CN105482821A - Quantum dot composite microsphere with bi-component shell layer and preparation method of quantum dot composite microsphere - Google Patents
Quantum dot composite microsphere with bi-component shell layer and preparation method of quantum dot composite microsphere Download PDFInfo
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- CN105482821A CN105482821A CN201510995510.1A CN201510995510A CN105482821A CN 105482821 A CN105482821 A CN 105482821A CN 201510995510 A CN201510995510 A CN 201510995510A CN 105482821 A CN105482821 A CN 105482821A
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 115
- 239000004005 microsphere Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title abstract description 10
- 239000003094 microcapsule Substances 0.000 claims abstract description 54
- 239000012188 paraffin wax Substances 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004793 Polystyrene Substances 0.000 claims abstract description 18
- 229920002223 polystyrene Polymers 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 63
- 238000003756 stirring Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 25
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 21
- -1 mercaptan carboxylic acid Chemical class 0.000 claims description 21
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 20
- 229960001866 silicon dioxide Drugs 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000004160 Ammonium persulphate Substances 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 9
- DDSWIYVVHBOISO-UHFFFAOYSA-N ctk0i1982 Chemical compound N[SiH](N)N DDSWIYVVHBOISO-UHFFFAOYSA-N 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- 239000013543 active substance Substances 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000011162 core material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910004613 CdTe Inorganic materials 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 claims description 3
- AQQPJNOXVZFTGE-UHFFFAOYSA-N 2-octadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O AQQPJNOXVZFTGE-UHFFFAOYSA-N 0.000 claims description 2
- 229910004262 HgTe Inorganic materials 0.000 claims description 2
- 229910000673 Indium arsenide Inorganic materials 0.000 claims description 2
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229950008882 polysorbate Drugs 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 6
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000002245 particle Substances 0.000 description 13
- 238000004945 emulsification Methods 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 description 10
- 239000012279 sodium borohydride Substances 0.000 description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 241001411320 Eriogonum inflatum Species 0.000 description 8
- 239000000284 extract Substances 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000004530 micro-emulsion Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000012782 phase change material Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000237502 Ostreidae Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000090 biomarker Substances 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000799 fluorescence microscopy Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 235000020636 oyster Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011540 sensing material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a quantum dot composite microsphere with a bi-component shell layer and a preparation method of the quantum dot composite microsphere. The quantum dot composite microsphere comprises quantum dots and a microcapsule, wherein the quantum dots are self-assembled to the surface of the microcapsule; the microcapsule comprises a shell layer and a kernel; the shell layer contains polystyrene and silicon dioxide; the kernel is paraffin. According to the quantum dot composite microsphere, the quantum dots can preserve excellent properties including high light emitting efficiency, photochemistry stability and the like of normal quantum dots, and furthermore, the light emitting intensity further has a specific temperature sensitivity value, so that the quantum dot composite microsphere can be applied to the correlation of the specific temperature; the quantum dots further have excellent reusability and do not fall.
Description
Technical field
The present invention relates to a kind of quantum dot, more particularly, relate to a kind of quantum dot complex microsphere with two-pack shell and preparation method thereof.
Background technology
When scantling reduces to nanometer scale, due to its nano effect, material, by producing the various functional performances being better than traditional material of many novelties and uniqueness, is with a wide range of applications in fields such as microelectronics, biotechnology, chemical industry, medical science.
In recent years, take transition metal as the nano luminescent material of active ions, due to the optical characteristics of its excellence, as wide in absorbing wavelength and continuously, fluorescence emission peak is tunable, fluorescence lifetime is long, shows wide application prospect in fields such as luminescent device, fluorescence imaging, solar cell, fluoroscopic examination and biomarkers.But when quantum dot is used for luminescent device or fluoroscopic examination, within the scope of 25-100 DEG C, the red shift that quantum dot absorption peak wavelength and photoluminescence spectra wavelength occur generally all is less than 10nm.Moreover although luminous intensity and temperature have certain linear relationship, vary with temperature, its luminous intensity is very little, lower than at thermal quenching temperature, less temperature variation can not cause luminous intensity significantly strengthen or weaken.Therefore, prior art can not prepare the very high quantum dot of temperature sensitivity.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides the quantum dot complex microsphere with two-pack shell that a kind of temperature sensitivity is very high.
The invention provides a kind of quantum dot complex microsphere with two-pack shell, it comprises quantum dot and microcapsule, and described quantum dot self-assembly is on the surface of described microcapsule, and described microcapsule comprise shell and kernel, described shell contains polystyrene and silicon-dioxide, and described kernel is paraffin.
