CN101343540B - Method for preparing quantum point with hyperbranched polymer supermolecule nano-reactor - Google Patents
Method for preparing quantum point with hyperbranched polymer supermolecule nano-reactor Download PDFInfo
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- CN101343540B CN101343540B CN2008100421607A CN200810042160A CN101343540B CN 101343540 B CN101343540 B CN 101343540B CN 2008100421607 A CN2008100421607 A CN 2008100421607A CN 200810042160 A CN200810042160 A CN 200810042160A CN 101343540 B CN101343540 B CN 101343540B
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- hyperbranched polymer
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Abstract
The invention relates to a preparation method for quantum dot by using an ultra-branch type polymer supermolecule nano-reactor, which belongs to the chemical field. The method of the invention adopts a principle that the assembling precedes the sealing, the ultra-branch type polymer and long chain fatty acld can become amphiphilic supermolecule nano-micelle by self-assemble after compounding, and then quantum dots with homogeneous dimensions can be prepared by using the supermolecule nano-micellse in an oil-water biphasic system. The synthetic CdS quantum dots of the invention are provided with a narrow size distribution and a good stability. Because the dimensions of ultra-branch type polymer and long chain fatty acld are adjustable, the dimension and the shape of the obtained supermolecule nano-micelle are easy to be controlled, so that the supermolecule nano-micelle can be used for preparing quantum dots with various dimensions and shapes. In addition, the supermolecule nano-micelle is provided with invertibility, the micelle can be destroyed through adding spasmolytol or adjusting pH value, thus the CdS quantum dots synthesized in an organic system can be transferred into an aqueous phase system.
Description
Technical field
The present invention relates to a kind of preparation method of chemical technology field, particularly, relate to a kind of method of utilizing hyperbranched polymer supermolecule nano-reactor to prepare quantum dot.
Background technology
Hyperbranched polymer molecule is irregular three-dimensional torispherical structure, comprises linearity, branching and end structure unit in the molecule, and part functional group is positioned at molecular surface, and part is present in intramolecule; Hyperbranched polymer has good solubility, and less solution and melt viscosity have a large amount of functional end-groups and intramolecularly space or the like.In addition, the hyperbranched polymer building-up process is simple, can be synthetic by single stage method.Hyperbranched polymer has a good application prospect at aspects such as pharmaceutical carrier, polymer catalyst, solidifying agent, solventless coatings and polymer processing aidses, has therefore caused the extensive concern of polymer science circle.In recent years, except the applied research in above several fields, hyperbranched polymer also begins to show up prominently in the fields such as preparation of polymer encapsulated, supramolecule self-assembly, functional film material, nanocrystal.
Find through literature search prior art, the system of utilizing hyperbranched polymer to prepare nanocrystal at present mainly is divided into two big classes: a class is to utilize the water-soluble ultrabranching polymkeric substance directly to prepare nanocrystal, NellyP é rignon etc. are at " Chem.Mater. " (materials chemistry, 2004, the 16th phase, 4856-4858 page or leaf) reported with over-branched polyamidoamine and prepared nanometer Au particle; Another kind of is to prepare nanocrystal behind the hyperbranched polymer end-blocking in the oil soluble system, Stefan Mecking etc. are at " macromolecules " (macromole, 2000, the 33rd phase, 3958-3960 page or leaf) reported that the hyperbranched polyether with the hexadecyl acyl chloride terminated prepares Pd nano particle.Hyperbranched polymer and longer chain fatty acid can be self-assembled into after compound be amphipathic supermolecule nano micella, yet utilize the method for this supermolecule nano micella quantum dot of preparation size homogeneous in water oil two-phase system not appear in the newspapers so far.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of method of utilizing hyperbranched polymer supermolecule nano-reactor to prepare quantum dot is provided.The present invention is the principle that utilization " is assembled afterwards earlier and encapsulated ", hyperbranched polymer and longer chain fatty acid be self-assembled into after compound be amphipathic supermolecule nano micella, utilize the quantum dot of this supermolecule nano micella preparation size homogeneous in water oil two-phase system then.Because the size adjustable of hyperbranched polymer and longer chain fatty acid, gained supramolecule micellar size and form are easy to control, thereby can be used for preparing the quantum dot of different size and form.
