CN100462416C - Nanometer luminescent core-shell zinc oxide-polymer particle and its prepn - Google Patents
Nanometer luminescent core-shell zinc oxide-polymer particle and its prepn Download PDFInfo
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- CN100462416C CN100462416C CNB2005101104598A CN200510110459A CN100462416C CN 100462416 C CN100462416 C CN 100462416C CN B2005101104598 A CNB2005101104598 A CN B2005101104598A CN 200510110459 A CN200510110459 A CN 200510110459A CN 100462416 C CN100462416 C CN 100462416C
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Abstract
The present invention relates to nanometer material technology, and is especially covalent bond formed nanometer luminescent zinc oxide-polymer particle in core-shell structure and its preparation process. The nanometer particle has nanometer size ZnO monocrystal as core and thin nanometer size polymer layer as shell and these two components are connected via covalent bond with high stability. The material as one new type of compound has fixed smelting point, dissolubility, conductivity, viscosity, etc. It has the type, composition and size of both core and shell capable of being controlled via chemical reaction, and thus controllable physical performance. What is more important is that the material as new type of luminescent material has light emitting wavelength, strength, quantum efficiency and other parameters capable of being altered via chemical preparation.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of " zinc oxide-polymkeric substance " luminescent core-shell nanoparticle and preparation method thereof.
Background technology
21 century has been full of opportunities and challenges, and information, the energy, environment, national defence high speed development all advance with day the demand that material proposes, and the microminiaturization of device, intellectuality all require the size of material more and more littler.Therefore nano material becomes in the novel material research field research object that the future economy and social development is had material impact, also is the most active in the contemporary fundamental research, the field of approaching application.Nano materials research of today no longer has been confined to simple quantum dot, unidimensional nanometer rod, nano belt, nanotube, and complicated two dimension, three-dimensional structure material, but marches to matrix material.Because nano composite material has the not available structure composition parameter of single-material, change these parameters and can change performance of composites significantly, wherein nano-component unit is performed to the limit with another component advantage separately; And owing to complex interactions between two components, matrix material often shows the peculiar property that two components did not originally have.In the candidate that all and nano-component are complementary, optimal is exactly polymkeric substance, because the character of organic materialss such as the plasticity-that polymkeric substance had, visco-elasticity, insulativity just in time forms complementation with inorganic nano material.This just perfect complementary relationship makes polymer nanocomposites become the focus of last decade fundamental research and application and development.
But usually the complex method of polymkeric substance and nano material all is a physical blending, no matter is grinding, fusion, solution soaking, gas phase diffusion, and what obtain all is simple mixtures, has only the effect of Van der Waals force or hydrogen bond between two components usually.Though such physical mixed is simple to operate, be fit to industrial production, shortcoming is conspicuous, promptly the bonding force of two components is more weak, the stable composite that forms is poor, and polymkeric substance can take place in long-term placement and nano material two is separated, the phenomenon of whole material character decline.
Summary of the invention
The objective of the invention is to propose good luminescent core-shell nanoparticle of a kind of two component bonding forces stable composite strong, that form and preparation method thereof.
The luminescent core-shell nanoparticle that the present invention proposes, its kernel is zinc oxide (ZnO) monocrystalline, and diameter can be regulated in 1～10 nanometer range, and shell is a polymkeric substance, and thickness can be regulated in 1～10 nanometer range, and kernel is connected by covalent linkage with shell.
Among the present invention, the ZnO nanoparticle can prepare by methods such as sol-gel processing, hydrothermal method, electrochemical depositions, and they can be dissolved in the organic solvent or the aqueous solution with monodispersed state, forms colloidal sol steady in a long-term.These nanoparticles are generally spherical in shape, and its diameter can change arbitrarily in 1～10 nanometer range by regulating synthesis condition.Because in this scope, the ZnO quantum size effect is fairly obvious.If less than 1 nanometer, be exactly cluster, if greater than 10 nanometers, the luminous efficient of ZnO is just very poor.Accurately the size of control ZnO nanoparticle can allow its emission wavelength change in 400～600 nanometer range.