Described quantum dot is the quantum dot that mercaptan carboxylic acid modifies; The surface of described microcapsule is through triamino silane and polymerize aluminum chloride modification, and the chemical formula of described triamino silane is H
2n-CH
2-CH
2-NH-CH
2-CH
2-NH-(CH
2)
3-Si-(OCH
3)
3.
In described quantum dot complex microsphere, the part by weight of described paraffin, polystyrene and silicon-dioxide is (2 ~ 6): (2 ~ 10): 0.29.The described quantum dot of 1-20 layer is had at the surface self-organization of described microcapsule.
The median size of described quantum dot complex microsphere is 55nm ~ 600nm, is preferably 65nm ~ 500nm.The particle diameter of described microcapsule is 50nm ~ 600nm, is preferably 60nm ~ 500nm.The particle diameter of described quantum dot is 2 ~ 150nm, is preferably 5 ~ 100nm;
Described quantum dot is one or more in CdTe, CdSe, InP, InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot.
Paraffin is preferably 18
#paraffin, 20
#paraffin, 25
#paraffin, 30
#paraffin, 35
#paraffin, 45
#paraffin, 58
#one or more in paraffin.
Of the present inventionly provide the above-mentioned preparation method with the quantum dot complex microsphere of two-pack shell, it is characterized in that, the method comprises the steps:
(1) will be (2 ~ 6) by weight proportion: (2 ~ 10): 1 blended wax, vinylbenzene and tetraethoxy, then heating makes paraffin melting and stirs, obtained mixture, then water phase surfactant mixture is joined and add in described mixture, dispersed with stirring evenly obtains emulsion, then in described emulsion, drip the aqueous solution of ammonium persulphate, react 0.5 ~ 6h at 60 ~ 95 DEG C after, after being down to room temperature, then breakdown of emulsion is carried out, leave standstill, vacuum filters, washing and drying, finally obtain taking paraffin as core, polystyrene and silicon-dioxide are the microcapsule of shell,
(2) be immersed in the aqueous solution of quantum dot by described microcapsule, then filter, washing and drying, can obtain quantum dot complex microsphere.
The ratio of the quality sum of the quality of the tensio-active agent in described water phase surfactant mixture and paraffin, vinylbenzene and tetraethoxy is 1:(10 ~ 30), the concentration of the aqueous solution of described tensio-active agent is 0.5wt% ~ 5wt%; The ratio of the quality sum of the quality of the ammonium persulphate in described ammonium persulfate solution and paraffin, vinylbenzene and tetraethoxy is 1:(10 ~ 50), the concentration of described ammonium persulfate solution is 1wt% ~ 10wt%; Described tensio-active agent is one or more in polyoxyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, sodium lauryl sulphate, Trombovar, Sodium palmityl sulfate, Sodium dodecylbenzene sulfonate.
In (2) step, the aqueous solution of described quantum dot is the aqueous solution of the quantum dot that mercaptan carboxylic acid modifies.The time of described immersion is 5min ~ 240min.
Before the aqueous solution described microcapsule being joined quantum dot, with polymeric aluminum chlorides solution and triamino solution of silane modification microcapsule, concrete steps are as follows: entered by described microcapsule in the solution of polymerize aluminum chloride, then filter and drying, and then join in triamino solution of silane, stir, filter and drying.Concentration 0.20wt% ~ the 0.01wt% of described polymeric aluminum chlorides solution, described triamino solution of silane is the ethanolic soln containing 0.5wt% ~ 2.0wt% triamino silane.The consumption submergence microcapsule of polymeric aluminum chlorides solution and triamino solution of silane, but be not restricted to this.Microcapsule and triamino solution of silane mass ratio can be 1:(5 ~ 20).Microcapsule and polymeric aluminum chlorides solution mass ratio can be 1:(5 ~ 20).
The aqueous solution of described quantum dot is the water-soluble quantum dot that mercaptan carboxylic acid modifies, and is the water-soluble quantum dot of mercaptan carboxylic acid's modification that routine uses, the solution of conventional working concentration.Its preparation method is as follows: tellurium powder and sodium borohydride are mixed with water, inert ambient environment and constant temperature is reacted, obtained quantum dot precursor liquid; Cadmium chloride fine powder is dissolved in water, then mercaptan carboxylic acid and sodium hydroxide solution is added successively, obtain mixed solution, whole mixed solution is moved to autoclave inside liner, letting nitrogen in and deoxidizing, then described quantum dot precursor liquid is joined in described mixed solution, carry out hydro-thermal reaction at autoclave, obtain the water-soluble quantum dot that described mercaptan carboxylic acid modifies.The molar ratio of described tellurium powder, sodium borohydride, Cadmium chloride fine powder and mercaptan carboxylic acid is 1:(20 ~ 60): (15 ~ 45): (6 ~ 15).Mercaptan carboxylic acid is preferably Thiovanic acid, 2 mercaptopropionic acid and 3-thiohydracrylic acid.
Compared with prior art, tool of the present invention has the following advantages:
(1) quantum dot complex microsphere of the present invention, quantum dot of the present invention not only can keep the excellent properties such as general quantum dot luminous efficiency is high, photochemical stability, and luminous intensity also has specific temperature sensitive value, can be used for associating specific temperature.Be embodied in: when envrionment temperature raises the transformation temperature of paraffin, paraffin in quantum dot complex microsphere undergoes phase transition, solid-stately transparent liquid state is become by lighttight, the light transmission of such microcapsule significantly increases, and the intensity (luminous intensity) of its photoluminescence spectra can occur significantly to increase; When the transformation temperature of envrionment temperature lower than paraffin, become lighttight solid-state by transparent liquid state, the light transmission of such microcapsule significantly reduces, and the intensity (luminous intensity) of its photoluminescence spectra can decline to a great extent.Therefore, quantum dot is compounded near phase transformation temperature points and has very strong temperature sensitivity.
When quantum dot complex microsphere of the present invention is applied to fluoroscopic examination, by the place of fluorescence generation ANOMALOUS VARIATIONS in on-line real time monitoring integral system, the temperature subtle change near temperature sensitive value can be monitored out.When device for quantum dot, by regulating temperature value, the significantly change of quantum dot light emitting intensity can be regulated and controled.
Quantum dot complex microsphere of the present invention is applicable to the close sample monitoring with the phase transformation temperature points of paraffin, because paraffin has very many temperature trade mark, can by selecting the paraffin of the differing temps trade mark, change the temperature sensitive value of paraffin in quantum dot complex microsphere, thus the Real-Time Monitoring of different sample can be realized.
(2) quantum dot complex microsphere of the present invention, polystyrene and silicon-dioxide form thicker coated shell, and polystyrene has stronger shock strength, be conducive to the thermostability and the structural stability that improve these microcapsule, and the elasticity of silicon-dioxide and the poor shortcoming of compactness can be made up well, be conducive to forming fine and close shell and avoiding phase change material to leak, improve stability.
Silicon-dioxide has the characteristic such as high structural strength, thermally-stabilised, mechanically stable, chemically stable, high heat conduction, can be good at making up thermally-stabilised poor, the mechanical characteristics relatively poor and heat conductivility relatively poor shortcoming relative to chemical stability of polystyrene.
Polystyrene and silicon dioxide composite material combine the advantage of polystyrene and silicon-dioxide, and mutually can make up the shortcoming existed separately, have complementary advantages, thus the thermostability of these microcapsule, chemical stability, mechanical stability and structural stability can be improved, thus make the stability of microcapsule higher.
(3) the present invention is in the preparation process of quantum dot complex microsphere, ammonium persulphate causes the poly-polystyrene of polystyrene polymerization generation as the initiator of polyreaction, generate silicon-dioxide as ester-type hydrolysis catalyst teos hydrolysis simultaneously, make the interface polymerization reaction of polystyrene and the interface hydrolysis reaction of tetraethoxy carry out so simultaneously, interface polymerization reaction and hydrolysis reaction synergy each other, well control the W-response speed of reaction system, the microcapsule of preparation are made to have good structural uniformity and stability, thus can even particle size distribution be realized, the preparation of constitutionally stable microcapsule.
The microcapsule of preparation are again through polymerize aluminum chloride and the process of triamino solution of silane, thus modified microcapsule surface electric charge, and be combined at the polyamino of triamino silane the multidigit point grafting forming three-dimensional with mercaptan carboxylic acid, like this under the dual function of surface charge and the grafting of multidigit point, quantum dot is assembled in the surface of microcapsule very securely, can effectively prevent coming off of quantum dot surface sulfydryl class part, quantum dot originally has extraordinary time stability, and in certain acid, alkali, acid in well-oxygenated environment, alkaline stability and antioxidative stabilizer, the good biological meanwhile also maintaining quantum dot is compatible, thus substantially increase quantum dot stability in a particular application.
(4) quantum dot complex microsphere of the present invention, may be used at quantum dot in luminescent device, fluorescence imaging, solar cell, fluoroscopic examination and biomarker etc.
Embodiment
Further illustrate below by embodiment the preparation process that the present invention has the quantum dot complex microsphere of two-pack shell, but invention should not be deemed limited in following embodiment, wherein wt% is massfraction.
