure when the temperature rises to 220 ℃, pouring the mixed solution into distilled water, reducing the temperature to room temperature, carrying out suction filtration, and carrying out vacuum drying on the obtained product to obtain low molecular weight polyethylene glycol terephthalate;
and (4) synthesizing the composite nano-particles modified by the surface low-molecular polymer: performing surface treatment on the composite nano-particles by using 3-isocyanate propyl trimethyl siloxane to enable the surfaces of the composite nano-particles to have isocyanate groups; then grafting of the low molecular weight polyethylene glycol is completed under the action of a catalyst dibutyltin dilaurate;
step (5), synthesis of diblock polymer: then grafting low molecular weight polyethylene glycol terephthalate through polycondensation reaction to obtain the final product.
The method comprises the steps of (1) synthesizing and silanizing the quantum dots with the core-shell structure, namely adding 0.5mmol of cadmium oxide and 0.5mmol of octadecylphosphonic acid into 5ml of trioctylamine, heating to 300 ℃ to be dissolved, then injecting 1ml of 1 mol/L trioctylphosphine solution with selenium dissolved, reacting for two minutes at 300 ℃, then cooling to room temperature to obtain CdSe quantum dot core solution, placing 0.05mmol of cadmium acetate dihydrate and 0.05mmol of anhydrous zinc acetate into 10ml of trioctylamine, heating to 300 ℃ and sequentially injecting 0.5-1.5 ml of CdSe quantum dot core solution and 0.4 mol/L of trioctylphosphine solution with sulfur dissolved at 0.5 ml/300 ℃ for 1.5h, then cooling to room temperature to obtain quantum dot solution with the core-shell structure, then re-dispersing the quantum dot solution with the core-shell structure into 1ml of toluene, adding 2-20 mul of tetraethoxysilane, and stirring for 20h silanizing.
In the step (2), 1-1.5 g of lgepal co-520 is dispersed into 10ml of cyclohexane, then 1ml of redispersed silanized core-shell structure quantum dot solution, 0.15-0.3 ml of 6.25 omega t% ammonia water and 3-30 mul of ethyl orthosilicate are sequentially added to obtain an inverse microemulsion system, and after stirring for 5-15 h, the coating of a nano silicon dioxide layer is completed to obtain the composite nano particles coated with nano silicon dioxide outside the core-shell quantum dots.
In the step (2), the concentration of ammonia water is 6.25-12.5 omega t% when ethyl orthosilicate is hydrolyzed.
The method comprises the following steps of (3) preparing the low molecular weight polyethylene terephthalate: adding 8-10 g of dimethyl terephthalate, 4-6 ml of ethylene glycol and 0.03g of zinc acetate into a 50ml container, reacting at 190 ℃ for 2h, and mechanically stirring; and then adding 0.03g of antimony trioxide to react with 2-3 drops of triphenyl phosphite for 0.5h, distilling under reduced pressure for 1h when the temperature rises to 220 ℃, pouring the mixed solution into distilled water, reducing the temperature to room temperature, carrying out suction filtration, and carrying out vacuum drying on the obtained product to obtain the low-molecular-weight polyethylene terephthalate.
