CN108315008A - Oil-soluble quantum dot is converted into the method and method of purification of water-soluble quantum dot - Google Patents
Oil-soluble quantum dot is converted into the method and method of purification of water-soluble quantum dot Download PDFInfo
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Abstract
The present invention discloses the method and method of purification that oil-soluble quantum dot is converted into water-soluble quantum dot, and method includes：It takes the dissolving of oil-soluble quantum dot in organic solvent, oil-soluble quantum dot solution is made；It takes sulfydryl glycol monomethyl ether to be dissolved in water and is stirred by ultrasonic to being completely dissolved, sulfydryl glycol monomethyl ether solution is made；Oil-soluble quantum dot solution is added in sulfydryl glycol monomethyl ether solution, is then stirred to react at certain temperature and atmosphere after a certain period of time, organic solvent is volatilized completely, obtains water-soluble quantum dot.The pH use scopes for the water-soluble quantum dot that the present invention obtains are wide, stability is good, is uniformly dispersed, and the coagulation of quantum dot will not be caused under higher salt concentration conditions, widened the application range of quantum dot.The present invention also by the way that sulfydryl glycol monomethyl ether is added in the oil phase quantum dot reaction system of the excessive presoma of residual, recycles aliphatic hydrocarbon to be post-processed, obtains the quantum dot of high-purity.
Description
Technical field
The present invention relates to quantum dot field more particularly to a kind of methods that oil-soluble quantum dot is converted into water-soluble quantum dot
With the method for purification of oil-soluble quantum dot.
Background technology
Quantum dot (QDs) since with quantum size effect, excitation wavelength range is wide, emission peak it is narrow and in Gaussian symmetric,
Without hangover, the advantages that photochemical stability is strong and be widely used in photoelectric device, solar cell and fluorescent marker etc.
Application field.Typically directly low, the half-breadth peak width by the quantum dot light emitting efficiency of synthesis in water, which greatly limits water solubilitys to measure
Application of the son point in fields such as LED, biomedicines.And the quantum dot of high quality is prepared often by organic phase high-temperature cracking method
It obtains, is oil-soluble quantum dot.Therefore, in order to widen the application range of quantum dot, more and more researchers pass through table
The method of face chemistry modifies quantum dot surface, converts oil-soluble quantum dot to water-soluble quantum dot.At present to quantum
The method that point surface is modified mainly has：（1）By coating silane or silica in quantum dot surface；This method modification with
Quantum dot afterwards is stable, water-soluble preferable, but modification is extremely cumbersome, the period is long and is difficult to repeat, and fluorescence property reduces.
（2）Quantum dot is coated or is directly embedded in by the effect of the alkyl chain of amphiphilic macromolecular and quantum dot surface the sky of polymer
In chamber；Such method does not destroy the organic molecule of quantum dot surface, and optical property is substantially unaffected, but introduces a large amount of organic
Solvent purification is difficult, and the stability of the water-soluble quantum dot obtained is difficult to control.（3）Large biological molecule is modified；Although raw
The quantum dot fluorescence stability of object macromolecular modification is good, but the method for the covalent coupling of quantum dot and albumen is also excessively cumbersome, behaviour
It is big to make difficulty.Further, since the size of large biological molecule is bigger, on the one hand free large biological molecule is difficult to remove, quantum
The purifying complex of point；On the other hand, quantum dot becomes large-sized.（4）Utilize the sulphur atom and the metallic atoms such as Cd, Zn in sulfydryl
Between stronger combination, modified using anionic or cationic sulfydryl small molecule or amphiphilic surfactant；Due to
Both methods is simple, reproducible, it can be achieved that industrialized production, becomes the common method of modification quantum dot at present；But it is logical
The pH use scopes for crossing the water-soluble quantum dot after such methods modification are too narrow；And when salinity is excessively high or special electrolyte exists
When be easy to cause quantum dot occur coagulation, so as to cause fluorescent quenching.
Oil phase quantum dot is prepared generally by the method that metallorganic thermally decomposes, during this process, it is common to a certain
Presoma excessively contributes to the homoepitaxial of quantum dot and reduces the defect of lattice mismatch, in addition different presoma reactivities
There is also larger differences.Therefore, after the completion of quantum dot reacts, often there are one or more excessive remnants in reaction system
Precursor reagent.In order to purify quantum dot, generally use addition precipitating reagent is centrifuged washing and removes impurity.Clear
It elutes in pure procedure, the type and dosage that precipitating reagent is added in quantum dot are very sensitive.Precipitating reagent type and dosage are added
The improper unreacted precursor reagent of residue that is easy to cause is precipitated out simultaneously with quantum dot, not up to refining effect；And it sinks
Shallow lake agent addition is very few and can cause quantum dot that can not be precipitated out, and seriously affects yield；It is also easy in addition, cleaning way is improper
Quantum dot fluorescence efficiency is caused to quench.
