CN111334279A - Composite material and preparation method thereof - Google Patents
Composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of display, and particularly relates to a composite material and a preparation method thereof. The composite material comprises a carbon quantum dot and an organic luminescent material; an amphiphilic polymer bonded to the carbon quantum dots and the organic light emitting material; the amphiphilic polymer comprises a first hydrophilic group and a second hydrophilic group, and the first hydrophilic group is combined with the carbon quantum dots; the second hydrophilic group is bonded to the organic light emitting material. The composite material not only has good luminous intensity, but also can improve the solubility of the composite material in different inks, and is beneficial to the application of the carbon quantum dots in the printing display field.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a composite material and a preparation method thereof.
Background
The nano material represented by Quantum Dots (QDs) is a new concept proposed in 90 s of the 20 th century, and structurally binds conduction band electrons, valence band holes and excitons in three-dimensional directions, thereby being a nano-structured particle having a Quantum effect. The structure enables the quantum dots to have a plurality of novel properties, and the quantum dots have wide application prospects in the aspects of solar cells, luminescent devices, photocatalysis, biological fluorescence labeling and the like.
Carbon quantum Dots (CDs) are called Carbon Dots for short, the appearance of the Carbon Dots is a new breakthrough in the field of nano materials, and the Carbon Dots are a zero-dimensional semiconductor nanocrystal which is approximately spherical and has the diameter of less than 10nm, and a nanocluster consisting of few molecules or atoms. The semiconductor quantum dot has the advantages of excellent optical performance, small size and the like of the traditional semiconductor quantum dot, and also has the advantages of incomparable low toxicity, no light flicker, low preparation cost, relatively simple manufacturing process and the like of the traditional semiconductor quantum dot. However, in general, the fluorescence quantum yield of the synthesized bare carbon dot is less than 10%, and the bare carbon dot directly prepared without functional modification generally has poor fluorescence performance and no specific function in the formation of surface groups, so that the application of the bare carbon dot is limited. Therefore, modification based on the traditional synthesis method is necessary to improve the quantum yield of the carbon dots and broaden the application performance of the carbon dots.
The luminous intensity of the carbon quantum dots is generally enhanced by changing a synthesis method to make the quantum dots more stable or by preparing the quantum dots into a composite material with a resonant metal. Even if the preparation method of the quantum dot is optimized, a series of steps of ligand exchange, coating a shell, phase transfer and the like are required in the application process of the quantum dot, and the quantum dot may be seriously damaged to reduce the luminous intensity of the quantum dot. For example, the luminescent intensity of quantum dots is enhanced by using the surface plasmon resonance of nano-metals, and the quantum dots are often required to be fixed on a certain substrate or prepared into a thin film, which limits the advantages of quantum dot colloidal solutions. Furthermore, the luminous intensity is enhanced by the metal, and the interval between the quantum dots and the metal needs to be strictly controlled in the process, so that the non-radiative transition caused by too short distance is avoided.
Disclosure of Invention
The invention aims to provide a composite material and a preparation method thereof, and aims to solve the technical problem that the existing carbon quantum dots are low in light intensity and limited in application.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a composite material comprising: carbon quantum dots and organic light emitting materials; an amphiphilic polymer bonded to the carbon quantum dots and the organic light emitting material; the amphiphilic polymer comprises a first hydrophilic group and a second hydrophilic group, and the first hydrophilic group is combined with the carbon quantum dots; the second hydrophilic group is bonded to the organic light emitting material.
According to the composite material provided by the invention, the carbon quantum dots and the organic luminescent material are connected by the amphiphilic polymer, namely the first hydrophilic group and the second hydrophilic group on the same side of the amphiphilic polymer are respectively combined with the carbon quantum dots and the organic luminescent material, so that the organic luminescent material can be indirectly compounded on the carbon quantum dots, and therefore, the luminous intensity of the carbon quantum dots can be effectively improved by utilizing the long transient fluorescence life characteristic (namely, relatively long excited state) of the organic luminescent material and the energy transfer between the carbon quantum dots and the organic luminescent material; in addition, the carbon quantum dots connected by using different kinds of amphiphilic polymers can be dispersed in organic solvents with different polarities, so that the solubility of the composite material in different inks can be further improved, and the application of the carbon quantum dots in the field of printing and displaying is facilitated.