The method comprises the following steps of (4) synthesizing low molecular weight polymer modified composite nano particles: performing surface treatment on the composite nano-particles obtained in the step (2) by using 3-isocyanate propyl trimethyl siloxane to enable the surfaces of the composite nano-particles to have isocyanate groups; in the surface treatment process of the step, the mass ratio of the 3-isocyanatopropyltrimethylsiloxane to the composite nanoparticles obtained in the step (2) is 1-2: 1; then mixing the nano composite particles treated by the silane coupling agent with a small amount of PEG and dibutyltin dilaurate serving as a catalyst, heating to 80 ℃, and reacting for 10 hours under the catalysis effect to complete grafting; centrifuging at 8000r/min for 8min, washing with ethanol for three times, and vacuum drying to obtain sample;
the method comprises the following steps of (5): synthesis of diblock Polymer: dissolving 10g of low molecular weight polyethylene terephthalate in 60ml of phenol/tetrachloroethane mixed solution, adding 5ml of cross-linking agent ethylene glycol, and reacting for 1h at 60 ℃; and (3) adding 0.5g of the sample obtained in the step (4), 0.03g of a polycondensation catalyst antimony trioxide and 2-3 drops of a heat stabilizer triphenyl phosphite, and continuing to react for 2 hours at 100 ℃. Washing with phenol and carbon tetrachloride solution in the mass ratio of 1 to remove residual low molecular weight polyethylene terephthalate, washing with acetone and ethanol twice, centrifuging to remove residual impurities, and vacuum drying. Centrifuging at 8000r/min for 8min, and drying at 100 deg.C to obtain final product.
The surface is grafted with a short soft polyalcohol chain segment, and a relatively long linear polyester low molecular chain with certain rigidity is introduced to obtain the modified nano silicon dioxide composite particle with the surface grafted rigid-flexible combination, the polymer molecular chains with different properties and suitable length and short length, and the modified nano silicon dioxide composite particle has stable chemical structure, greatly improved amphipathy, chemical activity, dispersibility and organic compatibility. The nano-particles have good compatibility with most resin matrixes, wherein polyester chain segments can nucleate and crystallize, and quantum dots have excellent luminescence property and are stable luminescence nucleating agents.
Drawings
FIG. 1 is a high resolution TEM photograph of QDs @ SiO 2;
FIG. 2 is a DSC cooling (a) and warming (b) curves for PET/QDs @ SiO2 composites;
FIG. 3 is a comparison of fluorescence intensity of samples before and after doping;
FIG. 4 is an infrared spectrum of graft block polymer L MPET-PEG (infra);
FIG. 5 shows XPS spectra (a), N spectra (b), Si spectra (c) of IPTES-PEG-L MPET block copolymer modified with IPTES silane coupling agent;
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
The first step is that 0.5mmol of cadmium oxide and 0.5mmol of octadecylphosphonic acid are added into 5ml of trioctylamine and heated to 300 ℃ to be dissolved, 1ml of tri-n-octylphosphine solution with selenium dissolved in 1 mol/L is injected, the mixture reacts for two minutes at 300 ℃ and is cooled to room temperature to obtain CdSe quantum dot core solution, 0.05mmol of cadmium diacetate and 0.05mmol of anhydrous zinc acetate are placed into 10ml of trioctylamine and heated to 300 ℃, 0.5-1.5 ml of CdSe quantum dot core solution and 0.4 mol/L of tri-n-octylphosphine solution with sulfur dissolved are injected in sequence and kept at 0.5 ml/300 ℃ for 1.5 hours, the mixture is cooled to room temperature to obtain quantum dot solution with the core-shell structure, and then the quantum dot solution with the core-shell structure is re-dispersed into 1ml of toluene, 2-20 mu l of ethyl orthosilicate is added and stirred for 20 hours to be silanized.
Step two: coating of nano silicon dioxide on the surface of the quantum dot: dispersing 1-1.5 g of lgepal co-520 into 10ml of cyclohexane, then sequentially adding 1ml of the redispersed silanized core-shell structure quantum dot solution, 0.15-0.3 ml of 6.25 omega t% ammonia water and 3-30 mu l of ethyl orthosilicate to obtain an inverse microemulsion system, stirring for 5-15 h to complete coating of a nano silicon dioxide layer, and obtaining the composite nano particle coated with nano silicon dioxide outside the core-shell quantum dot.
