Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
The embodiment of the present invention provides a kind of nanocomposite.The nanocomposite includes ligand modified quantum dot
With the expanding material for being coated on the ligand modified quantum dot surface, wherein the expanding material has fatty acid carbon chain and activity
Functional group, the fatty acid carbon chain be combined with each other with the ligand.
Nanocomposite of the invention passes through expanding material and ligand by coating one layer of expanding material in quantum dot and surface
Effect, reduce even avoid the reunion between quantum dot from thus imparting nanocomposite so that quantum dot is uniformly dispersed
When mixing with other high-molecular compounds, show high transparency, and it is stimulated after can emit strong fluorescence.
Further, the nanocomposite further includes high-molecular compound.Contain the above-mentioned of high-molecular compound
Nanocomposite can also be effectively prevented from the contact of quantum dot and water, oxygen etc., greatly improve the efficiency of quantum dot.
Preferably, the high-molecular compound is epoxy resin.
In the present invention, the structure that quantum dot and expanding material are formed can be core-shell structure, may not be, nanometer of the present invention
Therefore the microstructure of composite material is not limited.
Quantum dot of the present invention can be the nano particle being made of II-VI group or iii-v element, and partial size exists
Between 1-10nm.
Preferably, the quantum dot is CdSe, CdS, CdTe, CdSe/ZnS, CdZnS/ZnS, PbSe, PbS, PbSe/
Any one of ZnS, PbSe/CdS.This few class quantum dot forms good ligand structure in the effect with ligand oleic acid, can
To greatly improve the compatibility of quantum dot Yu other polar organic matters.
Preferably, ligand used in the ligand modified quantum dot is the organic matter containing carboxyl and carbochain, carboxylic
Base and quantum dot form ligand, and carbochain then hangs on quantum dot surface, improve the compatibility of quantum dot and other substances.
It is further preferred that the organic matter containing carboxyl and carbochain is fatty acid, since fatty acid has carboxyl and carbochain,
Carboxyl can form good ligand with quantum dot, and carbochain then modifies quantum dot surface so that quantum dot and other
Organic matter has better compatibility.Certainly, fatty acid of the present invention can be packet and fatty acid, be also possible to unsaturated lipid
Fat acid.
It is further preferred that above-mentioned fatty acid be oleic acid (also known as cis-18-ene--9-acid), oleic acid have carboxyl end group and
Nonpolar carbon-chain structure can form good ligand structure by the carboxyl of end with quantum dot, and nonpolar carbon
Chain then modifies quantum dot surface, so that the compatibility of quantum dot and other polar organic matters is greatly improved.
With the expanding material coated quantum dots with epoxy-functional, there is epoxy-functional on expanding material, can be improved increase-volume
The compatibility of agent and high-molecular compound material, so that the expanding material of quantum dot surface and the dispersion with other high-molecular compounds
Effect is more preferable, avoids the agglomeration of quantum dot.
Preferably, the expanding material is the fatty acid of epoxy functionalized dough.On the one hand the fatty acid of epoxy functionalized dough has
There is the functional group of epoxy group, on the other hand, the carbochain with fatty acid.It is mixed with by the quantum dot of ligand of fatty acid
When conjunction, self assembly occurs for the carbochain of quantum dot surface and the carbochain of expanding material, and epoxy group then forms one layer and is surrounded on quantum
Point surface and towards external structure, at this point, the fatty acid ligands on quantum dot also act as the effect of Passivation modified quantum dot, is protected
The optical strength and performance of quantum dot are demonstrate,proved, and realizes that quantum dot surface has epoxy-functional, so that quantum dot uniformly divides
It is dispersed in other high-molecular compounds.
It is further preferred that the expanding material is the modified oleic acid of epoxy-functional.When expanding material is epoxy-functional
The oleic acid of change, and the ligand of quantum dot is oleic acid, when expanding material and ligand modified quantum dot are carried out mixed processing, increase-volume
The structure that carbochain in carbochain and ligand in agent occurs self-assemble, is mutually organized into rule, so that expanding material and quantum dot
It is combined into orderly aligned nanostructure, at this point, the cycloalkyl groups on the oleic acid of epoxy functionalized dough are unanimously outwardly, so that
Quantum dot can be dispersed in well in other high-molecular compounds, well-proportioned can such as be dispersed in the epoxy.
Preferably, the high-molecular compound is epoxy resin.
Nanocomposite of the present invention, above structure and composition on, effectively improve quantum dot skin effect and
Interphase match, quantum dot are uniformly arranged in high-molecular compound so that nanocomposite show the high grade of transparency and
The characteristic of high fluorescent.
Correspondingly, the present invention is on the basis of providing above-mentioned nanocomposite, it is further provided the nano combined material
The preparation method of material.That is, the nanocomposite of above structure, can be prepared by this preparation method.
In one embodiment, the preparation method of the nanocomposite, at least includes the following steps:
S01. cladding processing is carried out to ligand modified quantum dot using expanding material,
Make the expanding material and the ligand that self assembly occur and be coated on the ligand modified quantum dot surface, obtains
The quantum dot of expanding material cladding.