The invention also provides a preparation method of the composite material, which comprises the following steps:
providing an amphiphilic polymer; the hydrophilic polymer comprises a first hydrophilic group and a second hydrophilic group;
dissolving an organic light emitting material and the amphiphilic polymer in a first solvent, and combining the organic light emitting material and the second hydrophilic group of the amphiphilic polymer;
and dissolving the carbon quantum dot and the amphiphilic polymer connected with the organic luminescent material in a second solvent, so that the carbon quantum dot and the first hydrophilic group of the amphiphilic polymer are combined to obtain the composite material.
The preparation method of the composite material provided by the invention firstly dissolves the organic luminescent material and the amphiphilic polymer in a first solvent, connecting the organic luminescent material with the second hydrophilic group of the amphiphilic polymer to form the amphiphilic polymer modified by the organic luminescent material, then dissolving the carbon quantum dots in a second solvent, so that the residues (such as hydroxyl or carboxyl) on the carbon quantum dots are connected with the first hydrophilic group which is not connected with the organic luminescent material, thereby the amphiphilic polymer connects the organic luminescent material and the carbon quantum dots together, thereby avoiding the defect that the organic luminescent material is difficult to be directly connected with the carbon quantum dots, the organic luminescent material can be indirectly compounded on the carbon quantum dots, so that the prepared composite material not only has good luminous intensity, and the solubility of the composite material in different inks can be improved, and the application of the carbon quantum dots in the printing display field is facilitated.
Drawings
Fig. 1 is a schematic structural diagram of a composite material according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, embodiments of the present invention provide a composite material, as shown in fig. 1, including: carbon quantum dots and organic light emitting materials; an amphiphilic polymer bonded to the carbon quantum dots and the organic light emitting material; the amphiphilic polymer comprises a first hydrophilic group and a second hydrophilic group, and the first hydrophilic group is combined with the carbon quantum dots; the second hydrophilic group is bonded to the organic light emitting material.
According to the composite material provided by the embodiment of the invention, the carbon quantum dots and the organic luminescent material are connected by the amphiphilic polymer, namely the first hydrophilic group and the second hydrophilic group on the same side of the amphiphilic polymer are respectively combined with the carbon quantum dots and the organic luminescent material, so that the organic luminescent material can be indirectly compounded on the carbon quantum dots, and therefore, the luminous intensity of the carbon quantum dots can be effectively improved by utilizing the long transient fluorescence life characteristic (namely, relatively long excited state) of the organic luminescent material and the energy transfer of the organic luminescent material and the quantum dots; in addition, the carbon quantum dots connected by using different kinds of amphiphilic polymers can be dispersed in organic solvents with different polarities, so that the solubility of the composite material in different inks can be further improved, and the application of the carbon quantum dots in the field of printing and displaying is facilitated.
The amphiphilic polymer generally has a hydrophilic group at one end and a hydrophobic group at one end, and in the amphiphilic polymer of the embodiment of the invention, the carbon quantum dots and the organic light-emitting material are coated by the amphiphilic polymer. The amphiphilic polymer coats the carbon quantum dots, and the organic light-emitting material is bonded on the second hydrophilic group between the carbon quantum dots and the amphiphilic polymer. The amphiphilic polymer forms a coating layer, and the carbon quantum dots and the organic luminescent material can be coated in the coating layer, so that the organic luminescent material and the carbon quantum dots are packaged in the amphiphilic polymer and isolated from the external environment, the influence of external factors on the organic luminescent material and the carbon quantum dots in the application process is avoided, and the overall stability of the composite material is improved. Furthermore, in the composite material of the embodiment of the invention, after the amphiphilic polymer coats the carbon quantum dots and the organic luminescent material to form a coating layer, the whole composite material is granular, and the particle size is 8-10 nm; the composite material in the size range can better encapsulate the carbon quantum dots and the organic luminescent material, and has optimal stability.
Further, in the composite material of the embodiment of the present invention, the amphiphilic polymer is selected from at least one of distearoylphosphatidylethanolamine-polyethylene glycol (DSPE-mPEG-method 2000), polyurethane, poly (vinylbenzylthymine) -b-poly (vinylbenzyltriethylammonium chloride) (PSVM), poly (isobutylene-maleic anhydride), polyacrylic acid n-butyl acetate-b-polyacrylic acid (PnBuA-b-PAA), poly (acrylic acid-co-styrene) (P (AA-co-St)), and polystyrene-ethyl polymethacrylatecinnamate.