Step three: the preparation method of the low molecular weight polyethylene terephthalate comprises the following steps: adding 8-10 g of dimethyl terephthalate, 4-6 ml of ethylene glycol and 003g of zinc acetate into a 50ml flask, reacting at 190 ℃ for 2h, and mechanically stirring. And then adding 0.03g of antimony trioxide to react with 2-3 drops of triphenyl phosphite for 0.5h, distilling under reduced pressure for 1h when the temperature rises to 220 ℃, pouring the mixed solution into distilled water, reducing the temperature to room temperature, carrying out suction filtration, and carrying out vacuum drying on the obtained product to obtain the low-molecular-weight polyethylene terephthalate.
Step four: synthesis of low-molecular polymer modified composite nanoparticles: and (3) carrying out surface treatment on the composite nano-particles obtained in the second step by using 3-isocyanate propyl trimethyl siloxane so as to enable the surfaces of the composite nano-particles to have isocyanate groups. In the surface treatment process of the step, the mass ratio of the 3-isocyanatopropyl trimethyl siloxane to the composite nano particles obtained in the step two is 1-2: 1. And then mixing the nano composite particles treated by the silane coupling agent with a small amount of PEG and dibutyltin dilaurate serving as a catalyst, heating to 80 ℃, and reacting for 10 hours under the catalysis effect to complete grafting. Centrifuging at 8000r/min for 8min, washing with ethanol for three times, and vacuum drying to obtain the sample.
Step five: synthesis of diblock Polymer: 10g of low molecular weight polyethylene terephthalate is dissolved in 60ml of a phenol/tetrachloroethane (mass ratio of 1: 1) mixed solution, 5ml of cross-linking agent ethylene glycol is added, and the reaction is carried out for 1 hour at 60 ℃. And then adding 0.5g of the sample obtained in the fourth step, 0.03g of a polycondensation catalyst antimony trioxide and 2-3 drops of a heat stabilizer triphenyl phosphite, and continuing to react for 2 hours at 100 ℃. Washing with phenol and carbon tetrachloride solution in the mass ratio of 1 to remove residual low molecular weight polyethylene terephthalate, washing with acetone and ethanol twice, centrifuging to remove residual impurities, and vacuum drying. Centrifuging at 8000r/min for 8min, and drying at 100 deg.C to obtain final product.
The transmission electron micrograph of FIG. 1 shows that the synthesis of quantum dots and SiO deposition are performed in the examples2The coating step successfully obtains QDs @ SiO with the diameter of about 20nm2With QDs of about 6 nm.
FIG. 2 is a DSC measurement of a sample, and the right is a temperature rise curve of DSC, in which the area of the temperature rise peak indicates the crystallinity of the sample. It can be seen that the crystallinity of the PET matrix tends to increase and decrease with the increase of the content of the nucleating agent, and the crystallinity reaches the maximum value when the addition amount is between 2 and 3 percent; the left panel is the cooling curve of the DSC, and the position of the cooling peak indicates the crystallization temperature of the sample. It can thus be seen that the addition of the nucleating agent has little effect on the crystallization temperature of the PET matrix.
FIG. 3 shows QDs @ SiO2Comparison of fluorescence intensity before and after treatment. It can be seen that the sample still retains the original 43% fluorescence intensity after the grafting and blending process.
FIG. 4 is an IR spectrum of a grafted block polymer, L MPET-PEG grafted with PEG at 2960cm compared to the IR spectrum of pure L MPET-1The change in the peak indicates the appearance of a new methylene group, indicating that the step of low molecular weight block copolymer synthesis in the examples completes the grafting of PEG to L MPET.
In FIG. 5, (a) XPS spectrum of IPTES-PEG-L MPET block copolymer modified by IPTES as silane coupling agent, (b) N spectrum, (c) Si spectrum, and N peak and Si peak are detected in XPS spectrum of IPTES-PEG-PET, and the appearance of nitrogen element and silicon element shows that the step of treating low molecular weight block copolymer with silane coupling agent IPTES in the example realizes modification of PEG-PET by silane coupling agent IPTES.