Therefore, surface modification method easy to operate need to be developed and converts oil-soluble quantum dot to water-soluble quantum dot, made
Prepared water-soluble quantum dot is with good fluorescent stability, good aqueous stability and suitable for various soda acids
Salting liquid, to widen the application range of quantum dot.And a kind of effective method of purification is developed, so that oil phase synthesis quantum dot is had
Keep fluorescence intensity stability also very necessary after high-purity, high yield and cleaning.
Invention content
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of oil-soluble quantum dot be converted into it is water-soluble
Property quantum dot method and oil-soluble quantum dot method of purification, it is intended to or solve existing method preparation water-soluble quantum dot
Fluorescent stability reduces or aqueous stability is relatively low or pH use scopes are too narrow, cause the application range of quantum dot by
To the problem of limitation.
A kind of method that oil-soluble quantum dot is converted into water-soluble quantum dot, wherein including：
Step A, it takes the dissolving of oil-soluble quantum dot in organic solvent, oil-soluble quantum dot solution is made；
Step B, it takes sulfydryl glycol monomethyl ether to be dissolved in water and is stirred by ultrasonic to being completely dissolved, it is molten that sulfydryl glycol monomethyl ether is made
Liquid；
Step C, oil-soluble quantum dot solution is added in sulfydryl glycol monomethyl ether solution, then at certain temperature and atmosphere
It is stirred to react after a certain period of time, organic solvent is volatilized completely, obtains water-soluble quantum dot.
The method that the oil-soluble quantum dot is converted into water-soluble quantum dot, wherein in the step A, the oil is molten
Property quantum dot be II-VI group quantum dot, iii-v quantum dot, group IV-VI quantum dot and core-shell type quantum point and mixed type quantum
It is one or more in point.
The method that the oil-soluble quantum dot is converted into water-soluble quantum dot, wherein described organic in the step A
Solvent is one or more in chloroform, toluene, chlorobenzene, n-hexane, normal octane.
The method that the oil-soluble quantum dot is converted into water-soluble quantum dot, wherein in the step B, the sulfydryl
The molecular formula of glycol monomethyl ether is CH3(OCH2CH2)nSH, wherein n are any integer in 2-20.
The method that the oil-soluble quantum dot is converted into water-soluble quantum dot, wherein in the step B, the oil is molten
Property quantum dot solution and sulfydryl glycol monomethyl ether solution volume ratio be 1:3-3:1.
The method that the oil-soluble quantum dot is converted into water-soluble quantum dot, wherein in the step A, the oil is molten
A concentration of the 10 of property quantum dot solution-4mol/L-10-1mol/L；In the step B, the sulfydryl glycol monomethyl ether solution it is dense
Degree is 10-4mol/L-10-1mol/L。
The method that the oil-soluble quantum dot is converted into water-soluble quantum dot, wherein in the step C, the temperature
It it is 20-100 DEG C, the atmosphere is one kind in air, inert atmosphere, vacuum, and the time of the reaction is 5 min-5 h.
The method that the oil-soluble quantum dot is converted into water-soluble quantum dot, wherein described organic in the step C
The condition that solvent volatilizees completely is one or more in nature volatilization, vacuum drying, heating volatilization.
A kind of method of purification of oil-soluble quantum dot, wherein including step：In the quantum of the excessive unreacted precursor of residual
Sulfydryl glycol monomethyl ether is added in point reaction system, after then being reacted at a certain temperature, toward quantum dot reaction system
Middle addition aliphatic hydrocarbon, is then centrifuged for detaching, the quantum dot after being purified.
The method of purification of the oil-soluble quantum dot, wherein the amount that the sulfydryl glycol monomethyl ether is added is quantum dot
0.001 times to 0.1 times of reaction system total volume.
The method of purification of the oil-soluble quantum dot, wherein the temperature of reaction is 50-200 DEG C, and the time of reaction is 5
Minute was to 5 hours.