The present invention is achieved by the following technical solutions:
The present invention includes following steps:
The first step, lipid acid is dissolved in the chloroform, adds the hyperbranched polymer that end group is an amido then, magnetic agitation makes amphipathic supermolecule nano micellar solution; Wherein: fatty acid concentration be the 7.5-20 mmole/liter, the concentration of hyperbranched polymer is 1 to 3 mg/ml; The primary amine in the hyperbranched polymer and the mol ratio of lipid acid are 1:1;
Adding the quality volumetric concentration in second step, the amphipathic supermolecule nano micellar solution that obtains in the first step is the cadmium precursor aqueous solution of 1.6mg/ml, stirring; The add-on of cadmium precursor is 3 to 8 milligrams;
The 3rd step, stirring are left standstill in separating funnel after 48 hours and are deposited, and separate lower floor's chloroformic solution in reaction flask;
The 4th step, logical nitrogen 10 to 15 minutes add 2 milliliters of Na after the deoxygenation then
2The S aqueous solution continued logical nitrogen 10 minutes in reaction flask, and stirred at normal temperatures, and standing separation can obtain the chloroformic solution of CdS quantum dot; Na wherein
2The concentration of the S aqueous solution is that 0.39mg/ml is to 1.17mg/ml.
Hyperbranched polymer in the described the first step is meant: end group is hyperbranched acid amides-amine polymer, polymine (PEI), sulfone-amine polymer or the ester-amine polymer of amido.
Lipid acid in the described the first step is meant: capric acid, stearic acid, palmitinic acid, lauric acid or tetradecanoic acid.
Cadmium precursor in described second step is Cd (AC)
2, Cd (ClO
4)
2, Cd (NO
3)
2Perhaps CdCl
2
The supermolecule nano micella that the present invention utilizes end group to dress up for the hyperbranched polymer and the lipid acid static complex group of amido has a large amount of cavitys and amido, as template, can encapsulate cadmium precursor with it, and then obtains the CdS quantum dot with the sulfonium ion reaction.Amphipathic supermolecule nano micella both as the synthetic CdS quantum dot of nano-reactor, is lighted stabilization as stablizer to synthetic CdS quantum at this again.Use method synthetic CdS quantum dot of the present invention to have narrower distribution of sizes and stable preferably.Adopt such supramolecule micella to prepare the advantage that quantum dot combines hyperbranched polymer and quantum dot, help regulating the performance such as mechanics, optics, electricity of quantum dot.In addition, such supermolecule nano micella has reversibility, can destroy this micella by adding methods such as triethylamine or adjusting pH value, thereby make that synthetic CdS quantum dot can be transferred to aqueous phase system in organic system.
Description of drawings
The ultraviolet-visible spectrogram of Fig. 1 CdS quantum dot.
The transmission electron microscope picture of Fig. 2 CdS quantum dot;
Wherein: A is the transmission electron microscope picture of palmitinic acid and hyperbranched acid amides-CdS quantum dot that the amine polymer reaction makes; B is the transmission electron microscope picture that palmitinic acid and hyperbranched polyethyleneimine react the CdS quantum dot that makes; C is the transmission electron microscope picture of palmitinic acid and hyperbranched sulfone-CdS quantum dot that the amine polymer reaction makes.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The first step: add 197 milligrams of palmitinic acids in 100 milliliters reaction flask, add 40 milliliters of chloroforms and make it dissolving, add 117 milligrams of hyperbranched acid amides-amine polymers again, normal temperature stirred 12 hours down.
Second step: in the above-mentioned chloroformic solution that obtains, add and contain 8 milligrams of Cd (AC)
25 milliliters of the aqueous solution, with the glass stopper sealing, stirred at normal temperatures 48 hours.