TABLE 1PET/QDs @ SiO2Mechanical property test results of composite materials
| The addition amount of | Elongation at break/%) | Tensile strength/MPa | Yield strength/MPa | Tensile modulus/MPa |
| 0 | 143 | 60.523 | 60.523 | 1229.41 |
| 1 | 180 | 60.689 | 60.689 | 1374.48 |
| 2 | 183 | 62.896 | 62.896 | 1374.29 |
| 3 | 156 | 63.52 | 63.52 | 1370.73 |
| 4 | 143 | 62.76 | 62.76 | 1364.87 |
Example 2
The first step is that 0.5mmol of cadmium oxide and 0.5mmol of octadecylphosphonic acid are added into 5ml of trioctylamine and heated to 300 ℃ to be dissolved, 1ml of tri-n-octylphosphine solution with selenium dissolved in 1 mol/L is injected, the mixture reacts for two minutes at 300 ℃ and is cooled to room temperature to obtain CdSe quantum dot core solution, 0.05mmol of cadmium diacetate and 0.05mmol of anhydrous zinc acetate are placed into 10ml of trioctylamine and heated to 300 ℃, 0.5-1.5 ml of CdSe quantum dot core solution and 0.4 mol/L of tri-n-octylphosphine solution with sulfur dissolved are injected in sequence and kept at 0.5 ml/300 ℃ for 1.5 hours, the mixture is cooled to room temperature to obtain quantum dot solution with the core-shell structure, and then the quantum dot solution with the core-shell structure is re-dispersed into 1ml of toluene, 2-20 mu l of ethyl orthosilicate is added and stirred for 20 hours to be silanized.
Step two: coating of nano silicon dioxide on the surface of the quantum dot: dispersing 1-1.5 g of lgepal co-520 into 10ml of cyclohexane, then sequentially adding 1ml of the redispersed silanized core-shell structure quantum dot solution, 0.15-0.3 ml of 6.25 omega t% ammonia water and 3-30 mu l of ethyl orthosilicate to obtain an inverse microemulsion system, stirring for 5-15 h to complete coating of a nano silicon dioxide layer, and obtaining the composite nano particle coated with nano silicon dioxide outside the core-shell quantum dot.
Step three: the preparation method of the low molecular weight polyethylene terephthalate comprises the following steps: 8-10 g of dimethyl terephthalate, 4-6 ml of ethylene glycol and 0.03g of zinc acetate are added into a 50ml flask and reacted for 2 hours at 190 ℃, and mechanical stirring is carried out. And then adding 0.03g of antimony trioxide to react with 2-3 drops of triphenyl phosphite for 0.5h, distilling under reduced pressure for 1h when the temperature rises to 220 ℃, pouring the mixed solution into distilled water, reducing the temperature to room temperature, carrying out suction filtration, and carrying out vacuum drying on the obtained product to obtain the low-molecular-weight polyethylene terephthalate.
Step four: synthesis of Low molecular weight diblock Polymer: 5g of low molecular weight polyethylene terephthalate is dissolved in 10ml of a phenol/tetrachloroethane (mass ratio of 1: 1) mixed solution, 5ml of cross-linking agent ethylene glycol is added, and the reaction is carried out for 1 hour at 60 ℃. And then adding 8ml of PEG-400, 0.03g of polycondensation catalyst antimony trioxide and 2-3 drops of heat stabilizer triphenyl phosphite, continuing to react for 2 hours at 100 ℃, washing with phenol and carbon tetrachloride solution with the mass ratio of 1: 1 to remove residual low molecular weight polyethylene glycol terephthalate, washing with acetone and ethanol twice respectively, centrifugally separating the mixed solution to remove residual impurities, and vacuum-drying the product. Centrifuging at 8000r/min for 8min, and drying at 100 deg.C to obtain low molecular weight diblock polymer PET-PEG.
