CN109988338A - Nanocomposite and its preparation method and application - Google Patents
Nanocomposite and its preparation method and application Download PDFInfo
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- CN109988338A CN109988338A CN201711470784.4A CN201711470784A CN109988338A CN 109988338 A CN109988338 A CN 109988338A CN 201711470784 A CN201711470784 A CN 201711470784A CN 109988338 A CN109988338 A CN 109988338A
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002096 quantum dot Substances 0.000 claims abstract description 133
- 239000000463 material Substances 0.000 claims abstract description 92
- 239000003446 ligand Substances 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 238000005253 cladding Methods 0.000 claims abstract description 24
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 19
- 229930195729 fatty acid Natural products 0.000 claims abstract description 19
- 239000000194 fatty acid Substances 0.000 claims abstract description 19
- 238000012545 processing Methods 0.000 claims abstract description 11
- 238000001338 self-assembly Methods 0.000 claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims description 24
- 229920000647 polyepoxide Polymers 0.000 claims description 24
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 23
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 23
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 23
- 239000005642 Oleic acid Substances 0.000 claims description 23
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 23
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 23
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 23
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 230000003287 optical effect Effects 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910004613 CdTe Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000002889 oleic acids Chemical class 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 3
- 239000000090 biomarker Substances 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 19
- 230000000694 effects Effects 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- -1 epoxy resin Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002500 effect on skin Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000016507 interphase Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
- C08K2003/3027—Sulfides of cadmium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
- C08K2003/3036—Sulfides of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Luminescent Compositions (AREA)
- Led Device Packages (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to quanta point material technical fields, specifically provide a kind of nanocomposite and its preparation method and application.The nanocomposite includes ligand modified quantum dot and the expanding material for being coated on the ligand modified quantum dot surface, and the expanding material has fatty acid carbon chain and active function groups, and fatty acid carbon chain be combined with each other with the ligand.Preparation method includes the following steps: carrying out cladding processing to ligand modified quantum dot using expanding material, makes the expanding material and the ligand that self assembly occur and be coated on the ligand modified quantum dot surface, obtain the quantum dot of expanding material cladding.Nanocomposite of the invention, since ligand modified quantum dot surface coats expanding material, so that quantum dot favorable dispersibility, and it is greatly improved with other polymer-polymer miscibilities, it can be very good to be scattered in other high-molecular compounds, the nanocomposite of acquisition has good transparency and high fluorescence intensity.
Description
Technical field
The invention belongs to quanta point material technical field more particularly to a kind of nanocomposite and preparation method thereof and answer
With.
Background technique
Quantum dot is also known as nanocrystalline, is a kind of nano particle being made of II-VI group or iii-v element.Quantum dot
Partial size generally between 1-10nm, since electrons and holes are by quantum confinement, continuous band structure become with molecule spy
The discrete energy level structure of property, can emit fluorescence after being stimulated.Based on quantum effect, quantum dot is in solar battery, hair
The fields such as optical device, optical bio label are with a wide range of applications.
Since the partial size of quantum dot is small, there is very big specific surface area, increasing for surface phase atomicity results in
The coordination of surface atom is insufficient, unsaturated bond and dangling bond (i.e. the unpaired electronics of crystalline surface) increase, and makes these surface atoms
It is extremely unstable with high activity, it is easy in conjunction with other atoms.Therefore, general quantum dot surface need to select suitably to match
Body to be coordinated with the metal of quantum dot surface, and the type of ligand has conclusive shadow to the efficiency and stability of quantum dot
It rings.With the development and optimization of quantum dot synthetic technology, the efficiency and stability of quantum dot have reached industrialization level.But
The unique skin effect of quantum dot also determines its sensibility to aqueous vapor and oxygen, and aqueous vapor and oxygen can destroy quantum dot surface
Ligand, reduce the efficiency of quantum dot.The size of quantum dot is smaller, and specific surface area is bigger, gets over to the sensibility of aqueous vapor and oxygen
It is high.
The study found that semiconductor-quantum-point/epoxy resin composite material excitation spectrum is very wide, and luminous intensity is high,
Therefore the extensive concern of society is caused using epoxy resin as the encapsulating material of white light LEDs in recent years.But since surface is imitated
It answers and the mismatch at interface, quantum dot is often intended to reunite in polar epoxy resin-base, cause to be difficult to prepare
The composite nano materials of the high grade of transparency, high fluorescent.
In composite nano materials, the polar matching degree of two-phase interface directly determines point of nano material in the base
The performance of bulk state and final nanocomposite.However, the presence of the non-polar carbon chains structure due to quantum dot surface,
So that quantum dot itself can not be directly effectively dispersed in polarity epoxy resin, and it will lead to the transparent of nanocomposite
Degree decline, fluorescence intensity weaken.
Summary of the invention
The purpose of the present invention is to provide a kind of composite nano materials and preparation method thereof, it is intended to solve existing quantum dot with
Mutually dispersibility is bad for the high-molecular compounds such as epoxy resin, is easy to happen and reunites and cause the nanocomposite obtained transparent
Spend the problems such as low, fluorescence intensity is weak.
Further, the present invention also provides the applications of the composite nano materials.
The present invention is implemented as follows: a kind of nanocomposite, the nanocomposite includes ligand modified amount
Son point and be coated on the expanding material of the ligand modified quantum dot surface, wherein the expanding material have fatty acid carbon chain and
Active function groups, the fatty acid carbon chain be combined with each other with the ligand.