Detailed explanation is done to technical solution of the present invention below.
In any embodiment, ligand modified quantum dot refers to using before carrying out the cladding processing of expanding material
Ligand and quantum dot carry out mixed processing, so that quantum dot is coordinated with ligand, form complex.
Preferably, the quantum dot is CdSe, CdS, CdTe, CdSe/ZnS, CdZnS/ZnS, PbSe, PbS, PbSe/
Any one of ZnS, PbSe/CdS.
And expanding material can use the existing expanding material with epoxy-functional, can also voluntarily prepare to obtain.With tool
For having expanding material such as the oleic acid that epoxy-functional is modified of epoxy-functional, it can prepare as follows:
By epoxy resin and oleic acid according to (1-4) g:(1-6) ratio of mL carries out mixing heat treatment, epoxy is prepared
The oleic acid of function dough.
It, can be under oil bath environment, such as in oil bath in order to guarantee the equilibrium of reaction temperature when specific preparation
In, 3-24h is reacted in 100-200 DEG C of temperature, the carboxylic group on oleic acid reacts with epoxy, can be obtained epoxy functionalized
The modified oleic acid of group.
Preferably, in step S01, according to mass ratio, the ingredient proportion of the quantum dot and the expanding material is (1-4):
(2-8), under the proportion, expanding material is adequately modified in quantum dot surface, avoids quantum dot from not coated completely, while also guaranteeing
Expanding material clad is unlikely to blocked up.
During expanding material and quantum dot carry out cladding processing, it can be ultrasonically treated, ultrasonic time 20-
60min, supersonic frequency only need to be handled according to conventional ultrasonic device, centrifugal treating are carried out after ultrasonic treatment, i.e.,
It can get the quantum dot of epoxy functionalized dough.And in order to enable covered effect is more preferable, first expanding material can be dissolved in solvent,
Expanding material can be such as dissolved in tetrahydrofuran, form the tetrahydrofuran solution that expanding material concentration is 5-20wt%.After cladding
Removal solvent can be heated, the quantum dot that expanding material coats can also be stayed in solvent and continue further cladding processing.
Using the modified oleic acid of epoxy-functional as expanding material, and when being coated using oleic acid as the quantum dot of ligand,
Self assembly occurs for the carbochain of carbochain and quantum dot ligand on expanding material, and uniform sequential self assembly knot is formed in quantum dot surface
Structure, expanding material is attached to quantum dot surface at this time, and the epoxy-functional on expanding material is outwardly, is and other high-molecular compounds
Equal materials occur good dispersion compatibility and provide good microcosmic surface.
After the quantum dot of expanding material that above-mentioned steps S01 is handled cladding, further include by high-molecular compound with
The quantum dot of the expanding material cladding carries out mixing and curing process.
When high-molecular compound is mixed with the quantum dot that the expanding material coats, according to mass ratio, the quantum
The ingredient proportion of point and the high-molecular compound is (1-2): (1-3).
It is carried out in mixed process in quantum dot and high-molecular compound, it can be directly by the quantum dot and height of expanding material cladding
Molecular compound carries out mixed processing, and first the quantum dot that expanding material coats can also be dissolved in solvent, it is dense to form quantum dot
Degree is about the tetrahydrofuran solution of 1-5wt%, then is mixed with high-molecular compound to uniform.
Preferably, the high-molecular compound is epoxy resin.Being primarily due to it using epoxy resin can be with increase-volume
Epoxy-functional in agent has good compatibility, so that quantum dot dispersibility greatly gets a promotion.Certainly, of the invention
High-molecular compound is not limited to epoxy resin, can also be polymethyl methacrylate (PMMA) etc..
The above-mentioned curing process being related to is referred to using curing agent to the quantum dot and macromolecule chemical combination for having coated expanding material
The mixed product of object carries out curing process, mainly to high-molecular compound into solidification.By solidification, so that macromolecule chemical combination
Object is cross-linked into the stable high molecular material of chemical property.
Preferably, the curing agent is pnenolic aldehyde amine hardener, acid anhydride type curing agent, imidazole curing agent, thio-alcohol solidification
Any one of agent.Curing agent cited by the present invention should match when in use with high-molecular compound, due to above-mentioned
High-molecular compound, curing agent and solidification process belong to existing technology, and its material proportion also belongs to common sense, because
This, is not unfolded to be described in detail to high-molecular compound, curing agent and solidification process in the present invention.
Before curing process, it is necessary to which heating removal solvent avoids the presence of solvent and causes to generate sand holes.Solidifying
Before, it is necessary to heating removing bubble excludes the gas in high-molecular compound and quantum dot mixed material, to reach better
Avoid generating the effect of sand holes.
, can be die-filling to nanocomposite progress according to different requirements, when solidification, it carries out at solidification in a mold
Reason, finally obtains the nanocomposite of different models.
The preparation method of nanocomposite provided in an embodiment of the present invention, directly ligand modified quantum dot surface into
The cladding of row expanding material is mixed again with high-molecular compound and curing process, improves quantum dot and high-molecular compound
Compatibility avoids quantum dot agglomeration, so that quantum dot is dispersed in high-molecular compound, finally obtains transparency
Nanocomposite high, fluorescence intensity is strong.Moreover, the preparation method of nanocomposite provided by the invention, simple process
It is easily-controllable, at low cost, industrialization production easy to accomplish.
Such as, using oleic acid as the quantum dot of ligand, since oleic acid being capable of matching by carboxyl and quantum dot surface unoccupied orbital
Position effect is adsorbed onto quantum dot surface, while making the carbon-chain structure of oleic acid therefore, quantum dot surface forms one layer of packet outwardly
The non-polar conformations wrapped up in, when carrying out cladding processing to quantum dot with expanding material, the carbochain self assembly of aliphatic lateral chain and oleic acid
In quantum dot surface, while the epoxy group of the other end is outwardly, so that the pole of the quantum dot of expanding material modified and epoxy matrix
Property is similar, when using epoxy resin as high-molecular compound, can play good interface com-patibilising effect.
Generally speaking, the nanocomposite that the embodiment of the present invention is prepared, interfacial effect and interphase match obtain
Great improvement, prevent with the contact of water, oxygen, have the characteristics that high transparency and fluorescence intensity.Therefore, it can apply
In the fields such as solar energy, luminescent device, optical bio label.
Technical solution in order to better illustrate the present invention, is illustrated combined with specific embodiments below.
Embodiment 2
A kind of preparation method of nanocomposite, the preparation process of the nanocomposite the following steps are included:
S21. the preparation of expanding material: weighing 20g epoxy resin (AG-80) and 30mL oleic acid, by the epoxy resin of acquisition with
Oleic acid is placed in single necked round bottom flask together, is reacted for 24 hours in 200 DEG C of oil baths, is obtained the expanding material with epoxy-functional;
S22. the preparation of the quantum dot of expanding material modification: the ligand (quantum containing CdSe that oleic acid and CdSe quantum dot are formed
Point 20g) it is dissolved in tetrahydrofuran together with the expanding material 20g for obtaining step S21, it is ultrasonically treated 60min, then in centrifuge
In 10min is centrifuged with the revolving speed of 8000rpm, obtain the functionalized quantum dot of epoxy group, realize expanding material in quantum dot surface
Cladding;
S23. the quantum dot of expanding material cladding 5g step S22 obtained is added in tetrahydrofuran, forms solution, and to its
The middle epoxy resin (AG-80) that 5g is added, is stirred at room temperature to uniform, is subsequently placed into 80 DEG C of vacuum ovens dry 3h, removal
Tetrahydrofuran solvent takes out after band is cooling, and the triethylene tetramine of about 0.85g is added thereto, stirs evenly in 60 DEG C same
When the bubble in mixed material is removed, then solidify 6h in 90 DEG C of baking ovens, can be obtained quantum dot and epoxy resin knot
The nanocomposite of conjunction.
Comparative example 1
A kind of preparation method of nanocomposite, the preparation process of the nanocomposite the following steps are included:
D11. 5g CdSe quantum dot is dissolved in tetrahydrofuran, and the epoxy resin (E51) of 5g, room temperature is added thereto
It is stirred until homogeneous, is subsequently placed into 40 DEG C of vacuum ovens dry 1h, remove tetrahydrofuran solvent, taken out after band is cooling, and to
The triethylene tetramine of about 0.55g is wherein added, stirred evenly in 40 DEG C while the bubble in mixed material is removed, then
Solidify 2h in 60 DEG C of baking ovens, can be obtained nanocomposite of the quantum dot in conjunction with epoxy resin.
In order to illustrate the technical effect of nanocomposite of the invention, the nanometer that embodiment 1-2 and comparative example 1 are obtained
Composite material carries out the test analysis of transparent characteristic, fluorescent characteristic.
One, the specific implementation method of transparent characteristic is as follows:
The nanocomposite obtained is characterized using 3500 types (Japanese Shimadzu Corporation) ultraviolet-visible spectrophotometer
Transparent performance, test when carried out under through mode mode using air as background, every kind testing of materials 5 times, be averaged, and general
Average value is reported in Table 1 below.
Two, fluorescent characteristic is tested
The fluorescence of nanocomposite obtained is characterized using F4500 type (Hitachi, Japan) sepectrophotofluorometer
Characteristic, every kind testing of materials 5 times, be averaged, and testing mean is reported in Table 1 below.
The nanocomposite the performance test results of 1 embodiment 1-2 of table and comparative example 1
Group |
Embodiment 1 |
Embodiment 2 |
Comparative example 1 |
800nm visible light transmittance average value |
76% |
81% |
43% |
550nm mean value of fluorescence intensity |
1682000 |
1750027 |
607108 |
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.