Step five: synthesis of organic polymer-modified nanocomposite particles: 2g of 3-isocyanatopropyltrimethylsiloxane and 0.5g of the PET-PEG prepared in step four were placed in 10ml of a phenol/tetrachloroethane mixture (mass ratio: 1), 0.5ml of dibutyltin dilaurate was added, and the mixture was stirred at 110 ℃ for 12 hours. And then putting the reacted system into a dialysis bag, dialyzing with ethanol for 24 hours, and centrifuging to obtain the PET-PEG modified by the silane coupling agent. And then placing the PET-PEG modified by the silane coupling agent and the nanoparticles prepared in the step two in water, and stirring for 30min at normal temperature to complete grafting, thereby obtaining a final product.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (7)
1. A preparation method of quantum dots coated by organic polymer grafted nano silicon dioxide is characterized by comprising the following steps:
step (1), synthesis and silanization of core-shell structure quantum dots: adding a certain amount of cadmium oxide and octadecylphosphonic acid into trioctylamine, and heating to 300 ℃ until the cadmium oxide and the octadecylphosphonic acid are dissolved; then adding a certain amount of tri-n-octylphosphine solution of selenium, reacting for two minutes at 300 ℃, and then cooling to room temperature to obtain CdSe quantum dot core solution; placing cadmium acetate dihydrate and anhydrous zinc acetate in trioctylamine, heating to 300 ℃, and sequentially injecting a quantum dot solution and a sulfur tri-n-octylphosphine solution; keeping the temperature at 300 ℃ for 1.5h, and then cooling to room temperature to obtain a quantum dot solution with a core-shell structure; adding a certain amount of tetraethoxysilane and stirring for a period of time to silanize the tetraethoxysilane;
step (2), coating of nano silicon dioxide on the surface of the quantum dot: dispersing a certain amount of lgepal co-520 into cyclohexane, then sequentially adding the redispersed silanized core-shell structure quantum dot solution, ammonia water and ethyl orthosilicate to obtain a reverse microemulsion system, and stirring and reacting for a period of time to complete the coating of the nano silicon dioxide layer;
step (3), the preparation method of the low molecular weight polyethylene terephthalate comprises the following steps: dimethyl terephthalate, ethylene glycol and zinc acetate are added into a flask for reaction, and mechanical stirring is carried out; adding antimony trioxide and triphenyl phosphite for reaction, distilling under reduced pressure when the temperature rises to 220 ℃, pouring the mixed solution into distilled water, reducing the temperature to room temperature, carrying out suction filtration, and carrying out vacuum drying on the obtained product to obtain low molecular weight polyethylene glycol terephthalate;
and (4) synthesizing the composite nano-particles modified by the surface low-molecular polymer: performing surface treatment on the composite nano-particles by using 3-isocyanate propyl trimethyl siloxane to enable the surfaces of the composite nano-particles to have isocyanate groups; then grafting of the low molecular weight polyethylene glycol is completed under the action of a catalyst dibutyltin dilaurate;
step (5), synthesis of diblock polymer: then grafting low molecular weight polyethylene glycol terephthalate through polycondensation reaction to obtain the final product.
2. The method as claimed in claim 1, wherein in the step (1), the synthesis and silanization of the quantum dots with the core-shell structure are carried out by adding 0.5mmol of cadmium oxide and 0.5mmol of octadecylphosphonic acid into 5ml of trioctylamine, heating to 300 ℃ for dissolution, injecting 1 mol/L of tri-n-octylphosphine solution with selenium dissolved, reacting for two minutes at 300 ℃, cooling to room temperature to obtain CdSe quantum dot core solution, placing 0.05mmol of cadmium acetate dihydrate and 0.05mmol of anhydrous zinc acetate into 10ml of trioctylamine, heating to 300 ℃, sequentially injecting 0.5-1.5 ml of CdSe quantum dot core solution and 0.4 mol/L of tri-n-octylphosphine solution with sulfur dissolved, keeping at 300 ℃ for 1.5h, cooling to room temperature to obtain quantum dot solution with the core-shell structure, adding 1ml of toluene with silicic acid, adding 2-20 μ l of n-octylphosphine, and silanizing for 20 μ l.