The method of purification of the oil-soluble quantum dot, wherein the system atmosphere of reaction be inert atmosphere, air atmosphere,
One kind in vacuum.
Advantageous effect：The present invention is surface modified oil-soluble quantum dot using sulfydryl glycol monomethyl ether, by sulfydryl
The pH use scopes for the water-soluble quantum dot that the modification of glycol monomethyl ether obtains are wide, are suitable for acidity, alkalinity and neutral environment, and institute
The water-soluble quantum dot stability of acquisition is good, is uniformly dispersed, and the poly- of quantum dot will not be caused under higher salt concentration conditions
It is heavy, to widen the application range of quantum dot significantly.In addition, this method is simple, operability is strong, is conducive to productionization.
Specific implementation mode
The present invention provides a kind of oil-soluble quantum dot and is converted into the method for water-soluble quantum dot and proposing for oil-soluble quantum dot
Pure method, to make the purpose of the present invention, technical solution and effect clearer, clear and definite, below further specifically to the present invention
It is bright.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
A kind of oil-soluble quantum dot of the present invention is converted into the method preferred embodiment of water-soluble quantum dot, wherein including：
Step A, it takes the dissolving of oil-soluble quantum dot in organic solvent, oil-soluble quantum dot solution is made；
Above-mentioned steps A of the present invention is specifically, take high-purity oil-soluble quantum dot or the oil-soluble quantum dot dissolving containing precursor solution
In organic solvent, certain density oil-soluble quantum dot solution is made, for use.
Oil-soluble quantum dot of the present invention can be the oil-soluble quantum dot and other any sides that oil phase directly synthesizes
The oil-soluble quantum dot that method obtains.The present invention oil-soluble quantum dot can be II-VI group quantum dot, iii-v quantum dot,
It is one or more in group IV-VI quantum dot and core-shell type quantum point and mixed type quantum dot.For example, II-VI group quantum dot can
Think but be not limited to CdTe, CdSe, ZnSe, CdS, ZnS, ZnO, CdZnS, CdZnSe, CdZnTe, ZnSeTe, ZnTeS,
One in CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe, CdZnSTe, CdSeSTe, ZnSeSTe, CdZnSeSTe etc.
Kind is a variety of；III-V quantum dots one or both of can be but be not limited to InP, GaAs etc.；Iii-v quantum dot can be with
For but it is one or more in being not limited to InP, InAs, InAsP etc.；Group IV-VI quantum dot can be but be not limited to PbS, PbSe,
It is one or more in PbTe, PbSeS, PbSeTe, PbSTe etc.；And all kinds of hud typed and mixed type quantum dot comprising on
The arbitrary combination of arbitrary a kind or a kind or more compound is stated, such as：CdZnSe/ZnS、 CdZnSeS/ZnS、CdTe/ZnS、CdTe/
CdS/ZnS, CdTe/CdSe, CdTe/ZnTe, CdSe/CdS, CdSe/ZnS etc..
The present invention dissolve oil-soluble quantum dot the preferred low boiling point organic solvent of organic solvent, as chloroform, toluene, chlorobenzene,
N-hexane, normal octane etc. but not limited to this.
Preferably, a concentration of the 10 of oil-soluble quantum dot solution of the present invention-4mol/L-10-1mol/L。
Step B, it takes sulfydryl glycol monomethyl ether to be dissolved in water and is stirred by ultrasonic to being completely dissolved, sulfydryl glycol list first is made
Ethereal solution；
Above-mentioned steps B of the present invention uses water specifically, take a certain amount of one or more sulfydryl glycol monomethyl ethers under ultrasound condition
It is allowed to be completely dissolved, is transferred in volumetric flask and is made into certain density sulfydryl glycol monomethyl ether solution, for use.Preferably, described
A concentration of the 10 of sulfydryl glycol monomethyl ether solution-4mol/L-10-1mol/L。
Sulfydryl glycol monomethyl ether of the present invention refers to sulfydryl there are one molecular end contains（-SH）Multiethylene-glycol shrink single first
Ether, molecular formula CH3(OCH2CH2)nSH, specific molecular structure are as follows；Wherein, n is integer, appointing in preferably 2-20
One integer, such as sulfydryl triethylene glycol monomethyl ether, sulfydryl tetraethylene glycol monomethyl ether, five glycol monomethyl ether of sulfydryl, sulfydryl hexaethylene glycol list first
Ether, seven glycol monomethyl ether of sulfydryl, eight glycol monomethyl ether of sulfydryl, nine glycol monomethyl ether of sulfydryl, ten glycol monomethyl ether of sulfydryl, sulfydryl ten
One glycol monomethyl ether, ten diethylene glycol monomethyl ether of sulfydryl etc., but not limited to this.
Preferably, a concentration of the 10 of sulfydryl glycol monomethyl ether solution of the present invention-4mol/L-10-1mol/L。
Step C, oil-soluble quantum dot solution is added in sulfydryl glycol monomethyl ether solution, it is then gentle in certain temperature
It is stirred to react under atmosphere after a certain period of time, organic solvent is volatilized completely, obtains water-soluble quantum dot.
Above-mentioned steps C of the present invention is specifically, take a certain amount of above-mentioned sulfydryl glycol monomethyl ether solution in flask, addition is stirred
Mix son, under the mixing speed of 1500 rpm, by certain volume than oil-soluble quantum dot solution at the uniform velocity instill sulfydryl glycol list
It in methyl ether solution, is stirred continuously, is reacted after a certain period of time at certain temperature and atmosphere, after organic solvent is volatilized completely,
Obtain water-soluble quantum dot.Preferably, the volume ratio of the oil-soluble quantum dot solution and sulfydryl glycol monomethyl ether solution is
1:3-3:1。
Preferably, the temperature is 20-100 DEG C（Such as 30 DEG C, 60 DEG C or 80 DEG C）, the atmosphere be air, inert atmosphere,
The time of one kind in vacuum, the reaction is 5 min-5 h.
Preferably, the condition that the organic solvent volatilizees completely can be in nature volatilization, vacuum drying, heating volatilization etc.
It is one or more.
Sulfydryl glycol monomethyl ether of the present invention have good water soluble nature, by sulfydryl glycol monomethyl ether with oil
The strong coordination of metal ion in dissolubility quantum dot, to obtain the water-soluble quantum dot stablized；The sulfydryl glycol list first
Ether has good ph stability and freeze thaw stability, and after its modification, can effectively obtain pH makes oil-soluble quantum dot
With the wide quantum dot of range, and such quantum dot will not lead to coagulation under higher salt concentration conditions, to keep fluorescence
Stability.
The present invention also provides a kind of method of purification preferred embodiments of oil-soluble quantum dot, wherein including step：It is remaining
Sulfydryl glycol monomethyl ether is added in the quantum dot reaction system of excessive unreacted precursor, then carries out at a certain temperature anti-
Aliphatic hydrocarbon is added into quantum dot reaction system in Ying Hou, is then centrifuged for detaching, the quantum dot after being purified.
Aliphatic hydrocarbon of the present invention refers to the smaller aliphatic hydrocarbon of polarity, can be in aliphatic saturated hydrocarbon and unsaturated aliphatic hydrocarbon
One kind.
The method of purification of the above-mentioned oil-soluble quantum dot of the present invention, is as follows：
（1）It is added in the quantum dot reaction system containing residual or excessive unreacted precursor a certain proportion of one or more
Sulfydryl multiethylene-glycol monomethyl ether is added a certain amount of after reacting the regular hour at a certain temperature into quantum dot reaction system
One or more aliphatic hydrocarbons, centrifuge, remove supernatant, precipitated.Preferably, the dosage of the aliphatic hydrocarbon is quantum
0.1 times to 5 times of point reaction system total volume.
（2）Above-mentioned precipitation is scattered in solvent（Such as ethyl alcohol）In, a certain amount of one or more aliphatic hydrocarbons are added, make quantum
Point precipitation, centrifuges, and removes supernatant；It repeats above operation two and is precipitated to high-purity quantum dot three times, is obtained.Preferably,
The dosage of the aliphatic hydrocarbon is 0.1 times to 5 times of quantum dot reaction system total volume.
The present invention also can directly rinse a certain amount of one or more aliphatic hydrocarbons of above-mentioned precipitation 2-3 times, you can obtain
High-purity quantum dot precipitates.
（3）By step（2）The quantum dot precipitation of gained is scattered in ethanol solution, is dried in vacuo.
（4）Take step（3）Quantum dot after drying is scattered in organic solvent or water, spare.The organic solvent refers to
Highly polar organic solvent, such as methanol, ethyl alcohol, dimethyl sulfoxide (DMSO)（DMSO）, dimethylformamide（DMF）Deng but not limited to this.
Unreacted precursor of the present invention can be cationic one or both of presoma and anion presoma, wherein
Any one during the cation presoma can be but be not limited to aliphatic acid cadmium, fatty acid zinc, lead stearate etc., wherein fat
Acid can be unsaturated fatty acid, any one in saturated fatty acid or two kinds, wherein monounsaturated fatty acids can be oleic acid,
Any one in nutmeg oleic acid, palmitoleic acid, erucic acid, for example, aliphatic acid can be but be not limited to oleic acid, octadecenic acid, ten
Any one in tetraenoic acid etc..Anion presoma of the present invention can be formed by the elements such as organic solvent and sulphur, selenium, tellurium
Compound, wherein organic solvent can be tri octyl phosphine, octadecylene, oleic acid, octadecylamine, trioctylamine, octadecyl phosphine
It is one or more in acid etc..
Quantum dot reaction system of the present invention can be the oil-soluble quantum dot that directly synthesizes of oil phase and other any
The oil-soluble quantum dot that method obtains.The present invention oil-soluble quantum dot can be II-VI group quantum dot, iii-v quantum dot,
It is one or more in group IV-VI quantum dot and core-shell type quantum point and mixed type quantum dot.For example, II-VI group quantum dot can
Think but be not limited to CdTe, CdSe, ZnSe, CdS, ZnS, ZnO, CdZnS, CdZnSe, CdZnTe, ZnSeTe, ZnTeS,
One in CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe, CdZnSTe, CdSeSTe, ZnSeSTe, CdZnSeSTe etc.
Kind is a variety of；III-V quantum dots one or both of can be but be not limited to InP, GaAs etc.；Iii-v quantum dot can be with
For but it is one or more in being not limited to InP, InAs, InAsP etc.；Group IV-VI quantum dot can be but be not limited to PbS, PbSe,
It is one or more in PbTe, PbSeS, PbSeTe, PbSTe etc.；And all kinds of hud typed and mixed type quantum dot comprising on
The arbitrary combination of arbitrary a kind or a kind or more compound is stated, such as：CdZnSe/ZnS、 CdZnSeS/ZnS、CdTe/ZnS、CdTe/
CdS/ZnS, CdTe/CdSe, CdTe/ZnTe, CdSe/CdS, CdSe/ZnS etc..
Sulfydryl glycol monomethyl ether of the present invention refers to sulfydryl there are one molecular end contains（-SH）Multiethylene-glycol shrink single first
Ether, molecular formula CH3(OCH2CH2)nSH, specific molecular structure are as follows；Wherein, n is integer, appointing in preferably 2-20
One integer, such as sulfydryl triethylene glycol monomethyl ether, sulfydryl tetraethylene glycol monomethyl ether, five glycol monomethyl ether of sulfydryl, sulfydryl hexaethylene glycol list first
Ether, seven glycol monomethyl ether of sulfydryl, eight glycol monomethyl ether of sulfydryl, nine glycol monomethyl ether of sulfydryl, ten glycol monomethyl ether of sulfydryl, sulfydryl ten
One glycol monomethyl ether, ten diethylene glycol monomethyl ether of sulfydryl etc., but not limited to this.
The amount that sulfydryl glycol monomethyl ether of the present invention is added is 0.001 times to 0.1 of quantum dot reaction system total volume
Times.Preferably, the amount that the sulfydryl glycol monomethyl ether is added is 0.05 times to 0.1 times of quantum dot reaction system total volume.
The temperature that the present invention reacts is 50-200 DEG C, and the time of reaction is 5 minutes to 5 hours.Preferably, the temperature of reaction
It it is 100-160 DEG C, the time of reaction is 30 minutes to 3 hours.
The system atmosphere that the present invention reacts is inert atmosphere, air atmosphere, vacuum（Pressure<100 Pa）In one kind.
Sulfydryl glycol monomethyl ether of the present invention is added to the oil phase quantum dot containing residual or excessive unreacted precursor
In reaction system or solution, with the quantum dot in system ligand exchange reaction can occur for the sulfydryl glycol monomethyl ether, due to
Sulfydryl glycol monomethyl ether does not dissolve in aliphatic hydrocarbon, is added after aliphatic hydrocarbon with the quantum dot of sulfydryl glycol monomethyl ether coordination and group then easily occurs
Combinate form is at precipitation, and the residual or excessive unreacted precursor in system do not act on then with sulfydryl glycol monomethyl ether, and can be straight
It connects and is dispersed or dissolved in aliphatic hydrocarbon, be centrifuged removal, can both obtain high-purity quantum dot.It is repaiied through sulfydryl glycol monomethyl ether
Aliphatic hydrocarbon, easily coagulation are added in the quantum dot of decorations, is easily isolated, thus is unlikely to the loss of quantum dot yield after cleaning, and
Obtained quantum dot purity is high.In addition sulfydryl glycol monomethyl ether has protective effect, once purged quantum dot still can be with quantum dot
Fluorescence intensity is kept to stablize.
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
The preparation process of water-soluble CdSe/ZnS quantum dot is as follows：
（1）Oil-soluble CdSe/ZnS quantum dots are dissolved in n-hexane, are made a concentration of 10-2The oil-soluble quantum of mol/L
Point solution, for use.
（2）18 mg of sulfydryl triethylene glycol monomethyl ether is weighed, is allowed to be completely dissolved with appropriate distilled water under ultrasound condition, is turned
It moves in 100mL volumetric flasks, is made into a concentration of 10-3The sulfydryl triethylene glycol monomethyl ether solution of mol/L, for use.
（3）It takes the above-mentioned sulfydryl triethylene glycol monomethyl ether solution of 4 mL to be added in three-necked flask, in air atmosphere, magnetic is added
2 mL oil-solubles quantum dot solutions are instilled sulfydryl by power stirrer under the mixing speed of 1500 rpm with the speed of 1mL/min
In triethylene glycol monomethyl ether solution, microemulsion is formed, and be heated to 40 DEG C, be stirred continuously after normal hexane volatilizees completely, obtain
To water-soluble quantum dot；Obtained water-soluble quantum dot can be diluted for use with distilled water.
Embodiment 2
The preparation process of water-soluble CdZnSe/ZnS quantum dots is as follows：
（1）Oil-soluble CdZnSe/ZnS quantum dots are dissolved in chloroform, are made a concentration of 10-2The oil-soluble quantum of mol/L
Point solution, for use.
（2）Eight glycol monomethyl ether of sulfydryl, 40.5 mg is weighed, is allowed to be completely dissolved with appropriate distilled water under ultrasound condition
Afterwards, it is transferred in the volumetric flask of 100mL and is made into a concentration of 10-3The eight glycol monomethyl ether solution of sulfydryl of mol/L, for use.
（3）It takes the above-mentioned eight glycol monomethyl ether solution of sulfydryl of 5 mL in three-necked flask, in air atmosphere, magnetic force is added and stirs
Son is mixed, 2 mL oil-solubles quantum dot solutions are instilled into sulfydryl with the speed of 0.5 mL/min under the mixing speed of 1500 rpm
In eight glycol monomethyl ether solution, microemulsion is formed, and after 2h is stirred at room temperature, solution is positioned under ventilating kitchen, until chloroform is complete
After being evaporated completely entirely, water-soluble quantum dot is obtained；Obtained water-soluble quantum dot can be diluted for use with distilled water.
Embodiment 3
The purification step of the oil phase CdSe/CdS quantum dots of the excessive unreacted precursor of residual is as follows：
（1）The oil phase CdSe/CdS quantum dot reaction systems of end will be reacted in there-necked flask（Total volume is 15 milliliters）Temperature is protected
It holds to 120 DEG C；Entire reaction system is maintained at N2Under atmosphere；
（2）0.005mmol sulfydryl hexaethylene glycol monomethyl ethers are dissolved in the reaction system that step (1) is then added to after 1mL ethanol solutions
In, it maintains the temperature at 120 DEG C and reacts 20 minutes；
（3）Reaction system is cooled to 100 DEG C, 20 mL n-hexanes are added, mixture system is existed by supercentrifuge while hot
Liquid phase is discarded after being centrifuged 3 minutes under 7000 revs/min；After dissolving solid phase with 2 mL ethyl alcohol, 8 mL n-hexanes, centrifugation point are added
From and discard liquid phase, this process is repeated 1-2 times；
（3）Obtained solid phase quantum dot is scattered in ethyl alcohol, the quantum dot of high-purity is obtained after vacuum drying chamber drying
Sample.
（4）Quantum dot after drying can be scattered in it is spare in the larger solution of polarity, such as water, ethyl alcohol, DMSO, DMF etc..
In conclusion the present invention is surface modified oil-soluble quantum dot using sulfydryl glycol monomethyl ether, by sulfydryl
The pH use scopes for the water-soluble quantum dot that the modification of glycol monomethyl ether obtains are wide, are suitable for acidity, alkalinity and neutral environment, and institute
The water-soluble quantum dot stability of acquisition is good, is uniformly dispersed, and the poly- of quantum dot will not be caused under higher salt concentration conditions
It is heavy, to widen the application range of quantum dot.In addition, this method is simple, operability is strong, is conducive to productionization.The present invention
Also repaiied by the way that sulfydryl glycol monomethyl ether is added in the quantum dot reaction system of the excessive unreacted precursor of residual or solution
Decorations recycle aliphatic hydrocarbon simply to be post-processed, and effectively realize efficiently separating for quantum dot and presoma impurity, the amount of improving
The purity of son point product, makes it fully meet requirement of the practical application for quantum dot purity.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect range.
Claims (12)
1. a kind of method that oil-soluble quantum dot is converted into water-soluble quantum dot, which is characterized in that including：
Step A, it takes the dissolving of oil-soluble quantum dot in organic solvent, oil-soluble quantum dot solution is made；
Step B, it takes sulfydryl glycol monomethyl ether to be dissolved in water and is stirred by ultrasonic to being completely dissolved, it is molten that sulfydryl glycol monomethyl ether is made
Liquid；
Step C, oil-soluble quantum dot solution is added in sulfydryl glycol monomethyl ether solution, then at certain temperature and atmosphere
It is stirred to react after a certain period of time, organic solvent is volatilized completely, obtains water-soluble quantum dot.
2. the method that oil-soluble quantum dot according to claim 1 is converted into water-soluble quantum dot, which is characterized in that described
In step A, the oil-soluble quantum dot is II-VI group quantum dot, iii-v quantum dot, group IV-VI quantum dot and hud typed amount
It is one or more in son point and mixed type quantum dot.
3. the method that oil-soluble quantum dot according to claim 1 is converted into water-soluble quantum dot, which is characterized in that described
In step A, the organic solvent is one or more in chloroform, toluene, chlorobenzene, n-hexane, normal octane.
4. the method that oil-soluble quantum dot according to claim 1 is converted into water-soluble quantum dot, which is characterized in that described
In step B, the molecular formula of the sulfydryl glycol monomethyl ether is CH3(OCH2CH2)nSH, wherein n are any integer in 2-20.
5. the method that oil-soluble quantum dot according to claim 1 is converted into water-soluble quantum dot, which is characterized in that described
In step B, the volume ratio of the oil-soluble quantum dot solution and sulfydryl glycol monomethyl ether solution is 1:3-3:1.
6. the method that oil-soluble quantum dot according to claim 1 is converted into water-soluble quantum dot, which is characterized in that described
In step A, a concentration of the 10 of the oil-soluble quantum dot solution-4mol/L-10-1mol/L；In the step B, the sulfydryl is sweet
A concentration of the 10 of alcohol monomethyl ether solution-4mol/L-10-1mol/L。
7. the method that oil-soluble quantum dot according to claim 1 is converted into water-soluble quantum dot, which is characterized in that described
In step C, the temperature is 20-100 DEG C, and the atmosphere is air, inert atmosphere, one kind in vacuum, the reaction when
Between be 5 min-5 h.
8. the method that oil-soluble quantum dot according to claim 1 is converted into water-soluble quantum dot, which is characterized in that described
In step C, the condition that the organic solvent volatilizees completely is one or more in nature volatilization, vacuum drying, heating volatilization.
9. a kind of method of purification of oil-soluble quantum dot, which is characterized in that including step：In the excessive unreacted precursor of residual
Sulfydryl glycol monomethyl ether is added in quantum dot reaction system, after then being reacted at a certain temperature, is reacted toward quantum dot
Aliphatic hydrocarbon is added in system, is then centrifuged for detaching, the quantum dot after being purified.
10. the method for purification of oil-soluble quantum dot according to claim 9, which is characterized in that the sulfydryl glycol list first
The amount that ether is added is 0.001 times to 0.1 times of quantum dot reaction system total volume.
11. the method for purification of oil-soluble quantum dot according to claim 9, which is characterized in that the temperature of reaction is 50-
200 DEG C, the time of reaction is 5 minutes to 5 hours.
12. the method for purification of oil-soluble quantum dot according to claim 9, which is characterized in that the system atmosphere of reaction is
One kind in inert atmosphere, air atmosphere, vacuum.
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