The preparation method of the quantum dot solution that mercaptan carboxylic acid modifies adopts the preparation method of this area routine use.The present invention will (cat ions be as being Zn containing the cationic metal-salt of quantum dot
2+, Cd
2+or Hg
2+) generate positively charged ion precursor with mercaptan carboxylic acid's complexing, then (negatively charged ion can be such as S with negatively charged ion precursor
2-, Se
2-or Te
2-) reflux makes quantum dot nucleation and grows, thus the quantum dot solution that obtained mercaptan carboxylic acid modifies.The temperature of reflux is 60 ~ 90 DEG C, and the time is 3 ~ 12h.Such as, the cadmium telluride that mercaptan carboxylic acid modifies, the preparation method of CdSe quantum dots solution can with reference to CN102786037A, and the preparation method of the ZnS quantum dots solution that mercaptan carboxylic acid modifies can with reference to CN103242829A.Cadmium Sulfide, zinc selenide or the self-chambering of zinc telluridse solution that quantum dot can also be modified by mercaptan carboxylic acid form.The preparation method of the cadmium telluride of each embodiment detailed description mercaptan carboxylic acid modification that the present invention is following.
Embodiment 1
(1) in mass ratio for 6:9:1 combined phase-change temperature be 25 DEG C 25
#paraffin, vinylbenzene and tetraethoxy, obtain mixture;
Said mixture is added in 500mL round-bottomed flask, sheet stainless steel is adopted to stir, heating in water bath to 60 DEG C under the stirring velocity of 1500 turns/min, the Sodium dodecylbenzene sulfonate of 1g is joined in 100mL water, be uniformly dispersed, and to add in round-bottomed flask after emulsification 20min, and then be warming up to 80 DEG C, emulsification 10min is continued under the stirring velocity of 1500 turns/min, obtain uniform microemulsion, wherein, the ratio of the quality of Sodium dodecylbenzene sulfonate and the quality sum of paraffin, vinylbenzene and tetraethoxy is 1:13;
After emulsification completes, the temperature of water-bath is adjusted to 85 DEG C.The ammonium persulphate of 1g is dissolved in the deionized water of 7.5mL, and drops in round-bottomed flask slowly completely.After stirring 30min with the stirring velocity of 1500 turns/min, churned mechanically speed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to 80 DEG C, after reaction 1.5h, hydrolysis reaction and polyreaction are carried out completely.After reaction solution is down to room temperature, in the reaction solution of room temperature, add saturated NaCl aqueous solution 10mL carry out breakdown of emulsion, after leaving standstill 30min, there is demixing phenomenon, the mode distilled water wash that the emulsion of layering is filtered by vacuum 6 times, and with vacuum drying oven vacuum-drying 6h under the condition of 45 DEG C, finally obtain taking phase change material as core, polystyrene and silicon-dioxide are the microcapsule of shell, and wherein, the ratio of the quality sum of the quality of ammonium persulphate and paraffin, vinylbenzene and tetraethoxy is 1:16.
Characterized known by electron scanning micrograph: Microcapsules Size is 160nm ~ 200nm, even particle size distribution, and the shape matching of microcapsule is regular, smooth surface.
(2) take 2mg tellurium powder and 24mg sodium borohydride, in the middle of the bottle moving to band bottle stopper, logical nitrogen 5min, builds bottle stopper.Syringe extracts high purity water 2mL, is expelled in bottle, and then discharges the gas that in bottle, reaction produces.Put in water-bath by whole small bottle packing, temperature of reaction is 32 DEG C, takes out after 2h, is prepared into the precursor liquid that purple is fresh.
100mg Cadmium chloride fine powder adds in 100mL water, and glass stick is stirred to Cadmium chloride fine powder particle and dissolves completely, and add Thiovanic acid (TGA) and more whole liquid is moved to autoclave inside liner, letting nitrogen in and deoxidizing 30min, obtains mixed solution.
Good seal is except the cadmium chloride solution of peroxide, syringe extracts the fresh precursor liquid for preparing of 1mL and is quickly moved to (molar ratio of tellurium powder, sodium borohydride, Cadmium chloride fine powder and Thiovanic acid is 1:41:33:9) in cadmium chloride solution, add sodium hydroxide solution and PH is adjusted to 10, build lid, assemble autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum dot aqueous solution that Thiovanic acid is modified.
(3) 5g microcapsule are joined in 50mL polymeric aluminum chlorides solution, the concentration 0.05wt% of polymeric aluminum chlorides solution, after stirring 10min, carry out filtering and drying, and then microcapsule are joined 50mL triamino solution of silane, the solvent dehydrated alcohol of this solution, the concentration of triamino solution of silane is 0.5wt%, and the chemical formula of triamino silane is H
2n-CH
2-CH
2-NH-CH
2-CH
2-NH-(CH
2)
3-Si-(OCH
3)
3, stir 30min at 20 DEG C, and then filter, to wash and drying obtains the microcapsule of modification.
(4) microcapsule of the modification of step (3) gained are soaked in the quantum dot aqueous solution that above-mentioned Thiovanic acid modifies, under room temperature, react 15min, filter, wash with water, dry, obtain quantum dot complex microsphere.
(5) the quantum dot complex microsphere of step (4) gained is joined in 20mL phosphate buffered mixing solutions (pH value is 6.8), mixed solution system under adopting spectrophotofluorometer to detect differing temps, the excitation wavelength 400nm of quantum dot, under spectrophotofluorometer incidence and exit slit spectral band-width are the condition of 5nm, the fluorescence spectrum of mensuration system, obtains relative intensity of fluorescence.
Table 1
| 10℃ | 20℃ | 23℃ | 26℃ | 30℃ | 40℃ | |
| Relative intensity of fluorescence (a.u.) | 164 | 173 | 187 | 806 | 824 | 827 |
Embodiment 2
(1) in mass ratio for 10:15:4 combined phase-change temperature be 35 DEG C 35
#paraffin, vinylbenzene and tetraethoxy, obtain mixture;
Said mixture is added in 500mL round-bottomed flask, sheet stainless steel is adopted to stir, heating in water bath to 60 DEG C under the stirring velocity of 1500 turns/min, the Sodium dodecylbenzene sulfonate of 1g is joined in the deionized water of 100mL and be uniformly dispersed, and to add in round-bottomed flask after emulsification 10min, and then be warming up to 80 DEG C, emulsification 20min is continued under the stirring velocity of 1500 turns/min, obtain uniform oyster white microemulsion, wherein, the ratio of the quality of Trombovar and the quality sum of paraffin, vinylbenzene and tetraethoxy is 1:25;
After emulsification completes, the temperature of water-bath is adjusted to 85 DEG C.The ammonium persulphate of 1g is dissolved in the deionized water of 7.5mL, and drops in round-bottomed flask slowly completely.After stirring 15min with the stirring velocity of 1500 turns/min, churned mechanically speed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to 85 DEG C, after reaction 1h, hydrolysis reaction and polyreaction are carried out completely.After reaction solution is down to room temperature, in the reaction solution of room temperature, add saturated NaCl aqueous solution 10mL carry out breakdown of emulsion, after leaving standstill 30min, there is demixing phenomenon, the mode distilled water wash that the emulsion of layering is filtered by vacuum 5 times, and with vacuum drying oven vacuum-drying 4h under the condition of 50 DEG C, finally obtain taking phase change material as core, polystyrene and silicon-dioxide are the microcapsule of shell, and wherein, the ratio of the quality sum of the quality of ammonium persulphate and paraffin, vinylbenzene and tetraethoxy is 1:25.
Characterized known by electron scanning micrograph: Microcapsules Size is 100nm ~ 140nm, even particle size distribution, and the shape matching of microcapsule is regular, smooth surface.
(2) take 2mg selenium powder and 24mg sodium borohydride, in the middle of the bottle moving to band bottle stopper, logical nitrogen 5min, builds bottle stopper.Syringe extracts high purity water 2mL, is expelled in bottle, and then discharges the gas that in bottle, reaction produces.Put in water-bath by whole small bottle packing, temperature of reaction is 32 DEG C, takes out after 2h, is prepared into the precursor liquid that purple is fresh.
100mg Cadmium chloride fine powder adds in 100mL water, and glass stick is stirred to Cadmium chloride fine powder particle and dissolves completely, and add Thiovanic acid (TGA) and more whole liquid is moved to autoclave inside liner, letting nitrogen in and deoxidizing 30min, obtains mixed solution.
Good seal is except the cadmium chloride solution of peroxide, syringe extracts the fresh precursor liquid for preparing of 1mL and is quickly moved to (molar ratio of selenium powder, sodium borohydride, Cadmium chloride fine powder and Thiovanic acid is 1:41:33:9) in cadmium chloride solution, add sodium hydroxide solution and PH is adjusted to 10, build lid, assemble autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum dot aqueous solution that Thiovanic acid is modified.
(3) 5g microcapsule are soaked in the quantum dot aqueous solution that above-mentioned Thiovanic acid modifies, under room temperature, react 15min, filter, wash with water, dry, obtain quantum dot complex microsphere.
(4) the quantum dot complex microsphere of step (3) gained is joined in 20mL phosphate buffered mixing solutions (pH value is 6.8), mixed solution system under adopting spectrophotofluorometer to detect differing temps, the excitation wavelength of quantum dot is 540nm.Under spectrophotofluorometer incidence and exit slit spectral band-width are the condition of 5nm, measure the fluorescence spectrum of system, obtain maximum relative intensity of fluorescence.
Table 2
| 20℃ | 30℃ | 33℃ | 36℃ | 40℃ | 50℃ | |
| Relative intensity of fluorescence (a.u.) | 167 | 163 | 161 | 740 | 748 | 742 |
Embodiment 3
(1) in mass ratio for 8:12:2 combined phase-change temperature be 58 DEG C 58
#paraffin, vinylbenzene and tetraethoxy obtain mixture;
Said mixture is added in 500mL round-bottomed flask, sheet stainless steel is adopted to stir, heating in water bath to 65 DEG C under the stirring velocity of 1500 turns/min, the sodium lauryl sulphate of 1g is joined in the deionized water of 42.5mL and be uniformly dispersed, and to add in round-bottomed flask after emulsification 15min, and then be warming up to 80 DEG C, emulsification 15min is continued under the stirring velocity of 1500 turns/min, obtain uniform oyster white microemulsion, wherein, the ratio of the quality of Sodium dodecylbenzene sulfonate and the quality sum of paraffin, vinylbenzene and tetraethoxy is 1:20;
After emulsification completes, the temperature of water-bath is adjusted to 85 DEG C.The initiator of 1g and catalyzer ammonium persulphate are dissolved in the deionized water of 7.5mL, and drop in round-bottomed flask slowly completely.After stirring 25min with the stirring velocity of 1500 turns/min, churned mechanically speed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to 82 DEG C, after reaction 5h, hydrolysis reaction and polyreaction are carried out completely.After reaction solution is down to room temperature, in the reaction solution of room temperature, add saturated NaCl aqueous solution 10mL carry out breakdown of emulsion, after leaving standstill 30min, there is demixing phenomenon, the mode distilled water wash that the emulsion of layering is filtered by vacuum 4 times, and with vacuum drying oven vacuum-drying 5h under the condition of 48 DEG C, finally obtain taking phase change material as core, polystyrene and silicon-dioxide are the microcapsule of shell, and wherein, the ratio of the quality sum of the quality of ammonium persulphate and paraffin, vinylbenzene and tetraethoxy is 1:20.
Characterized known by electron scanning micrograph: Microcapsules Size is 80nm ~ 110nm, even particle size distribution, and the shape matching of microcapsule is regular, smooth surface.
(2) take 2mg selenium powder and 24mg sodium borohydride, in the middle of the bottle moving to band bottle stopper, logical nitrogen 5min, builds bottle stopper.Syringe extracts high purity water 2mL, is expelled in bottle, and then discharges the gas that in bottle, reaction produces.Put in water-bath by whole small bottle packing, temperature of reaction is 32 DEG C, takes out after 2h, is prepared into the precursor liquid that purple is fresh.
100mg zinc nitrate adds in 100mL water, and glass stick is stirred to zinc nitrate particle and dissolves completely, and add Thiovanic acid (TGA) and more whole liquid is moved to autoclave inside liner, letting nitrogen in and deoxidizing 30min, obtains mixed solution.
Good seal is except the zinc nitrate solution of peroxide, syringe extracts the fresh precursor liquid for preparing of 1mL and is quickly moved to (molar ratio of selenium powder, sodium borohydride, zinc nitrate and Thiovanic acid is 1:41:33:9) in zinc nitrate solution, add sodium hydroxide solution and PH is adjusted to 10, build lid, assemble autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum dot aqueous solution that Thiovanic acid is modified.
(3) 5g microcapsule are joined in 50mL polymeric aluminum chlorides solution, the concentration 0.08wt% of polymeric aluminum chlorides solution, after stirring 10min, carry out filtering and drying, and then microcapsule are joined 50mL triamino solution of silane, the solvent dehydrated alcohol of this solution, the concentration of triamino solution of silane is 1wt%, and the chemistry of triamino silane is H
2n-CH
2-CH
2-NH-CH
2-CH2-NH-(CH
2)
3-Si-(OCH
3)
3), stir 30min at 20 DEG C, filtration, washing and drying obtain the microcapsule of modification.
(4) microcapsule of the modification of step (3) gained are added in the quantum dot aqueous solution that above-mentioned Thiovanic acid modifies, dispersed with stirring, under room temperature, react 15min, filter, wash with water, dry, obtain quantum dot complex microsphere.
(5) the quantum dot complex microsphere of step (4) gained is joined in 20mL phosphate buffered mixing solutions (pH value is 6.8), mixed solution system under adopting spectrophotofluorometer to detect differing temps, the excitation wavelength of quantum dot is 470nm.Under spectrophotofluorometer incidence and exit slit spectral band-width are the condition of 5nm, measure the fluorescence spectrum of system, obtain maximum relative intensity of fluorescence.
Table 3
| 40℃ | 50℃ | 56℃ | 59℃ | 65℃ | 70℃ | |
| Relative intensity of fluorescence (a.u.) | 163 | 159 | 157 | 724 | 726 | 723 |
Comparative example 1
(1) tetraethoxy is added in 500mL round-bottomed flask, sheet stainless steel is adopted to stir, heating in water bath to 60 DEG C under the stirring velocity of 1500 turns/min, the Sodium dodecylbenzene sulfonate of 1g is joined in 100mL water, be uniformly dispersed, and to add in round-bottomed flask after emulsification 20min, and then be warming up to 80 DEG C, emulsification 10min is continued under the stirring velocity of 1500 turns/min, obtain uniform microemulsion, wherein, the quality of Sodium dodecylbenzene sulfonate and the ratio of tetraethoxy are 1:13;
After emulsification completes, the temperature of water-bath is adjusted to 85 DEG C.The ammonium persulphate of 1g is dissolved in the deionized water of 7.5mL, and drops in round-bottomed flask slowly completely.After stirring 30min with the stirring velocity of 1500 turns/min, churned mechanically speed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to 80 DEG C, after reaction 1.5h, hydrolysis reaction and polyreaction are carried out completely.After reaction solution is down to room temperature, in the reaction solution of room temperature, add saturated NaCl aqueous solution 10mL carry out breakdown of emulsion, after leaving standstill 30min, there is demixing phenomenon, the mode distilled water wash that the emulsion of layering is filtered by vacuum 6 times, and with vacuum drying oven vacuum-drying 6h under the condition of 45 DEG C, obtain silicon dioxide particles, wherein, the quality of ammonium persulphate and the ratio of silicon-dioxide are 1:16.Characterized known by electron scanning micrograph: particle diameter is 110nm ~ 150nm.
(2) take 2mg tellurium powder and 24mg sodium borohydride, in the middle of the bottle moving to band bottle stopper, logical nitrogen 5min, builds bottle stopper.Syringe extracts high purity water 2mL, is expelled in bottle, and then discharges the gas that in bottle, reaction produces.Put in water-bath by whole small bottle packing, temperature of reaction is 32 DEG C, takes out after 2h, is prepared into the precursor liquid that purple is fresh.
100mg Cadmium chloride fine powder adds in 100mL water, and glass stick is stirred to Cadmium chloride fine powder particle and dissolves completely, and add Thiovanic acid (TGA) and more whole liquid is moved to autoclave inside liner, letting nitrogen in and deoxidizing 30min, obtains mixed solution.
Good seal is except the cadmium chloride solution of peroxide, syringe extracts the fresh precursor liquid for preparing of 1mL and is quickly moved to (molar ratio of tellurium powder, sodium borohydride, Cadmium chloride fine powder and Thiovanic acid is 1:41:33:9) in cadmium chloride solution, add sodium hydroxide solution and PH is adjusted to 10, build lid, assemble autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum dot aqueous solution that Thiovanic acid is modified.
(3) 5g silicon dioxide particles is added in the quantum dot aqueous solution that Thiovanic acid modifies, dispersed with stirring, under room temperature, reacts 15min, filter, washes with water, dry, obtain quantum dot complex microsphere.
(4) the quantum dot complex microsphere of step (3) gained is joined in 20mL phosphate buffered mixing solutions (pH value is 6.8), mixed solution system under adopting spectrophotofluorometer to detect differing temps, the excitation wavelength 400nm of quantum dot, under spectrophotofluorometer incidence and exit slit spectral band-width are the condition of 5nm, the fluorescence spectrum of mensuration system, obtains relative intensity of fluorescence.
Table 4
| 10℃ | 20℃ | 23℃ | 26℃ | 30℃ | 40℃ | |
| Relative intensity of fluorescence (a.u.) | 891 | 888 | 887 | 883 | 882 | 878 |
Known by showing the data of 1-4: the envrionment temperature of the quantum dot complex microsphere of each embodiment is once a little more than the transformation temperature of paraffin, paraffin in quantum dot complex microsphere undergoes phase transition, solid-stately transparent liquid state is become by lighttight, the light transmission of such quantum dot complex microsphere significantly increases, the intensity (luminous intensity) of its photoluminescence spectra can occur significantly to increase, and such quantum dot is compounded in phase transformation temperature points annex and has very strong temperature sensitivity.And the envrionment temperature of the quantum dot complex microsphere of comparative example 1 is at elevation process, fluorescence intensity change is very little, and under the impact of fluorescent noise, be unfavorable for that instrument is monitored, temperature sensitivity is poor.
Test case 1
The quantum dot complex microsphere of Example 1-3 and comparative example 1, then adopts the spin-coating film technology film forming on conductive glass respectively that this area is conventional, thus obtained different fluorescence membrane sensing materials.The test of reusing of fluorescence membrane sensing material contains 0.5 μ g/L copper ion solution.Result shows: after the fluorescence membrane sensing composite material of embodiment 1-3 uses 10 times, fluorescence can return to original more than 95%, does not occur that quantum dot comes off problem; And the fluorescence membrane sensing composite material of comparative example 1, after use 5 times, fluorescence drops to original 90%, after using 8 times, fluorescence drops to less than 80%, and occurs quantum dot obscission, after use 10 times, there is severe detachment problem, can not continue again to use.
Claims (10)
1. have a quantum dot complex microsphere for two-pack shell, it is characterized in that, it comprises quantum dot and microcapsule, described quantum dot self-assembly is on the surface of described microcapsule, described microcapsule comprise shell and kernel, and described shell contains polystyrene and silicon-dioxide, and described kernel is paraffin.
2. according to quantum dot complex microsphere according to claim 1, it is characterized in that: described quantum dot is the quantum dot that mercaptan carboxylic acid modifies; The surface of described microcapsule is through triamino silane and polymerize aluminum chloride modification, and the chemical formula of described triamino silane is H
2n-CH
2-CH
2-NH-CH
2-CH
2-NH-(CH
2)
3-Si-(OCH
3)
3.
3. according to the quantum dot complex microsphere described in claim 1 or 2, it is characterized in that: in described quantum dot complex microsphere, the part by weight of described paraffin, polystyrene and silicon-dioxide is (2 ~ 6): (2 ~ 10): 0.29.
4. according to the quantum dot complex microsphere described in claim 1 or 2, it is characterized in that: the median size of described quantum dot complex microsphere is 55nm ~ 600nm, be preferably 65nm ~ 500nm.
5. according to the quantum dot complex microsphere described in claim 1 or 2, it is characterized in that: described quantum dot is one or more in CdTe, CdSe, InP, InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot.
6., as the preparation method with the quantum dot complex microsphere of two-pack shell in claim 1-5 as described in any one, it is characterized in that, the method comprises the steps:
(1) will be (2 ~ 6) by weight proportion: (2 ~ 10): 1 blended wax, vinylbenzene and tetraethoxy, then heating makes paraffin melting and stirs, obtained mixture, then water phase surfactant mixture is joined and add in described mixture, dispersed with stirring evenly obtains emulsion, then in described emulsion, drip the aqueous solution of ammonium persulphate, react 0.5 ~ 6h at 60 ~ 95 DEG C after, after being down to room temperature, then breakdown of emulsion is carried out, leave standstill, vacuum filters, washing and drying, finally obtain taking paraffin as core, polystyrene and silicon-dioxide are the microcapsule of shell,
(2) be immersed in the aqueous solution of quantum dot by described microcapsule, then filter, washing and drying, can obtain quantum dot complex microsphere.
7. in accordance with the method for claim 6, it is characterized in that: the ratio of the quality sum of the quality of the tensio-active agent in described water phase surfactant mixture and paraffin, vinylbenzene and tetraethoxy is 1:(10 ~ 30), the concentration of the aqueous solution of described tensio-active agent is 0.5wt% ~ 5wt%; The ratio of the quality sum of the quality of the ammonium persulphate in described ammonium persulfate solution and paraffin, vinylbenzene and tetraethoxy is 1:(10 ~ 50), the concentration of described ammonium persulfate solution is 1wt% ~ 10wt%; Described tensio-active agent is one or more in polyoxyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, sodium lauryl sulphate, Trombovar, Sodium palmityl sulfate, Sodium dodecylbenzene sulfonate.
8. according to the method described in claim 6 or 7, it is characterized in that: the aqueous solution of described quantum dot is the aqueous solution of the quantum dot that mercaptan carboxylic acid modifies.
9. according to the method described in claim 6 or 7, it is characterized in that: before the aqueous solution described microcapsule being joined quantum dot, with polymeric aluminum chlorides solution and triamino solution of silane modification microcapsule, concrete steps are as follows: entered by described microcapsule in the solution of polymerize aluminum chloride, then filter and drying, and then join in triamino solution of silane, stir, filter and drying.
10. in accordance with the method for claim 9, it is characterized in that: the concentration 0.20wt% ~ 0.01wt% of described polymeric aluminum chlorides solution, described triamino solution of silane is the ethanolic soln containing 0.5wt% ~ 2.0wt% triamino silane.
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