3. The method of claim 1, wherein: in the step (2), 1-1.5 g of lgepal co-520 is dispersed into 10ml of cyclohexane, then 1ml of redispersed silanized core-shell structure quantum dot solution, 0.15-0.3 ml of 6.25 omega t% ammonia water and 3-30 mu l of ethyl orthosilicate are sequentially added to obtain a reverse microemulsion system, and after stirring for 5-15 h, the coating of a nano silicon dioxide layer is completed to obtain the composite nano particle with the core-shell quantum dots coated with nano silicon dioxide.
4. The method of claim 1, wherein: in the step (2), the concentration of ammonia water is 6.25-12.5 omega t% when the tetraethoxysilane is hydrolyzed.
5. The method of claim 1, wherein: in the step (3), the preparation method of the low molecular weight polyethylene terephthalate comprises the following steps: adding 8-10 g of dimethyl terephthalate, 4-6 ml of ethylene glycol and 0.03g of zinc acetate into a 50ml container, reacting at 190 ℃ for 2h, and mechanically stirring; and then adding 0.03g of antimony trioxide to react with 2-3 drops of triphenyl phosphite for 0.5h, distilling under reduced pressure for 1h when the temperature rises to 220 ℃, pouring the mixed solution into distilled water, reducing the temperature to room temperature, carrying out suction filtration, and carrying out vacuum drying on the obtained product to obtain the low-molecular-weight polyethylene terephthalate.
6. The method of claim 1, wherein: in the step (4), synthesizing the low molecular weight polymer modified composite nano-particles: performing surface treatment on the composite nano-particles obtained in the step (2) by using 3-isocyanate propyl trimethyl siloxane to enable the surfaces of the composite nano-particles to have isocyanate groups; in the surface treatment process of the step, the mass ratio of the 3-isocyanatopropyltrimethylsiloxane to the composite nanoparticles obtained in the step (2) is 1-2: 1; then mixing the nano composite particles treated by the silane coupling agent with a small amount of PEG and dibutyltin dilaurate serving as a catalyst, heating to 80 ℃, and reacting for 10 hours under the catalysis effect to complete grafting; centrifuging at 8000r/min for 8min, washing with ethanol for three times, and vacuum drying to obtain the sample.
7. The method of claim 1, wherein: in the step (5): synthesis of diblock Polymer: dissolving low molecular weight polyethylene terephthalate in a phenol/tetrachloroethane mixed solution, adding a cross-linking agent ethylene glycol, and reacting for 1h at 60 ℃; then adding the sample obtained in the step (4), adding a polycondensation catalyst antimony trioxide and a heat stabilizer triphenyl phosphite, and continuing to react for 2 hours at 100 ℃; washing with a solution of phenol and carbon tetrachloride in a mass ratio of 1: 1 to remove residual low molecular weight polyethylene terephthalate, washing with acetone and ethanol twice, centrifuging to separate a mixed solution to remove residual impurities, and vacuum-drying the product; centrifuging at 8000r/min for 8min, and drying at 100 deg.C to obtain final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010341735.6A CN111423874A (en) | 2020-04-27 | 2020-04-27 | Preparation method of organic polymer grafted nano-silica coated quantum dot |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010341735.6A CN111423874A (en) | 2020-04-27 | 2020-04-27 | Preparation method of organic polymer grafted nano-silica coated quantum dot |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111423874A true CN111423874A (en) | 2020-07-17 |
Family
ID=71559026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010341735.6A Pending CN111423874A (en) | 2020-04-27 | 2020-04-27 | Preparation method of organic polymer grafted nano-silica coated quantum dot |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111423874A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524300A (en) * | 2016-01-12 | 2016-04-27 | 宁波大学 | Modified nano-silica and preparation method thereof |