Further, the hydrophilic group of the amphiphilic polymer includes at least one of an amino group and a carboxyl group. Examples of amphiphilic polymers having an amino hydrophilic group include distearoylphosphatidylethanolamine-polyethylene glycol, polyurethane, poly (vinylbenzylthymine) -b-poly (vinylbenzyltriethylammonium chloride), etc.; examples of the amphiphilic polymer having a carboxyl group as a hydrophilic group include poly (isobutylene-maleic anhydride), poly (n-butyl acrylate-b-polyacrylic acid), poly (acrylic acid-co-styrene), and polystyrene-ethyl polymethacrylatecinnamate.
Further, in the composite material of the embodiment of the present invention, the organic light emitting material is selected from at least one of an organic fluorescent dye and a rare earth organic light emitting material.
Specifically, the organic fluorescent dye is at least one selected from coumarin compounds, quinoxaline derivatives and anthranilic acid amide derivatives.
The structure of the coumarin compound is shown as follows,
wherein R is1Is one of hydroxyl, amino and nitro.
As shown in the following, the structure of the quinoxaline derivative,
wherein R is2And R3Are identical or different hydrocarbon radicals, R4And R5Respectively is one of the same or different aldehyde group, amino group, alkoxy group and alkyl group.
The structure of the anthranilic acid amide derivative is shown as follows,
wherein R is6And R7Is one of the same or different hydrogen atom, halogen atom, hydroxyl and amino.
Specifically, the rare earth organic luminescent material is a rare earth complex consisting of a rare earth organic ligand and rare earth ions, wherein the rare earth organic ligand is selected from at least one of β -diketone compounds and aromatic carboxylic acid, and the rare earth ions are selected from Eu2+、Eu3+、La+、Er3+、Tm3+And Yb3+At least one of (1).
The structure of β -diketone compound is shown as follows,
wherein R is8And R9Respectively one of the same or different alkyl and aromatic hydrocarbon.
In an embodiment of the present invention, if the first hydrophilic group and the second hydrophilic group are both amino groups, the amphiphilic polymer is selected from at least one of distearoylphosphatidylethanolamine-polyethylene glycol, polyurethane, and poly (vinylbenzylthymine) -b-poly (vinylbenzyltriethylammonium chloride), and the organic light emitting material is selected from at least one of quinoxaline derivatives, anthranilamide derivatives, and rare earth organic light emitting materials; in another embodiment of the present invention, if the first hydrophilic group and the second hydrophilic group are carboxyl groups, the amphiphilic polymer is at least one selected from poly (isobutylene-maleic anhydride), poly (n-butyl acrylate-b-polyacrylic acid), poly (acrylic acid-co-styrene), and polystyrene-ethyl polymethacrylate, and the organic light emitting material is at least one selected from coumarins, quinoxaline derivatives, and anthranilamide derivatives. Thus, a composite material having high and stable emission intensity can be formed in both cases.
Further, the molar ratio of the amphiphilic polymer to the organic light-emitting material is (1-2): (0.01-0.1); the molar mass ratio of the amphiphilic polymer to the carbon in the carbon quantum dots is (1-2) to (0.01-0.1). Within this molar ratio range, the composite material can obtain the best luminous intensity.
On the other hand, the embodiment of the invention also provides a preparation method of the composite material, which comprises the following steps:
s01: providing an amphiphilic polymer; the hydrophilic polymer comprises a first hydrophilic group and a second hydrophilic group;
s02: dissolving an organic light emitting material and the amphiphilic polymer in a first solvent, and combining the organic light emitting material and the second hydrophilic group of the amphiphilic polymer;
s03: and dissolving the carbon quantum dot and the amphiphilic polymer connected with the organic luminescent material in a second solvent, so that the carbon quantum dot and the first hydrophilic group of the amphiphilic polymer are combined to obtain the composite material.
The preparation method of the composite material provided by the embodiment of the invention comprises the steps of firstly dissolving the organic luminescent material and the amphiphilic polymer in the first solvent, connecting the organic luminescent material with the second hydrophilic group of the amphiphilic polymer to form the amphiphilic polymer modified by the organic luminescent material, then dissolving the amphiphilic polymer and the carbon quantum dot in the second solvent, so that the residue (such as hydroxyl or carboxyl) on the carbon quantum dot is connected with the first hydrophilic group which is not connected with the organic luminescent material, and the amphiphilic polymer connects the organic luminescent material and the carbon quantum dot together, thereby avoiding the defect that the organic luminescent material is difficult to be directly connected with the carbon quantum dot, and indirectly compounding the organic luminescent material on the carbon quantum dot, so that the prepared composite material not only has good luminescent intensity, but also can improve the solubility of the composite material in different inks, the application of the carbon quantum dots in the printing display field is facilitated.
Further, in the above production method, the amphiphilic polymer is at least one selected from the group consisting of distearoylphosphatidylethanolamine-polyethylene glycol, polyurethane, poly (vinylbenzylthymine) -b-poly (vinylbenzyltriethylammonium chloride), poly (isobutylene-maleic anhydride), poly (n-butyl acrylate-b-polyacrylic acid), poly (acrylic acid-co-styrene), and polystyrene-ethyl polymethacrylatecinnamate; the hydrophilic group includes at least one of an amino group and a carboxyl group; the organic luminescent material is selected from at least one of organic fluorescent dye and rare earth organic luminescent material. The selection of these materials has been described in detail above. The first solvent and the second solvent are each independently selected from any one of acetonitrile, methanol, ethanol, propanol, butanol, and chloroform.
The carbon quantum dots prepared by the hydrothermal method have the defects of surface branched chains and unstable groups due to the reaction of the carbon source at high temperature and high pressure, and the limited groups of the organic luminescent material are difficult to be directly connected with the carbon quantum dots. The incomplete groups on the surface of the carbon quantum dots comprise hydroxyl and carboxyl; thus, the carboxyl contained in the amphiphilic polymer and the hydroxyl on the surface of the carbon quantum dot are subjected to dehydration condensation under certain conditions to generate esterification reaction, and a lipid compound is generated; the amido contained in the amphiphilic polymer and the carboxyl on the surface of the carbon quantum dot are dehydrated under certain conditions to carry out acylation reaction, and the amide compound is generated.
Specifically, when the organic light-emitting material and the amphiphilic polymer are dissolved in a first solvent, a first chemical reaction occurs, and when the organic light-emitting material contains a hydroxyl group and the amphiphilic polymer contains a carboxyl group, the first chemical reaction is an esterification reaction to generate an ester group; or, when the organic light-emitting material contains an amino group and the amphiphilic polymer contains a carboxyl group, the first chemical reaction is an acylation reaction to generate an acyl group; or, when the organic luminescent material contains halogen atoms and the amphiphilic polymer contains amino groups, the first chemical reaction is a halogenation reaction to generate secondary amino groups; or, when the organic light-emitting material contains aldehyde group and the amphiphilic polymer contains amino group, the first chemical reaction is nucleophilic addition reaction to generate an imino compound; when the organic light-emitting material contains carbonyl which is ketone and the amphiphilic polymer contains amino, the first chemical reaction is Schiff base reaction to generate imine with carbon-nitrogen double bonds. After the second hydrophilic group in the amphiphilic polymer is subjected to the first chemical reaction, the hydrophilic property cannot be changed, when the amphiphilic polymer is dispersed in a solvent, a micelle or a reverse micelle is formed in the solvent, the first hydrophilic group and the second hydrophilic group are positioned on the same side, and the first hydrophilic group and the carbon quantum dot are combined after the second chemical reaction. And coating the carbon quantum dots and the organic light-emitting material by the amphiphilic polymer. The amphiphilic polymer coats the carbon quantum dots, and the organic light-emitting material is bonded on the second hydrophilic group between the carbon quantum dots and the amphiphilic polymer.
Dissolving a carbon quantum dot and an amphiphilic polymer connected with the organic luminescent material in a second solvent to generate a second chemical reaction, wherein for the second chemical reaction, when the amphiphilic polymer contains carboxyl, the second chemical reaction is an esterification reaction; alternatively, when the amphiphilic polymer contains an amino group, the second chemical reaction is an acylation reaction.
In one embodiment of the present invention, the amphiphilic polymer is selected from at least one of distearoylphosphatidylethanolamine-polyethylene glycol, polyurethane, and poly (vinylbenzylthymine) -b-poly (vinylbenzyltriethylammonium chloride), and the organic light emitting material is selected from at least one of quinoxaline derivatives, anthranilic acid amide derivatives, and rare earth organic light emitting materials; in another embodiment of the present invention, the amphiphilic polymer is at least one selected from the group consisting of poly (isobutylene-maleic anhydride), poly (n-butylacetic-b-polyacrylic acid), poly (acrylic acid-co-styrene), and polystyrene-poly (ethyl methacrylate), and the organic light emitting material is at least one selected from the group consisting of coumarins, quinoxaline derivatives, and anthranilic acid amide derivatives.
Further, the above-mentioned first chemical reaction and second chemical reaction are carried out under different catalysts depending on the type of reaction. Further, the temperature of the first chemical reaction is 25-80 ℃; the time of the first chemical reaction is 1-7 h. The temperature of the second chemical reaction is 25-80 ℃; the time of the second chemical reaction is 1.5-6 h.
In some embodiments, the molar ratio of the amphiphilic polymer to the organic luminescent material is 1-2:0.01-0.1, the amphiphilic polymer and the organic luminescent material are dissolved in a first solvent, and under certain conditions and the action of a catalyst, the product is separated, purified and dissolved in chloroform;
in some embodiments, the molar ratio of the carbon quantum dot to the organic luminescent material is 1-2:0.01-0.1, the carbon quantum dot and the amphiphilic polymer connected with the organic luminescent material are dissolved in a second solvent, and react with the amphiphilic polymer molecules connected with the organic luminescent material under the action of a catalyst under certain conditions, and simultaneously, the amphiphilic polymer is aggregated to form a coating layer, and finally, the amphiphilic polymer encapsulated organic luminescent material/carbon quantum dot composite is obtained.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
A preparation method of a composite material comprises the following steps:
dissolving 1mmol of polyacrylic acid n-butyl acetate-b-polyacrylic acid in acetonitrile, adding 0.1ml of p-toluenesulfonic acid (catalyst), adding 0.06mmol of 7-amino-3-phenylcoumarin under stirring, heating to 60 ℃ for reaction for 1h, carrying out acylation reaction on amino and carboxyl, connecting the 7-amino-3-phenylcoumarin dye with polyacrylic acid n-butyl acetate-b-polyacrylic acid molecules, separating and purifying, and dissolving in chloroform;
dissolving 0.05mmol of carbon quantum dots in chloroform, adding 0.1ml of concentrated sulfuric acid (catalyst), slowly dropwise adding the polyacrylic acid n-butyl acetate-b-polyacrylic acid connected with the 7-amino-3-phenylcoumarin dye, reacting at normal temperature for 2h, washing with ethanol, and aggregating the polyacrylic acid n-butyl acetate-b-polyacrylic acid to form a coating layer to obtain the 7-amino-3-phenylcoumarin/carbon quantum dots packaged by the polyacrylic acid n-butyl acetate-b-polyacrylic acid.
Example 2
A preparation method of a composite material comprises the following steps:
dissolving 1.5mmol of poly (isobutylene-maleic anhydride) in ethanol, adding 0.1g of boric acid (catalyst), adding 0.05mmol of 7-hydroxy-3-azido coumarin, stirring for 3 hours at normal temperature, allowing the hydroxyl and carboxyl to have esterification reaction, connecting the 7-hydroxy-3-azido coumarin dye with poly (isobutylene-maleic anhydride) molecules, separating and purifying, and dissolving in chloroform;
dissolving 0.06mmol of carbon quantum dots in chloroform, adding 0.1ml of concentrated sulfuric acid (catalyst), slowly dropwise adding the poly (isobutylene-maleic anhydride) connected with the 7-hydroxy-3-azido coumarin dye, reacting at normal temperature for 1.5h, cleaning with ethanol, and aggregating the poly (isobutylene-maleic anhydride) to form a coating layer to obtain the 7-hydroxy-3-azido coumarin/carbon quantum dots packaged by the poly (isobutylene-maleic anhydride).
Example 3
A preparation method of a composite material comprises the following steps:
dissolving 1.6mmol distearoylphosphatidylethanolamine-polyethylene glycol in butanol, adding 0.08mmol chloroanthranilamide, heating to 80 deg.C, refluxing for 7h to replace chloride ion with amino group, linking chloroanthranide dye and distearoylphosphatidylethanolamine-polyethylene glycol molecule, separating, purifying, and dissolving in chloroform;
dissolving 0.08mmol of carbon quantum dots in chloroform, adding 0.1mmol of benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBop, catalyst), slowly adding dropwise the distearoylphosphatidylethanolamine-polyethylene glycol connected with the chloroanthranilamide dye, heating and refluxing for 6h at 60 ℃, washing with ethanol, and aggregating distearoylphosphatidylethanolamine-polyethylene glycol to form a coating layer to obtain the distearoylphosphatidylethanolamine-polyethylene glycol encapsulated chloroanthranilate amide/carbon quantum dots.
Example 4
A preparation method of a composite material comprises the following steps:
dissolving 2mmol of polyurethane in butanol, adding 0.5mmol of triethylamine (catalyst), adding 0.01mmol of 2, 3-bis (4-aldehyde-phenylalkenyl) -6, 7-bis (3-methylbutoxy) -quinoxaline under stirring at normal temperature, reacting for 3h, reacting aldehyde group with amino group to connect 2, 3-bis (4-aldehyde-phenylalkenyl) -6, 7-bis (3-methylbutoxy) -quinoxaline dye with polyurethane molecule, separating and purifying, and dissolving in chloroform;
dissolving 0.04mmol of carbon quantum dots in chloroform, adding 0.1mmol of benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBop, catalyst), slowly dropwise adding the polyurethane connected with the 2, 3-bis (4-aldehyde-phenylalkenyl) -6, 7-bis (3-methylbutoxy) -quinoxaline dye, heating and refluxing for 6h at 60 ℃, washing with ethanol, and forming a coating layer by polyurethane aggregation to obtain the polyurethane-encapsulated 2, 3-bis (4-aldehyde-phenylalkenyl) -6, 7-bis (3-methylbutoxy) -quinoxaline/carbon quantum dots.
Example 5
A preparation method of a composite material comprises the following steps:
dissolving 1.7mmol of polyurethane in methanol, adding 0.1mmol of anhydrous sodium sulfate (catalyst), heating and refluxing at 70 ℃, adding 0.03mmol of β -diketone ligand 2-thenoyltrifluoroacetone coordinated Eu3+The compound is subjected to Schiff base reaction to ensure that β -diketone ligand 2-thenoyltrifluoroacetone coordinates Eu3+Connecting a compound rare earth organic luminescent material with polyurethane molecules, and dissolving the compound rare earth organic luminescent material in chloroform after separation and purification;
dissolving 0.06mmol of carbon quantum dots in butanol, adding 0.1mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI, catalyst), and slowly adding dropwise the above β -diketone ligand 2-thenoyltrifluoroacetone coordinated Eu3+Heating and refluxing polyurethane of the compound for 3h at 80 ℃, cleaning with ethanol, and performing polyurethane polymerization to form a coating layer to obtain β -diketone ligand 2-thenoyltrifluoroacetone coordinated Eu packaged by polyurethane3+Compound/carbon quantum dots.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A composite material, comprising:
carbon quantum dots and organic light emitting materials;
an amphiphilic polymer bonded to the carbon quantum dots and the organic light emitting material;
the amphiphilic polymer comprises a first hydrophilic group and a second hydrophilic group, and the first hydrophilic group is combined with the carbon quantum dots; the second hydrophilic group is bonded to the organic light emitting material.
2. The composite material of claim 1, wherein the amphiphilic polymer encapsulates the carbon quantum dots and the organic light emitting material.
3. The composite material of claim 1, wherein the amphiphilic polymer encapsulates the carbon quantum dots, and the organic light emitting material is bound to the second hydrophilic group between the carbon quantum dots and the amphiphilic polymer.
4. The composite material of any one of claims 1 to 3, wherein the first hydrophilic group and the second hydrophilic group are each independently selected from at least one of an amino group and a carboxyl group.
5. The composite material of any one of claims 1 to 3, wherein the amphiphilic polymer is selected from at least one of distearoylphosphatidylethanolamine-polyethylene glycol, polyurethane, poly (vinylbenzylthymine) -b-poly (vinylbenzyltriethylammonium chloride), poly (isobutylene-maleic anhydride), poly (n-butylacetic acid-b-polyacrylic acid), poly (acrylic acid-co-styrene), and polystyrene-poly (ethyl methacrylate); and/or the presence of a gas in the gas,
the organic luminescent material is selected from at least one of organic fluorescent dye and rare earth organic luminescent material.
6. The composite material according to claim 5, wherein the organic luminescent material is an organic fluorescent dye selected from at least one of coumarins represented by formula I, quinoxaline derivatives represented by formula II, and anthranilic acid amide derivatives represented by formula III;
wherein R is1Is one of hydroxyl, amino and nitro;
wherein R is2And R3Are identical or different hydrocarbon radicals, R4And R5Respectively is one of the same or different aldehyde group, amino group, alkoxy group and alkyl group;
wherein R is6And R7Is one of the same or different hydrogen atoms, halogen atoms, hydroxyl groups and amino groups; and/or
The organic luminescent material is selected from rare earth organic luminescent materials, the rare earth organic luminescent materials are rare earth complexes consisting of rare earth organic ligands and rare earth ions, the rare earth organic ligands are selected from at least one of β -diketone compounds and aromatic carboxylic acids, and the rare earth ions are selected from Eu2+、Eu3+、La+、Er3+、Tm3+And Yb3+At least one of (1).
7. The composite material according to any one of claims 1 to 3, wherein the amphiphilic polymer is selected from at least one of distearoylphosphatidylethanolamine-polyethylene glycol, polyurethane, and poly (vinylbenzylthymine) -b-poly (vinylbenzyltriethylammonium chloride), and the organic light emitting material is selected from at least one of quinoxaline derivatives, anthranilic acid amide derivatives, and rare earth organic light emitting materials; alternatively, the first and second electrodes may be,
the amphiphilic polymer is at least one selected from poly (isobutylene-maleic anhydride), poly (n-butyl acrylate-b-polyacrylic acid), poly (acrylic acid-co-styrene) and polystyrene-poly (ethyl methacrylate), and the organic luminescent material is at least one selected from coumarin compounds, quinoxaline derivatives and anthranilic acid amide derivatives.
8. The preparation method of the composite material is characterized by comprising the following steps:
providing an amphiphilic polymer; the hydrophilic polymer comprises a first hydrophilic group and a second hydrophilic group;
dissolving an organic light emitting material and the amphiphilic polymer in a first solvent, and combining the organic light emitting material and the second hydrophilic group of the amphiphilic polymer;
and dissolving the carbon quantum dot and the amphiphilic polymer connected with the organic luminescent material in a second solvent, so that the carbon quantum dot and the first hydrophilic group of the amphiphilic polymer are combined to obtain the composite material.
9. The method according to claim 8, wherein the amphiphilic polymer is at least one selected from the group consisting of distearoylphosphatidylethanolamine-polyethylene glycol, polyurethane, and poly (vinylbenzylthymine) -b-poly (vinylbenzyltriethylammonium chloride), and the organic light emitting material is at least one selected from the group consisting of quinoxaline derivatives, anthranilamide derivatives, and rare earth organic light emitting materials; alternatively, the first and second electrodes may be,
the amphiphilic polymer is at least one selected from poly (isobutylene-maleic anhydride), poly (n-butyl acrylate-b-polyacrylic acid), poly (acrylic acid-co-styrene) and polystyrene-poly (ethyl methacrylate), and the organic luminescent material is at least one selected from coumarin compounds, quinoxaline derivatives and anthranilic acid amide derivatives.
10. The method according to claim 8,
dissolving an amphiphilic polymer and an organic luminescent material in a first solvent according to the mol ratio of the amphiphilic polymer to the organic luminescent material of 1-2: 0.01-0.1; and/or the presence of a gas in the gas,
and dissolving the carbon quantum dots and the amphiphilic polymer connected with the organic luminescent material in a second solvent according to the molar ratio of the carbon quantum dots to the organic luminescent material of 1-2: 0.01-0.1.
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