Accordingly, a kind of preparation method of nanocomposite, at least includes the following steps:
Cladding processing is carried out to ligand modified quantum dot using expanding material, occurs that the expanding material and the ligand certainly
The ligand modified quantum dot surface is assembled and be coated on, the quantum dot of expanding material cladding is obtained.
Correspondingly, prepared by the preparation method of nanocomposite as described above or nanocomposite as described above
Application of the nanocomposite in solar battery, luminescent device, optical bio marker field.
Beneficial effects of the present invention are as follows: nanocomposite provided by the invention, due to ligand modified quantum dot table
Bread has covered expanding material, by the effect of expanding material, reduces the reuniting effect of quantum dot, quantum dot is uniformly dispersed
In the high-molecular compounds such as epoxy resin, the nanocomposite of acquisition shows good transparency and high fluorescence is strong
Degree.
The preparation method of nanocomposite provided by the invention directly carries out increase-volume in ligand modified quantum dot surface
The cladding of agent improves the compatibility of quantum dot and high-molecular compound, avoids quantum dot agglomeration, allow quantum dot equal
It is even to be dispersed in high-molecular compound, it is final to obtain the nanocomposite that transparency is high, fluorescence intensity is strong.Moreover, of the invention
The preparation method of the nanocomposite of offer, simple process is easily-controllable, at low cost, industrialization production easy to accomplish.
Nanocomposite provided by the invention, due to the features such as with good transparency, strong fluorescence can be issued,
It is highly suitable in the fields such as solar battery, luminescent device, optical bio label.
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 1
A kind of preparation method of nanocomposite, the preparation process of the nanocomposite the following steps are included:
S11. the preparation of expanding material: weighing 5g epoxy resin (E51) and 5mL oleic acid, by the epoxy resin and oleic acid of acquisition
It is placed in single necked round bottom flask together, 3h is reacted in 100 DEG C of oil baths, obtain the expanding material with epoxy-functional；
S12. 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 5g) it is dissolved in tetrahydrofuran together with the expanding material 10g for obtaining step S11, it is ultrasonically treated 20min, then in centrifuge
In 3min is centrifuged with the revolving speed of 3000rpm, obtain the functionalized quantum dot of epoxy group, realize expanding material in quantum dot surface
Cladding；
S13. the quantum dot for the expanding material cladding that 2g step S12 is obtained is mixed with tetrahydrofuran, forms solution, and
The epoxy resin (E51) of 2g is added thereto, is stirred at room temperature to uniform, is subsequently placed into 40 DEG C of vacuum ovens dry 1h, goes
Except tetrahydrofuran solvent, takes out after band is cooling, and the triethylene tetramine of about 0.25g is added thereto, stirred evenly in 40 DEG C
Simultaneously the bubble in mixed material is removed, then solidifies 2h in 60 DEG C of baking ovens, can be obtained quantum dot and epoxy resin
In conjunction with nanocomposite.
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.
Claims (13)
1. a kind of nanocomposite, which is characterized in that the nanocomposite includes ligand modified quantum dot and cladding
In the expanding material of the ligand modified quantum dot surface, wherein the expanding material has fatty acid carbon chain and active function groups,
The fatty acid carbon chain be combined with each other with the ligand.
2. nanocomposite as described in claim 1, which is characterized in that the active function groups are epoxy-functional.
3. nanocomposite as described in claim 1, which is characterized in that the expanding material is the modified oil of epoxy-functional
Acid；And/or the ligand is oleic acid；And/or the quantum dot be CdSe, CdS, CdTe, CdSe/ZnS, CdZnS/ZnS,
Any one of PbSe, PbS, PbSe/ZnS, PbSe/CdS.
4. nanocomposite as described in any one of claims 1-3, which is characterized in that the nanocomposite further includes
High-molecular compound.
5. nanocomposite as claimed in claim 4, which is characterized in that the high-molecular compound is epoxy resin.
6. a kind of preparation method of nanocomposite, which is characterized in that at least include the following steps:
Cladding processing is carried out to ligand modified quantum dot using expanding material, makes the expanding material and the ligand that self assembly occur
And it is coated on the ligand modified quantum dot surface, obtain the quantum dot of expanding material cladding.
7. the preparation method of nanocomposite as claimed in claim 6, which is characterized in that obtain the quantum of expanding material cladding
After the step of point, further includes: mixed high-molecular compound and curing process with the quantum dot that the expanding material coats.
8. the preparation method of nanocomposite as claimed in claim 6, which is characterized in that according to mass ratio, the quantum
The ingredient proportion of point and the expanding material is (1-4): (2-8).
9. the preparation method of nanocomposite as claimed in claims 6 or 7, which is characterized in that the expanding material has rouge
Fat acid carbochain and active function groups, the fatty acid carbon chain be combined with each other with the ligand.
10. the preparation method of nanocomposite as claimed in claim 9, which is characterized in that the active function groups are ring
Oxygen functional group.
11. such as the preparation method of the described in any item nanocomposites of claim 6 or 7, which is characterized in that the expanding material
For the modified oleic acid of epoxy-functional；And/or the ligand is oleic acid；And/or the quantum dot be CdSe, CdS, CdTe,
Any one of CdSe/ZnS, CdZnS/ZnS, PbSe, PbS, PbSe/ZnS, PbSe/CdS.
12. the preparation method of nanocomposite as claimed in claim 7, which is characterized in that the high-molecular compound is
Epoxy resin.
13. nanocomposite as described in any one in claim 1-5 is received as claim 6-12 is described in any item
The nanocomposite of the preparation method preparation of nano composite material is in solar battery, luminescent device, optical bio marker field
In application.
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