| CN106084196A (en) * | 2016-08-12 | 2016-11-09 | 青岛大学 | A kind of two block low polymer engrafted nanometer silicon dioxide granules, preparation method and polyester |
| CN109705843A (en) * | 2019-01-22 | 2019-05-03 | 青岛大学 | Silica modified terbium complex PET luminescent material and preparation method thereof |
-
2020
- 2020-04-27 CN CN202010341735.6A patent/CN111423874A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524300A (en) * | 2016-01-12 | 2016-04-27 | 宁波大学 | Modified nano-silica and preparation method thereof |
| CN106084196A (en) * | 2016-08-12 | 2016-11-09 | 青岛大学 | A kind of two block low polymer engrafted nanometer silicon dioxide granules, preparation method and polyester |
| CN109705843A (en) * | 2019-01-22 | 2019-05-03 | 青岛大学 | Silica modified terbium complex PET luminescent material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| H.Y.CHANG等: "Structure–property relationships in PEG/SiO2 based proton conducting hybrid membranes-A29SiCP/MAS solid-state NMR study", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| PING YANG等: "Highly Luminescent CdSe/CdxZn1-xS Quantum Dots Coated with Thickness-Controlled SiO2 Shell through Silanization", 《LANGMUIR》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6161620B2 (en) | Semiconductor structure having nanocrystalline shell with nanocrystalline core and insulating coating | |
| EP3092283B1 (en) | Surface-modified nanoparticles | |
| EP2424941B1 (en) | Functionalized matrixes for dispersion of nanostructures | |
| JP2011251283A (en) | Nanoparticle, nanocrystal, nanocrystal solution, and method for making water-soluble nanoparticle | |
| US7264874B2 (en) | Preparation of metal chalcogenide nanoparticles and nanocomposites therefrom | |
| US20040167257A1 (en) | Preparation of metal nanoparticles and nanocomposites therefrom | |
| CN106854368A (en) | Inorganic particle silicone composites, the dispersion comprising compound and solid material and preparation method | |
| KR101567327B1 (en) | Quantum dot containing composite particle and method for fabricating the same | |
| CN110408379A (en) | Preparation method, quantum dot and the quantum dot optoelectronic devices of narrow half-peak breadth quantum dot | |
| CN107140677B (en) | A kind of preparation method of function element metal oxide nanoparticles | |
| EP3430085A1 (en) | Materials for encapsulating leds | |
| Madhi et al. | Bio-based surface modification of wool fibers by chitosan-graphene quantum dots nanocomposites | |
| CN111423874A (en) | Preparation method of organic polymer grafted nano-silica coated quantum dot | |
| CN115491073A (en) | Hyperbranched polyester modified silicon dioxide nanowire and preparation method thereof | |
| CN112978793B (en) | TiO22W nano-particles, preparation method and application thereof | |
| CN1508198A (en) | Method for preparing nano-level particle surface modifier nano inorganic oxide dispersion and use thereof | |
| İlgün et al. | Methacrylate functionalized MWCNTs/PDMS-polyurethane methacrylate UV-curable nanocomposites | |
| Hao et al. | P‐93: Compact Stable Quantum Dots via Amide‐Mediated Synthesis of PMO‐Based Multifunctional Ligand | |
| CN116219571A (en) | High-resilience creep-resistant copolymerized nylon monofilament and preparation method and application thereof | |
| KR101800835B1 (en) | Composition including metal oxide submicrospheres, polymer thin film including the composition, photocatalyst material including the composition, and method for manufacturing the composition | |
| US20090270539A1 (en) | The method of preparation of polyethylene terephthalate nanocomposite with enhanced modulus | |
| CN113201208A (en) | PBAT composite material and preparation method and application thereof | |
| CN116948391A (en) | High-concentration PA 6/micro-nano structure Cu 2 O master batch and preparation method thereof | |
| CN116161653A (en) | Method for modifying amino on surface of graphene oxide sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |