CN106753328B - A kind of high stability polymer overmold quantum dot fluorescence powder material and preparation method thereof - Google Patents
A kind of high stability polymer overmold quantum dot fluorescence powder material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of high stability polymer overmold quantum dot fluorescence powder materials and preparation method thereof, the preparation method comprises the following steps: first preparing quantum dot solution, the quantum dot solution of preparation is purified again, polymer overmold quantum dot fluorescence powder material finally is made with polymer in the quantum dot solution after purification；High stability polymer overmold quantum dot fluorescence powder material provided through the invention and preparation method thereof, prepared high stability polymer overmold quantum dot fluorescence powder material has yield high, stability is high, heatproof moisture-proof is good, safety and environmental protection, not easy to reunite, long service life, simple and practical advantage, strong operability is suitble to be prepared on a large scale.
Description
Technical field
The present invention relates to quanta point material fields, particularly relate to a kind of high stability polymer overmold quantum dot fluorescence powder material
Material and preparation method thereof.
Background technique
Quantum dot is a kind of novel zero dimensional nanometer materials, and excellent fluorescence property, high quantum production rate, wavelength continuously may be used
Tonality, narrow half-peak breadth, wide colour gamut etc. make it have huge application prospect in illumination and display field.The cadmium class quantum currently prepared
Point usually can form nuclear-shell structure type quantum dot by cladding to reduce surface defect, improve quantum yield, but process is numerous
Trivial, condition is not easy to control, stability, heatproof moisture-proof or undesirable.Secondly, current most of quantum dots are in last drying
And pyroprocess can be related to during forming fluorescent powder, this may destroy surface ligand, and quantum dot is caused to be reunited, and reduce
Quantum yield.
Patent CN 101585517, publication date are on November 25th, 2009, and the patent proposes a kind of selenium for emitting blue light
The synthetic method of cadmium quantum dot powder, this method meaning quantum dot powder only includes cadmium selenide core, without it is any it is inorganic/have
The protection of machine layer can not only cause damages to environment, can not also measure the stability in its use process.
Patent CN 105885318A proposes a kind of preparation side of polychrome CdTe quantum/polymer fluorescent composite material
The polymer or molten condition mixed with polymers of CdTe quantum and dissolution, then cooling are obtained room temperature by method, this method.The party
Method needs to heat to accelerate that high temperature (170 DEG C), such nothing will be heated in solvent volatilization (100 DEG C), or melting internal mixing pass
Method guarantees whether quantum dot surface ligand is effectively protected, and then influences the yield and stability of quantum dot.
CN 103030822A proposes quantum dot powder and preparation method thereof, silica-gel lens and preparation method thereof and LED light
Tool, this method by quantum dot polymer dispersion be coated in plate on form coating film, then toast or ultraviolet irradiation formed solidification
Film finally grinds to obtain quantum dot powder again.Coating processes, complex procedures are used in quantum dot powder preparing processes；High temperature
Baking (150 DEG C) not can guarantee quantum dot surface ligand yet and not be destroyed, and will be unfavorable for the yield and stability of quantum dot.
Summary of the invention
The disadvantage low to the above-mentioned low yield of quantum dot in the prior art and stability, the present invention provides a kind of high
Stable polymers coated quantum dots phosphor material powder and preparation method thereof, adopts the following technical scheme that
Quantum dot solution is first prepared, then the quantum dot solution of preparation is purified, it is finally that the quantum dot after purification is molten
Polymer overmold quantum dot fluorescence powder material is made in liquid and polymer；The preparation method of polymer overmold quantum dot fluorescence powder material
Are as follows:
Step 1: first high molecular polymer is dissolved in organic solvent；
Step 2: at room temperature, quantum dot solution and mixing after purification is added into organic solvent made of step 1
Uniformly, quantum dot-high molecular polymer mixed liquor is made；
Step 3: quantum dot-high molecular polymer mixed liquor is placed in a vacuum drying oven carry out drying at room temperature, the amount of obtaining
Sub- point-high molecular polymer solid mixt；
Step 4: quantum dot-high molecular polymer solid mixt is crushed, and is sieved to get high stability polymer is arrived
Coated quantum dots phosphor material powder.
Further, the quantum dot solution is Cd0.58Zn0.42S@ZnS@ZnS quantum dot solution, preparation method are as follows:
Step a: taking cadmium oxide, anhydrous zinc acetate, oleic acid and octadecylene to be placed in container, in 100 DEG C of lower pumping 30min,
It is warming up to 150 DEG C again to continue to be evacuated 30min, is then warming up to 250 DEG C and cadmium oxide and zinc acetate is completely dissolved, form oleic acid
Cadmium and oleic acid zinc solution；
Step b: injecting the thio decane of 1- in cadmium oleate and oleic acid zinc solution, then heats to 270 DEG C, keeps the temperature 20min,
To grow Cd0.58Zn0.42S quantum dot core；
Step c: in Cd0.58Zn0.42The thio decane of 1- is slowly injected into S quantum dot core, 260 DEG C of heat preservation 40min are with growth regulation
One layer of ZnS shell continues to inject the thio decane of 1-, natural after reaction in 260 DEG C of heat preservation 30min to grow second layer ZnS shell
It is cooled to room temperature to get Cd is arrived0.58Zn0.42S@ZnS@ZnS quantum dot solution.
Further, the quantum dot solution is CdSe@ZnSe@ZnS quantum dot solution, and preparation method is as follows:
Step a: taking anhydrous zinc acetate, oleic acid and octadecylene to be placed in container, is heated to 150 DEG C of dissolutions, obtains solution A；
Step b: taking selenium powder and octadecylene, and ultrasonic disperse obtains dispersion liquid B；
Step c: it is evacuated 30min after taking cadmium oxide, stearic acid, octadecylene and octadecylamine to be heated to 100 DEG C, then is warming up to
250 DEG C are completely dissolved cadmium oxide, and the dispersion liquid B that at 280 DEG C prepared by injection step b after reacting 5min, then is cooled to
220 DEG C are slowly injected into solution A prepared by step a, keep the temperature 15min, that is, complete the cladding of ZnSe layer；
Step d: after the completion of step c, the injection thio decane of 1- is cooled in 250 DEG C of heat preservation 30min to grow ZnS layers
Room temperature obtains CdSe@ZnSe@ZnS quantum dot.
Further, in step 2, the mass ratio of quantum dot and high molecular polymer in quantum dot solution is 0.01:1
~0.2:1.
Further, the high molecular polymer is the high molecular polymer of translucency.
Further, the method for purification of the quantum dot solution are as follows:
Quantum dot solution and precipitating reagent are mixed according to volume ratio for 1:1~1:8, and stirs and mixes at 40 DEG C~100 DEG C
Close 30min~1h, then after carrying out ultrasonic disperse 10min~30min, by mixed solution be placed in a centrifuge with 6000r/min~
14000r/min is centrifuged 10min~30min, and then the precipitation solid that centrifugation obtains is dissolved in solvent；Repeat aforesaid operations two
After secondary to get arrive quantum dot precipitation solid；
It weighs and is repeatedly centrifuged the quantum dot solution that quantum dot precipitation solid dissolution obtained is purified in a solvent.
Further, the precipitating reagent be one of methanol, dehydrated alcohol, butanol, isopropanol, acetonitrile, acetone or
It is a variety of.
Further, the solvent is one or more of chloroform, n-hexane and toluene.
Further, quantum dot-high molecular polymer mixed liquor hybrid mode includes physical agitation, magnetic agitation, surpasses
Sound mixing, the one or more hybrid modes of ball milling mixing combination, incorporation time be 10min~48h, mixing temperature be 25 DEG C~
60℃；Quantum dot-high molecular polymer solid mixt breaking method includes mill crushing, mechanical crushing, ball mill grinding, gas
Stream crushes or the combination of many of grinding mode, and grinding time is 5min~100h.
A kind of a kind of high stability polymer overmold quantum dot fluorescence powder using as above any preparation method preparation
Material.
It is prepared the present invention provides a kind of high stability polymer overmold quantum dot fluorescence powder material and preparation method thereof
High stability polymer overmold quantum dot fluorescence powder material have yield high, stability is high, and heatproof moisture-proof is good, safety collar
It protects, not easy to reunite, long service life is simple and practical, and strong operability is suitble to the advantages of being prepared on a large scale.
Detailed description of the invention
Fig. 1 is Cd in embodiment one0.58Zn0.42S ZnS ZnS quantum dot and the yield of comparative sample 1 are with cladding number of plies variation
Comparison diagram；
Fig. 2 is the comparison that CdSe ZnSe ZnS quantum dot and the yield of comparative sample 2 change with the cladding number of plies in embodiment two
Figure；
Fig. 3 is the Cd of coated polymer in embodiment one0.58Zn0.42@ZnS@ZnS quantum dot phosphor material powder is wet 85%
Degree and 85 DEG C at a temperature of with Cd0.58Zn0.42The Cd of S quantum dot and uncoated organic matter0.58Zn0.42@ZnS@ZnS quantum dot aging
Test chart；
Fig. 4 be coated in embodiment two organic matter CdSe@ZnSe@ZnS quantum dot phosphor material powder in 85% humidity and
At a temperature of 85 DEG C with the burn-in test figure of CdSe quantum dot and the CdSe@ZnSe@ZnS quantum dot of uncoated organic matter；
Fig. 5 is the Cd of coated polymer in embodiment one0.58Zn0.42@ZnS@ZnS quantum dot phosphor material powder is wet 85%
Degree and 85 DEG C at a temperature of different time emission spectrum variation diagram；
Fig. 6 be coated in embodiment two organic matter CdSe@ZnSe@ZnS quantum dot phosphor material powder in 85% humidity and
The emission spectrum variation diagram of different time at a temperature of 85 DEG C.
Specific embodiment
The present invention provides a kind of high stability polymer overmold quantum dot fluorescence powder materials and preparation method thereof, use below
Embodiment is described further preparation method of the invention.
Embodiment one
Embodiment one is with Cd0.58Zn0.42S@ZnS@ZnS quantum dot prepares high stability polymer overmold quantum dot fluorescence powder
Material, preparation method include:
The preparation of step 1, quantum dot solution；
1mmol cadmium oxide, 10mmol anhydrous zinc acetate, 6ml oleic acid and 10ml octadecylene is taken to be placed in the three-necked flask of 100ml
In, 100 DEG C of pumping 30min, then be warming up to 150 DEG C and continue to be evacuated 30min, it then heats to 250 DEG C and makes cadmium oxide and acetic acid
Zinc is completely dissolved, and forms cadmium oleate and oleic acid zinc solution；It is thio that 2mmol 1- is rapidly injected in cadmium oleate and oleic acid zinc solution
Decane then heats to 270 DEG C, 20min is kept the temperature, to grow Cd0.58Zn0.42S quantum dot core；
In Cd0.58Zn0.42The thio decane of 2mmol 1- is slowly injected into S quantum dot core, 260 DEG C of heat preservation 40min are with growth regulation
One layer of ZnS shell continues to be slowly injected into the thio decane of 3mmol 1-, in 260 DEG C of heat preservation 30min to grow second layer ZnS shell, reaction
After cooled to room temperature to get arrive Cd0.58Zn0.42S@ZnS@ZnS quantum dot solution.
The purification of step 2, quantum dot solution；
Take Cd made from 6ml step 10.58Zn0.42S@ZnS@ZnS quantum dot solution is added 30ml dehydrated alcohol, is placed in
It is mixed in 50ml single-necked flask, at 50 °C ultrasonic disperse 10min after magnetic agitation 30min；By mixed solution be placed in from
12000r/min is centrifuged 10min in scheming, removes supernatant liquor, and the precipitation solid that centrifugation obtains is dissolved in 6ml toluene；Weight
Multiple aforesaid operations twice, obtain Cd0.58Zn0.42S@ZnS@ZnS quantum precipitation solid；
It weighs and is repeatedly centrifuged Cd obtained0.58Zn0.42S@ZnS@ZnS quantum precipitation solid 200mg is dissolved in 6ml toluene,
Cd after being purified0.58Zn0.42S@ZnS@ZnS quantum dot solution.