The 3rd step: leave standstill in the separating funnel and deposit, separate lower floor's chloroformic solution in reaction flask.Logical nitrogen 10-15 minute, and then add 2 milliliters, concentration is 0.39mg/ml, and the Na after the deoxygenation
2The S aqueous solution continued logical nitrogen 10 minutes, and continued stir about at normal temperatures 1 hour in reaction flask.Standing separation can obtain clarifying light yellow CdS chloroformic solution.
As shown in Figure 1, the ultraviolet-visible spectrogram of the CdS quantum dot for preparing in the present embodiment as can be known: the absorption peak of CdS quantum dot is about 370 nanometers, and the size that can be calculated the CdS quantum dot by the Brus experimental formula is about 3.0 nanometers.The transmission electron microscope picture of the CdS quantum dot of preparation is shown in Fig. 2 A.By transmission electron microscope picture CdS quantum dot distribution of sizes homogeneous relatively as can be known.
Embodiment 2
The first step: add 235 milligrams of palmitinic acids in 100 milliliters reaction flask, add 40 milliliters of chloroforms then and make it dissolving, add 120 milligrams of hyperbranched polyethyleneimines again, normal temperature stirred 12 hours down.
Second step: in the above-mentioned chloroformic solution that obtains, add and contain 8 milligrams of Cd (ClO
4)
25 milliliters of the aqueous solution, with the glass stopper sealing, stirred at normal temperatures 48 hours.
The 3rd step: leave standstill in the separating funnel and deposit, separate lower floor's chloroformic solution in reaction flask.Logical nitrogen 10-15 minute, and then add 2 milliliters, concentration is 0.98mg/ml, and the Na after the deoxygenation
2The S aqueous solution continued logical nitrogen 10 minutes, and continued stir about at normal temperatures 1 hour in reaction flask.Standing separation can obtain clarifying light yellow CdS chloroformic solution.
The transmission electron microscope picture of the CdS quantum dot of preparation is shown in Fig. 2 B.By transmission electron microscope picture CdS quantum dot distribution of sizes homogeneous relatively as can be known.
Embodiment 3
The first step: add 142 milligrams of palmitinic acids in 100 milliliters reaction flask, add 40 milliliters of chloroforms then and make it dissolving, add 124 milligrams of hyperbranched sulfone-amine polymers again, normal temperature stirred 12 hours down.
Second step: in the above-mentioned chloroformic solution that obtains, add and contain 8 milligrams of Cd (NO
3)
25 milliliters of the aqueous solution, with the glass stopper sealing, stirred at normal temperatures 48 hours.
The 3rd step: leave standstill in the separating funnel and deposit, separate lower floor's chloroformic solution in reaction flask.Logical nitrogen 10-15 minute, and then add 2 milliliters, concentration is 1.17mg/ml, and the Na after the deoxygenation
2The S aqueous solution continued logical nitrogen 10 minutes, and continued stir about at normal temperatures 1 hour in reaction flask.Standing separation can obtain the light yellow chloroformic solution of CdS quantum dot.
The resulting product of present embodiment proves its character through ultraviolet-visible spectrum, fluorescence spectrum, dynamic light scattering, transmission electron microscope, thermogravimetric analysis, examination of infrared spectrum.
The transmission electron microscope picture of CdS quantum dot of preparation is shown in Fig. 2 C, by transmission electron microscope picture CdS quantum dot distribution of sizes homogeneous relatively as can be known.
Claims (3)
1. a method of utilizing hyperbranched polymer supermolecule nano-reactor to prepare quantum dot is characterized in that, may further comprise the steps:
The first step, lipid acid is dissolved in the chloroform, adds the hyperbranched polymer that end group is an amido then, magnetic agitation makes amphipathic supermolecule nano micellar solution; Wherein: fatty acid concentration be the 7.5-20 mmole/liter, the concentration of hyperbranched polymer is 1 to 3 mg/ml; The primary amine in the hyperbranched polymer and the mol ratio of lipid acid are 1: 1;
Described hyperbranched polymer is meant: end group is hyperbranched acid amides-amine polymer, polymine, sulfone-amine polymer or the ester-amine polymer of amido;
Adding the quality volumetric concentration in second step, the amphipathic supermolecule nano micellar solution that obtains in the first step is the cadmium precursor aqueous solution of 1.6mg/ml, stirring; The add-on of cadmium precursor is 3 to 8 milligrams;
The 3rd step, stirring are left standstill in separating funnel after 48 hours and are deposited, and separate lower floor's chloroformic solution in reaction flask;
The 4th step, logical nitrogen 10 to 15 minutes add 2 milliliters of Na after the deoxygenation then
2The S aqueous solution continued logical nitrogen 10 minutes in reaction flask, and stirred at normal temperatures, and standing separation can obtain the chloroformic solution of CdS quantum dot; Na wherein
2The concentration of the S aqueous solution is that 0.39mg/ml is to 1.17mg/ml.
2. the method for utilizing hyperbranched polymer supermolecule nano-reactor to prepare quantum dot according to claim 1 is characterized in that: the lipid acid in the described the first step is meant: capric acid, stearic acid, palmitinic acid, lauric acid or tetradecanoic acid.
3. the method for utilizing hyperbranched polymer supermolecule nano-reactor to prepare quantum dot according to claim 1 is characterized in that: the cadmium precursor in described second step is Cd (Ac)
2, Cd (ClO
4)
2, Cd (NO
3)
2Perhaps CdCl
2
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| CN101665691B (en) * | 2009-09-04 | 2013-12-25 | 上海交通大学 | Method for using amphipathy hyperbranched polymer to prepare quantum dots |
| CN102585801A (en) * | 2012-01-29 | 2012-07-18 | 上海交通大学 | Preparation method of quantum dot-hyperbranched polyether nanocomposite-nitrogen oxide fluorescent probe |
| CN105511150A (en) * | 2016-02-01 | 2016-04-20 | 京东方科技集团股份有限公司 | Quantum bar, manufacturing method for quantum bar and display panel |
| CN105968774B (en) * | 2016-05-13 | 2018-06-19 | 吉林大学 | A kind of hyperbranched polyarylether ketone/CdS quantum dot nanocomposite and preparation method thereof |
| CN108003870B (en) * | 2017-11-22 | 2020-11-03 | 吉林化工学院 | Cadmium sulfide quantum dot fluorescent probe and preparation method and application thereof |
| CN109777423A (en) * | 2019-02-18 | 2019-05-21 | 南通创亿达新材料股份有限公司 | The method for preparing quantum dot using dissaving polymer |
| CN112897574A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院深圳先进技术研究院 | Preparation method and structure of nano-particle cadmium sulfide material |
| CN112080012B (en) * | 2020-09-14 | 2022-03-08 | 安阳师范学院 | Method for packaging and releasing semiconductor fluorescent quantum dots based on hyperbranched polyamine-fatty acid supermolecule self-assembly and application thereof |
Citations (3)
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|---|---|---|---|---|
| US20020045045A1 (en) * | 2000-10-13 | 2002-04-18 | Adams Edward William | Surface-modified semiconductive and metallic nanoparticles having enhanced dispersibility in aqueous media |
| CN1769182A (en) * | 2005-09-05 | 2006-05-10 | 北京化工大学 | Metal sulfide semiconductor nanometer composite material using hydrotalcite as model and its preparation method |
| CN101225227A (en) * | 2008-01-31 | 2008-07-23 | 上海交通大学 | Over-branched polyamidoamine and metal nano compound as well as preparation method and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020045045A1 (en) * | 2000-10-13 | 2002-04-18 | Adams Edward William | Surface-modified semiconductive and metallic nanoparticles having enhanced dispersibility in aqueous media |
| CN1769182A (en) * | 2005-09-05 | 2006-05-10 | 北京化工大学 | Metal sulfide semiconductor nanometer composite material using hydrotalcite as model and its preparation method |
| CN101225227A (en) * | 2008-01-31 | 2008-07-23 | 上海交通大学 | Over-branched polyamidoamine and metal nano compound as well as preparation method and uses thereof |
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