The preparation of step 3, polymer overmold quantum dot fluorescence powder material；
20g polymethyl methacrylate (PolymethylMethacrylate, abbreviation PMMA) solid powder is taken to be placed in
In 200ml chloroform, magnetic agitation 1h is completely dissolved PMMA powder at room temperature；Obtained in 6ml step 2 mention is added thereto
Cd after pure0.58Zn0.42S@ZnS@ZnS quantum dot solution, after magnetic agitation 1h, ultrasonic disperse 20min obtains quantum dot-high score
Sub- mixed with polymers liquid；Further quantum dot-high molecular polymer mixed liquor is put into beaker, be placed in a vacuum drying oven into
Row drying at room temperature 12h obtains quantum dot-high molecular polymer solid mixt；
Finally quantum dot-high molecular polymer solid mixt is placed in mortar and is milled, grinding time 30min, mistake
High stability polymer overmold quantum dot fluorescence powder material is obtained after 400 meshes.
Embodiment two
Embodiment two prepares high stability polymer overmold quantum dot fluorescence powder material with CdSe@ZnSe@ZnS quantum dot,
Preparation method includes:
Step 1 prepares quantum dot solution using SILAR method；
2mmol anhydrous zinc acetate, 2ml oleic acid and 2ml octadecylene are taken, 150 DEG C of dissolutions is heated to, obtains solution A；It takes
1mmol selenium powder and 2ml octadecylene, ultrasonic disperse obtain dispersion liquid B；Take 0.2mmol cadmium oxide, 1mmol stearic acid, 5ml 18
Alkene and 5g octadecylamine are heated to 100 DEG C, are evacuated 30min, are warming up to 250 DEG C and cadmium oxide is completely dissolved, fast at 280 DEG C
Speed injection 2ml dispersion liquid B after reacting 5min, then is cooled to 220 DEG C and is slowly injected into 2ml solution A, and heat preservation 15min coats ZnSe
Layer；It is slowly injected into the thio decane of 1.5mmol 1- again, 250 DEG C of heat preservation 30min are cooled to room temperature and obtain to grow ZnS layers
CdSe@ZnSe@ZnS quantum dot.
The purification of step 2, quantum dot solution；
CdSe@ZnSe@ZnS quantum dot solution made from 10ml step 1 is taken, 40ml acetone is added, is placed in 100ml single port burning
In bottle, the magnetic agitation 30min at 40 DEG C, progress ultrasonic disperse 10min is placed in centrifuge to be centrifuged with 10000r/min
20min removes supernatant liquor, and the precipitation solid that centrifugation obtains is dissolved in 10ml chloroform；It repeats aforesaid operations twice, obtains
CdSe@ZnSe@ZnS quantum precipitation solid；
CdSe@ZnSe@ZnS quantum precipitation solid 200mg made from being repeatedly centrifuged is weighed to be dissolved in 10ml chloroform to obtain the final product
CdSe@ZnSe@ZnS quantum dot solution after to purification.
The preparation of step 3, polymer overmold quantum dot fluorescence powder material；
20gPMMA solid powder is taken to be placed in 200ml chloroform, magnetic agitation 1h makes PMMA powder completely molten at room temperature
Solution；It is added CdSe@ZnSe@ZnS quantum dot solution after purification obtained in 10ml step 2 thereto, after magnetic agitation 1h, surpasses
Sound dispersion 20min obtains quantum dot-high molecular polymer mixed liquor；Further quantum dot-high molecular polymer mixed liquor is put
Enter in beaker, is placed in a vacuum drying oven drying at room temperature 12h and obtains quantum dot-high molecular polymer solid mixt；
Finally quantum dot-high molecular polymer solid mixt is placed in mortar and is milled, grinding time 30min, mistake
High stability polymer overmold quantum dot fluorescence powder material is obtained after 400 meshes.
In example 1 and example 2, high molecular polymer is the high molecular polymer of translucency, can guarantee height
The embodiment of stable polymers coated quantum dots phosphor material powder optical effect；High molecular polymer includes esters of acrylic acid tree
Rouge, polymerization of acrylic modified polyurethane, polystyrene, polycarbonate, styrene-acrylonitrile copolymer, gathers organosiloxane resins
Methyl isoprene, transparent polyurethane, acryl-modified silicone resin resin or epoxy resin, are also possible to different polyphosphazene polymers
The combination between object is closed, but is not limited to these types above-mentioned.
The present invention is coated after purifying quantum dot using multilayer inorganic matter, then is had with the high molecular polymer of translucency
Machine object coats the quantum dot for coating multilayer inorganic matter, has completely cut off the direct contact of quantum dot and external environment, the amount of avoiding
Heavy metal element and toxic component in son point ensure that quantum dot exists to external environmental and to the injury of human body
Stability and heatproof moisture-proof in use process, extend service life.
The present invention prepares quantum dot-high molecular polymer mixed liquor at normal temperature, and carries out room temperature in a vacuum drying oven
It is dry, quantum dot-high molecular polymer solid mixt is obtained, high stability polymer overmold quantum dot fluorescence powder is finally made
Material is avoided quantum dot in last drying and forms the process of fluorescent powder and led to using high temperature the ligand of quantum dot surface
It is destroyed, quantum dot is made to reunite, and then reduce quantum yield, while the present invention also saves the energy.
Wherein, quantum dot solution preparation method includes hot injection method, one kettle way, base exchange method, the suction of continuous ionic layer
One of reaction enclosure method is a variety of.
Wherein, for the too low meeting of quantum dot concentration so that luminous intensity is not high enough, quantum dot excessive concentration not only will affect quantum
The encapsulation process of point, so that quantum dot self-absorption is serious, so that shining for quantum dot is influenced, it is therefore, provided by the invention high steady
In qualitative polymer overmold quantum dot fluorescence powder material, the mass ratio of quantum dot and high molecular polymer in quantum dot solution is
On the one hand 0.01:1~0.2:1 can guarantee the luminous intensity of quantum dot under this ratio, another aspect quantum dot is reduced certainly
Absorbing phenomenon, while being also beneficial to encapsulate.
Wherein, in the prior art, it commonly uses one layer of ZnS and coats Cd0.58Zn0.42S, quantum dot yield are still lower；And frequently with
Sulphur source of the sulphur-tributylphosphine solution as cladding ZnS, reactivity is low, and reaction temperature is high.In specific embodiment one, use
Two layers of ZnS layers of cladding is so that Cd0.58Zn0.42S@ZnS@ZnS alloy quantum dot yield is higher；Using the thio decane of 1- as sulphur source,
Reactivity can be made higher, reaction temperature is lower, and then improves the stability of quantum dot.
Wherein, SILAR method is used in specific embodiment two, enormously simplifies quantum dot multilayer coating structure
Process, and selenium powder-tri octyl phosphine solution is replaced with selenium powder-octadecylene dispersion liquid, save cost；Using ZnSe as transition
Layer improves lattice, reduces the luminous probability of defect state, the CdSe@ZnSe@ZnS quantum dot yield finally prepared is high, property
It can stablize.
Further, quantum dot is single quantum dot, or the mixing of different quantum dots, but is not limited to above-mentioned several
Material quantum dot, further include by the II, the III in the periodic table of elements, IV, V, element forms in VI main group, including unitary amount
Sub- point C point and Si point；Binary Quantum dots CdS e, CdS, ZnS, ZnSe, CdTe, MgS, MgSe, MgTe, CaS, CaSe, CaTe,
SrS、SrTe、BaS、BaSe、BaTe、ZnTe、GaN、GaP、GaAs、InN、InP、InAs、PbS、PbSe、PbTe、HgTe、ZnO、
Ag2Se、Ag2S、Cu2+Adulterate ZnS, Mn2+ doping ZnSe and its nuclear shell structure quantum point；Ternary quantum dots CuInS2、
CuInSe2、CuInTe2、AgInS2, CdZnSe, CdZnS, CdZnTe, CdMgTe, AlGaN, GaPN, InPAs, InPN etc. and its
Core-shell structure or doped quantum dot；CsPbX3, X=Cl, Br, I；CsSnX3, X=Cl, Br, I；CH3NH3PbX3, X=Cl, Br, I；
Perovskite quantum dot.
High stability polymer overmold quantum dot fluorescence powder material preparation method provided by the invention is simple and practical, can operate
Property is strong, enormously simplifies the preparation process of quantum dot fluorescence powder, shorten the period be suitble to be prepared on a large scale high quality quantum dot it is glimmering
The preparation of light powder.
Fig. 1 is the Cd prepared in embodiment one0.58Zn0.42S@ZnS@ZnS quantum dot and in the prior art comparative sample
1Cd0.58Zn0.42For the yield of S ZnS quantum dot with the comparison diagram of cladding number of plies variation, the uncoated organic matter of the two can from figure
To find out, preparation method coats the Cd of bilayer ZnS through the invention0.58Zn0.42S@ZnS@ZnS yield is 88% single with only cladding
The yield of the comparative sample 1 of layer ZnS is compared for 69%, and yield is significantly improved；Meanwhile preparing through the invention
Cd0.58Zn0.42S@ZnS@ZnS, the yield when coating the ZnS of single layer are 73%, the production of the comparative sample 1 than only coating single layer ZnS
Rate is compared for 69%, and yield also has promotion, illustrates that the quantum dot of preparation method preparation of the invention has side to the promotion of yield
It helps；As seen in Figure 1, Cd prepared by the present invention0.58Zn0.42S ZnS ZnS quantum dot with cladding the number of plies raising, yield from
73% is promoted to 88%, illustrates that the cladding number of plies proposed by the present invention for increasing quantum dot ZnS has significantly the promotion of yield
Effect.
Fig. 2 is the CdSe@ZnSe@ZnS quantum dot prepared in the embodiment of the present invention two and comparative sample in the prior art
For the yield of 2CdSe ZnS ZnS quantum dot with the comparison diagram of cladding number of plies variation, the uncoated organic matter of the two can from Fig. 2
To find out, the yield of the CdSe@ZnSe@ZnS quantum dot of preparation method through the invention preparation is 87.3%, is significantly higher than pair
Than the yield of sample 2CdSe@ZnS@ZnS quantum dot 59%；Present invention employs ZnSe to make instead of the ZnS in comparative sample 2, ZnSe
Lattice is improved for transition zone, reduces the luminous probability of defect state, the preparation method provided through the invention can be seen that
CdSe@ZnSe@ZnS quantum dot yield is significantly improved.
Fig. 3 is Cd0.58Zn0.42The Cd of S quantum dot, uncoated organic matter0.58Zn0.42@ZnS@ZnS quantum dot and pass through this
Prepared by inventive embodiments one has coated organic matter Cd0.58Zn0.42@ZnS@ZnS quantum dot fluorescent powder is in 85% humidity and 85 DEG C of temperature
Burn-in test figure under degree.It can be seen that Cd0.58Zn0.42S quantum dot and Cd without polymer overmold organic matter0.58Zn0.42@
ZnS@ZnS quantum dot extends with the testing time, and yield declines quickly；The Cd of a preparation through the embodiment of the present invention0.58Zn0.42@
ZnS ZnS quantum dot fluorescent powder is still able to maintain 80% yield after 2800min burn-in test, it can be seen that height prepared by the present invention
Stable polymers coated quantum dots phosphor material powder has good heatproof moisture-proof, and excellent in stability.
Fig. 4 is CdSe quantum dot, the CdSe@ZnSe@ZnS quantum dot of uncoated organic matter and through the embodiment of the present invention two
Preparation has coated organic matter CdSe@ZnSe@ZnS quantum dot fluorescent powder burn-in test figure at a temperature of 85% humidity and 85 DEG C,
It can be seen that CdSe quantum dot and CdSe@ZnSe@ZnS quantum dot without polymer overmold organic matter prolong with the testing time
Long, yield declines rapidly；And the CdSe@ZnSe@ZnS quantum dot fluorescent powder of two preparations is in 2800min through the embodiment of the present invention
85% yield is still able to maintain after burn-in test, it can be seen that high stability polymer overmold quantum dot fluorescence powder prepared by the present invention
Material has good heatproof moisture-proof, and excellent in stability.
Fig. 5 and Fig. 6 is for high stability polymer overmold quantum dot fluorescence powder material embodiment one prepared by the present invention and in fact
Apply emission spectrum variation diagram at a temperature of 85% humidity and 85 DEG C of example two.It can be seen that compared with 0h and for 24 hours, 48h burn-in test
Afterwards, quantum dot fluorescence powder material is still able to maintain emission peak wavelength and does not move substantially, and half-peak breadth does not increase, i.e., launch wavelength has good
Good stability, it can be seen that high stability polymer overmold quantum dot fluorescence powder material prepared by the present invention has high stable
Property.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (9)
1. a kind of preparation method of polymer overmold quantum dot fluorescence powder material, first prepares quantum dot solution, then the amount to preparation
Son point solution is purified, and polymer overmold quantum dot fluorescence powder material finally is made with polymer in the quantum dot solution after purification
Material；It is characterized in that, polymer overmold quantum dot fluorescence powder material the preparation method comprises the following steps:
Step 1: first high molecular polymer is dissolved in organic solvent；
Step 2: at room temperature, into organic solvent made of step 1 be added purification after quantum dot solution and be uniformly mixed,
Quantum dot-high molecular polymer mixed liquor is made；
Step 3: quantum dot-high molecular polymer mixed liquor is placed in a vacuum drying oven carry out drying at room temperature, obtains quantum
Point-high molecular polymer solid mixt；
Step 4: quantum dot-high molecular polymer solid mixt is crushed, and sieving is to get glimmering to polymer overmold quantum dot
Light powder material；
Wherein, in step 1, the high molecular polymer is polymethyl methacrylate；
In step 2, the mass ratio of quantum dot and high molecular polymer in quantum dot solution is 0.01:1~0.2:1.
2. a kind of preparation method of polymer overmold quantum dot fluorescence powder material as described in claim 1, which is characterized in that described
Quantum dot solution is Cd0.58Zn0.42S@ZnS@ZnS quantum dot solution, preparation method are as follows:
Step a: taking cadmium oxide, anhydrous zinc acetate, oleic acid and octadecylene to be placed in container, in 100 DEG C of lower pumping 30min, then rises
Temperature to 150 DEG C continue be evacuated 30min, be then warming up to 250 DEG C and cadmium oxide and zinc acetate be completely dissolved, formed cadmium oleate and
Oleic acid zinc solution；
Step b: injecting the thio decane of 1- in cadmium oleate and oleic acid zinc solution, then heats to 270 DEG C, 20min is kept the temperature, with life
Long Cd0.58Zn0.42S quantum dot core；
Step c: in Cd0.58Zn0.42The thio decane of 1- is slowly injected into S quantum dot core, 260 DEG C of heat preservation 40min are to grow first layer
ZnS shell continues to inject the thio decane of 1-, in 260 DEG C of heat preservation 30min to grow second layer ZnS shell, natural cooling after reaction
To room temperature to get arrive Cd0.58Zn0.42S@ZnS@ZnS quantum dot solution.
3. a kind of preparation method of polymer overmold quantum dot fluorescence powder material as described in claim 1, which is characterized in that described
Quantum dot solution is CdSe@ZnSe@ZnS quantum dot solution, and preparation method is as follows:
Step a: taking anhydrous zinc acetate, oleic acid and octadecylene to be placed in container, is heated to 150 DEG C of dissolutions, obtains solution A；
Step b: taking selenium powder and octadecylene, and ultrasonic disperse obtains dispersion liquid B；
Step c: being evacuated 30min after taking cadmium oxide, stearic acid, octadecylene and octadecylamine to be heated to 100 DEG C, then is warming up to 250 DEG C
So that cadmium oxide is completely dissolved, the dispersion liquid B that at 280 DEG C prepared by injection step b after reacting 5min, then is cooled to 220 DEG C
It is slowly injected into the solution A of step a preparation, 15min is kept the temperature, that is, completes the cladding of ZnSe layer；
Step d: after the completion of step c, the injection thio decane of 1- is cooled to room temperature in 250 DEG C of heat preservation 30min to grow ZnS layers
Obtain CdSe ZnSe ZnS quantum dot.
4. a kind of preparation method of polymer overmold quantum dot fluorescence powder material as described in claim 1, it is characterised in that: described
High molecular polymer is the high molecular polymer of translucency.
5. a kind of preparation method of polymer overmold quantum dot fluorescence powder material as described in claim 1, which is characterized in that described
The method of purification of quantum dot solution are as follows:
Quantum dot solution and precipitating reagent are mixed according to volume ratio for 1:1~1:8, and are stirred at 40 DEG C~100 DEG C
30min~1h, then after carrying out ultrasonic disperse 10min~30min, by mixed solution be placed in a centrifuge with 6000r/min~
14000r/min is centrifuged 10min~30min, and then the precipitation solid that centrifugation obtains is dissolved in solvent；Repeat aforesaid operations two
After secondary to get arrive quantum dot precipitation solid；
It weighs and is repeatedly centrifuged the quantum dot solution that quantum dot precipitation solid dissolution obtained is purified in a solvent.
6. a kind of preparation method of polymer overmold quantum dot fluorescence powder material as claimed in claim 5, it is characterised in that: described
Precipitating reagent is one or more of methanol, dehydrated alcohol, butanol, isopropanol, acetonitrile, acetone.
7. a kind of preparation method of polymer overmold quantum dot fluorescence powder material as claimed in claim 5, it is characterised in that: described
Solvent is one or more of chloroform, n-hexane and toluene.
8. a kind of preparation method of polymer overmold quantum dot fluorescence powder material as claimed in claim 5, it is characterised in that: quantum
Select-hybrid mode of high molecular polymer mixed liquor includes magnetic agitation, ultrasonic mixing, the one or more mixing sides of ball milling mixing
The combination of formula, incorporation time are 10min~48h, and mixing temperature is 25 DEG C~60 DEG C；Quantum dot-high molecular polymer solid-state is mixed
The breaking method for closing object includes mill crushing, ball mill grinding, the combination of air-flow crushing or many of grinding mode, when crushing
Between be 5min~100h.
9. a kind of a kind of polymer overmold quantum dot fluorescence prepared using the preparation method as described in any one of claim 1~8
Powder material.
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| CN107163946B (en) * | 2017-07-18 | 2019-12-17 | 厦门世纳芯科技有限公司 | Preparation method of high-temperature-resistant hydrophobic quantum dot fluorescent powder material |
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| CN110373180A (en) * | 2019-07-25 | 2019-10-25 | 深圳市联宝威科技有限公司 | Cladded type quantum dot and preparation method thereof |
| CN111569678B (en) * | 2020-05-16 | 2022-05-24 | 青岛科技大学 | Method for preparing quantum dots with high yield and application of modified reverse osmosis membrane |
| CN114958376B (en) * | 2022-06-20 | 2023-11-03 | 滁州学院 | High-efficiency NaYF 4 Low-temperature preparation method of up-conversion nanocrystalline |
| CN115161026A (en) * | 2022-07-29 | 2022-10-11 | 厦门大学 | Core-shell quantum dot luminescent material and preparation method thereof |
| CN115433562B (en) * | 2022-08-29 | 2024-05-07 | 电子科技大学 | Method for improving particle size dispersity of quantum dots based on solvothermal method |
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