Among the present invention, polymkeric substance can be a kind of of polyoxyethylene glycol (PEG), polyaniline (PANI), polymethyl acrylic acid (PMAA), polyacrylic acid (PAA), polymethylmethacrylate (PMMA), polymethyl acrylate (PMA), polystyrene (PS) or several multipolymer among them, these polymkeric substance are connected by chemical bond with the ZnO nanoparticle, the surface that is present in ZnO, thickness generally are controlled at the scope of 1～10 nanometer.Control thickness is actually the mass percent of two components of control, and this directly has influence on the macroscopic property of whole nano material.Usually, the quality of polymkeric substance is 20%～80% of a whole core-shell nano quality, when organic component less than 20% the time, whole material repeats the solubility variation, when organic component greater than 80% the time, whole material shows as the feature of polymkeric substance, luminescent properties will descend.Here also be stressed that, the mode of connection of polymkeric substance of the present invention and nanoparticle and common be different with organic ligand decorated nanometer particle, the former is more much better than than latter's (coordination, adsorption, hydrogen bond action etc.), this intensive chemical bond has guaranteed that the ratio of whole material two components in dissolved process repeatedly remains unchanged, yet the latter is because coordination balance or adsorption equilibrium, in " evaporate to dryness-dissolving " process, can lose the part part, thereby cause the variation of whole material The Nomenclature Composition and Structure of Complexes.
Among the present invention, two component ways of connecting of polymkeric substance and ZnO nanoparticle are covalent linkage, and this can be confirmed in the infrared spectra of sample.And because this strong mode of connection, the decomposition temperature of sample generally all (can obtain by thermogravimetric analysis) more than 400 ℃, and the nanoparticle decomposition temperature of traditional organic molecule ligand protection generally is lower than 300 ℃.
The preparation of above-mentioned luminescent core-shell nanoparticle can color following method a kind of:
(1) prepares ZnO nanoparticle sol and the polymkeric substance that has strong coordinating group respectively,, allow two component direct reaction generate covalent linkage then both uniform mixing.Specific practice is:
The zinc salt (as zinc formate, zinc acetate etc.) of organic carboxyl acid is refluxed in dehydrated alcohol afterwards and the reaction of the ethanol solution of LiOH, obtain the ethanol colloidal sol of the ZnO nanoparticle of finishing organic carboxyl acid foundation group, rotary evaporation concentrates then, add " non-solvent " (as hexanaphthene or ether) and be settled out ZnO nanoparticle gel, gel is distributed to forms stable sols in the inert organic solvents again.Make polymkeric substance have strong coordinating group (as sulfydryl, amino or carboxyl) by organic synthesis, perhaps directly buy required organic chemicals, these polymer dissolution in above-mentioned inert organic solvents.Mix two parts of solution, allow ZnO nanoparticle and the polymkeric substance that has strong coordinating group in inert media, react, use " non-solvent " method to separate refined product then.
(2) in the polyreaction of ZnO nanoparticle surface trigger monomer, the product nucleus core/shell nano particle.Specific practice is:
Adopt aforesaid method (1) that the organic hydroxy-acid group (as methacrylic acid group or propylene acid group) that has two keys is modified on the ZnO nanoparticle surface, the principle of this nanoparticle according to " similar mixing " is distributed in the polymer monomer (as methyl methacrylate or methyl acrylate), in heating, illumination or ultrasonic trigger monomer polymerization down, and controlling polymers forms very thin one deck (1～10 nanometer) on the surface of each nanoparticle, stopped reaction is separated required sample from system immediately.Because the polymer monomer in the reaction medium and the monomer copolymerization of ZnO nanoparticle surface, the polymer shell of this reaction generation are that to be connected ZnO by covalent linkage lip-deep.
(3) synthetic ZnO nanoparticle in the polymeric media system makes synthetic ZnO surface have polymeric groups.Specific practice is:
The raw material (as zinc acrylate resin and quadrol) that in the medium (as liquid polypropylene acid) of polymkeric substance, adds preparation ZnO nanoparticle, initiating chamical reaction, allow it and polymer formation covalent linkage when generating the ZnO nanoparticle, use " non-solvent " method separation refined product then.
Perhaps, at first allow polymkeric substance have carboxyl, then with Zn (OH) by organic synthesis
2Reaction generates organic zinc salt, according to the ZnO nanoparticle sol of method (1) preparation finishing polymeric groups, uses " non-solvent " method to separate at last and purifies again.
(4) will prepare the raw material of ZnO nanoparticle and the raw material of preparation polymkeric substance and mix, single step reaction synthesizes " ZnO-polymkeric substance " nuclear shell type nano meter particle.Specific practice is:
The raw material (as vinylbenzene) of the raw material (as " zinc acrylate resin+quadrol ") of preparation ZnO nanoparticle and preparation polymkeric substance is mixed, initiating chamical reaction under heating or solvent thermal condition, one step generated " ZnO-polymkeric substance " nuclear shell type nano meter particle (normally throw out), by centrifugal product was separated from mixed system then.
" ZnO-polymkeric substance " luminescent core-shell nanoparticle that the present invention proposes shows as the novel compound of a class on the macroscopic view.The The Nomenclature Composition and Structure of Complexes of whole material is highly stable, can not change in physical processes such as dissolving, evaporation, extraction, fusing, and material has a series of physical constants such as own fixed fusing point, solubleness, specific conductivity, viscosity, refractive index.This class material can be dissolved in the multiple organic solvent, as ethanol, chloroform, toluene, acetonitrile or the like, evaporate to dryness can also dissolve later once more, and the character that keeps original solution, this repetition solubility is common nanoparticle sol not available (many nanoparticles can seriously be reunited behind the solution evaporate to dryness, once more dispersing and dissolving).The physical properties of this class material is very stable, stores several years under the usual conditions and also significant change can not take place.
Up to the present, also report is not modified the ZnO nanoparticle surface to polymer molecule with chemical reaction, perhaps forms core-shell composite nanoparticle at the nanoparticle surface initiated polymerization.Among the present invention, inorganic core with have the kind of casing, size to control by chemical reaction, so the physical properties of this class material can be regulated and control.In addition,, has quantum size effect, by regulating parameters such as emission wavelength that factors such as its size, shape, condition of surface just can change whole hybrid material, intensity, quantum yield because inorganic core itself is luminous semi-conductor nano particles ZnO.Therefore, this class material can be applicable to high-tech product fields such as electroluminescent display, optoelectron sensor.
Description of drawings
Fig. 1 is the photo of the product of embodiment 1.Wherein (a) is the high resolution transmission electron microscopy photo, (b) is the atomic force microscope picture.Can see on average about 2.1 nanometers of nuclear diameter (organism be can't see) in the ZnO of (ZnO) PMAA-PMMA nanoparticle from (a) figure.From (b) figure, can see that the diameter of (ZnO) PMAA-PMMA core-shell nano approximately is 4 nanometers, so the thickness of polymer shell approximately is that (this will judge according to the feature height scale on the particle vertical direction 1 nanometer, can not see the result from orthographic plan, because when sample has only several nanometer, AFM measurement in the horizontal direction exists the error that instrument causes).
Fig. 2 is raw material MAA among the embodiment 1, the infrared spectra of MMA and product (ZnO) PMAA-PMMA nanoparticle.Can see carbon-carbon double bond vibration peak 1635cm
-1In product, disappear emerging characteristic peak 1602 and 1446cm in the product
-1It is the typical infrared absorption of carboxyl and nano-ZnO surface Zn atom covalence bridging.
Fig. 3 is dissolved in photo behind the tetrahydrofuran (THF) for product among the embodiment 1.Wherein (A) is under sunlight, (B) is under ultraviolet lamp.
Embodiment
Embodiment 1
The 4.66g zinc methacrylate is dissolved in 200mL ethanol, and 80 ℃ of following backflows obtained water white solution in 3 hours, and wherein zinc salt concentration is about 0.1mol/L; The 5g lithium hydroxide is dissolved in 500mL ethanol, help dissolving with the high speed vigorous stirring, obtain water white LiOH solution behind the elimination insolubles, concentration is about 0.2mol/L, utilizes the accurate concentration of EDTA and oxalic acid standardized solution difference titration zinc methacrylate and lithium hydroxide.Then with the zinc methacrylate that obtains and lithium hydroxide ethanolic soln according to mol ratio [Zn
2+]/[LiOH]=3.5 mix.This mixed solution normal-temperature reaction boiled off most of solvent after 8 hours in Rotary Evaporators, stop evaporation when waiting white opacity to occur.4 ℃ the above-mentioned turbid solution of cooling is centrifugal after 1 hour down, and the gained solid places vacuum drying oven to remove residual solvent behind the supernatant liquid that inclines.The solid that obtains after the drying was distributed to rapidly in the methyl methacrylate in 60 ℃ of following circulator baths after ten minutes, by centrifugal remove insolubles after evaporate to dryness gained settled solution promptly get product.Use zinc acrylate resin to replace zinc methacrylate, use methyl acrylate to replace methyl methacrylate can obtain identical result.The measurement of quantum yield adopts the sulfuric acid quinoline (quantum yield 55%) that is dissolved in the 0.5mol/L aqueous sulfuric acid as benchmark.
This method is to utilize ZnO surface original free radical polymerization (the near infrared spectrum evidence is arranged), has obtained coating the ZnO nanometer bead particulate of polymkeric substance shell structure.This particle size homogeneous, diameter is about 4 nanometers, wherein diameter average out to 2.1 nanometers (accompanying drawing 1) of ZnO kernel.This material is soluble in multiple organic solvent and forms stable sols, even can reflux one month in 80 ℃ ethanol and aggregate and precipitate does not take place.Ir data proves that polymkeric substance and ZnO surface Zn atom link together by (accompanying drawing 2) by covalent linkage, and this is the most basic feature of material of the present invention.These colloidal sols can send intensive blue-fluorescence (about 420 nanometers of wavelength under UV-light the exciting of (comprising sunlight), accompanying drawing 3), and quantum yield is up to 85% (quantum yield of ZnO nanoparticle all is lower than 20% usually), therefore this material is at optics, and there is wide application prospect aspects such as fluorescence equipment.
Embodiment 2
The preparation method is identical with embodiment 1, but zinc methacrylate and lithium hydroxide ethanolic soln at normal temperatures the reaction times extend to 100 hours, other conditions are constant, finally obtaining the ZnO mean diameter is 4.6 nanometers, the product of thick 2 nanometers of polymer shell.Emission wavelength moves to 500 nanometers, quantum yield 30%.
Embodiment 3
The preparation method is identical with embodiment 1, but the reaction times extends to 48 hours at normal temperatures for zinc methacrylate and lithium hydroxide ethanolic soln, be distributed in the methyl methacrylate in 60 ℃ of following circulator baths 20 minutes, finally obtaining the ZnO mean diameter is 2.8 nanometers, the product of thick 7 nanometers of polymer shell.Emission wavelength moves to 480 nanometers, quantum yield 50%.
Embodiment 4
The preparation method is identical with embodiment 1, but the mol ratio of zinc methacrylate and the reaction of lithium hydroxide ethanolic soln changes [Zn into
2+]/[LiOH]=1.4, other conditions are constant, obtaining the ZnO mean diameter is 2.4 nanometers, the product of thick 2 nanometers of polymer shell, emission wavelength 450 nanometers, quantum yield 10%.
Embodiment 5
The preparation method is identical with embodiment 1, but the mol ratio of zinc methacrylate and the reaction of lithium hydroxide ethanolic soln changes [Zn into
2+]/[LiOH]=1.4, the reaction times extends to 100 hours at normal temperatures, finally obtaining the ZnO mean diameter is 5.8 nanometers, the product of thick 2 nanometers of polymer shell, emission wavelength 580 nanometers, quantum yield 1%.
Embodiment 6
The KMnO that in the aqueous solution of PEGME (polyoxyethylene glycol monomethyl ether, molecular weight 350) 0.01M, adds KOH and porphyrize
4, stirring reaction to green the disappearance (allows intermediate product Mn
2O
4 -Reacted), filter brown MnO
2Precipitation, dripping hydrochloric acid is rotated evaporate to dryness then to neutral in the gained clear liquid, behind the toluene lysate, filters insoluble KCl, and the mother liquor rotary evaporation removes and anhydrates and toluene, and that remaining is exactly the PEGME that end group is oxidized to carboxyl, and note is made MePEO-COOH.New sedimentary Zn (OH)
2With the aqueous solution of MePEO-COOH, heated and stirred filters excessive Zn (OH) after a few hours
2, rotation evaporate to dryness gained clear liquid, dried overnight in 100 ℃ of vacuum drying ovens then.Product is exactly anhydrous Zn (MePEO-COO)
2Zn (MePEO-COO)
2After being dissolved in dehydrated alcohol, with the ethanol solution of LiOH [Zn in molar ratio
2+]/[LiOH]=5 mix, promptly obtain ZnO colloidal sol luminous under ultraviolet lamp, change the composition and the proportioning of reactant, the emission wavelength of colloidal sol also changes thereupon.Allow colloidal sol concentrate at 40 ℃ of rotary evaporations, to wherein adding excessive anhydrous diethyl ether, fully be placed in the separating funnel after the vibration and leave standstill, liquid is divided into two-layer, allow lower floor's liquid dried overnight in 100 ℃ of vacuum drying ovens eliminate wherein ethanol and ether, just obtain MePEO-COO
-The ZnO nanoparticle of modifying.From infrared spectra, can find the charateristic avsorption band of carboxyl and nano-ZnO surface Zn atom covalence binding.See diameter average out to 1.6 nanometers of ZnO nanoparticle under the transmission electron microscope, polymer shell thickness average out to 2 nanometers that arrive by atomic force microscope observation.This nuclear shell type nano meter particle emission wavelength is 460 nanometers, and quantum yield is 35%.
Embodiment 7
The preparation method is identical with embodiment 6, but the molecular weight of PEGME is 750, and other conditions are all constant, and finally obtaining the ZnO mean diameter is 1.2 nanometers, the product of thick 4 nanometers of polymer shell.These nuclear shell type nano meter particle emission wavelength 450 nanometers, quantum yield 30%.
Embodiment 8
The preparation method is identical with embodiment 6, but the molecular weight of PEGME is 750, the mol ratio [Zn of reaction
2+]/[LiOH]=1.4, finally obtaining the ZnO mean diameter is 3.2 nanometers, the product of thick 4 nanometers of polymer shell.These nuclear shell type nano meter particle emission wavelength 520 nanometers, quantum yield 25%.
Embodiment 9
The preparation method is identical with embodiment 3, but the mol ratio [Zn of reaction
2+]/[LiOH]=1.0, be 48 hours at 60 ℃ of the reaction times, finally obtaining the ZnO mean diameter is 6.1 nanometers, the product of thick 2 nanometers of polymer shell.These nuclear shell type nano meter particle emission wavelength 550 nanometers, quantum yield 10%.
Embodiment 10
The preparation method is identical with embodiment 3, but the molecular weight of PEGME is 5000, the mol ratio [Zn of reaction
2+]/[LiOH]=1.0, be 48 hours at 60 ℃ of the reaction times, finally obtaining the ZnO mean diameter is 8.9 nanometers, the product of thick 10 nanometers of polymer shell.These nuclear shell type nano meter particle emission wavelength 600 nanometers, quantum yield 5%.
The foregoing description can be summarized as a form:
| Embodiment | Polymkeric substance | Particle dia (nm) | The thickness of shell (nm) | Emission wavelength (nm) | Quantum yield (%) |
| 1 | PMAA-PMMA | 2.1 | 1 | 420 | 85 |
| 2 | PMAA-PMMA | 4.6 | 2 | 500 | 30 |
| 3 | PMAA-PMMA | 2.8 | 7 | 480 | 50 |
| 4 | PMAA-PMMA | 2.4 | 2 | 450 | 10 |
| 5 | PMAA-PMMA | 5.8 | 2 | 580 | 1 |
| 6 | PEGME | 1.6 | 2 | 460 | 35 |
| 7 | PEGME | 1.2 | 4 | 450 | 30 |
| 8 | PEGME | 3.2 | 4 | 520 | 25 |
| 9 | PEGME | 6.1 | 2 | 550 | 10 |
| 10 | PEGME | 8.9 | 10 | 600 | 5 |
Claims (2)
1, a kind of zinc oxide-polyalcohol nucleocapsid type luminous nanoparticle is characterized in that kernel is the Zinc oxide single crystal particle, and diameter is 1～10 nanometer, and shell is a polymkeric substance, and thickness is 1～10 nanometer, and kernel is connected by covalent linkage with shell;
Wherein, described polymkeric substance is a kind of in polymethyl acrylic acid, polyacrylic acid, polymethylmethacrylate, polymethyl acrylate, polyoxyethylene glycol, polyaniline, the polystyrene.
2, a kind of zinc oxide as claimed in claim 1-polyalcohol nucleocapsid type luminous nanometer particle process method is characterized in that adopting the one of the following kind:
(1) prepares the polymkeric substance of ZnO nanoparticle sol and amino or carboxyl respectively,, allow two component direct reaction generate covalent linkage then both uniform mixing;
(2) in the polyreaction of ZnO nanoparticle surface trigger monomer, the product nucleus core/shell nano particle;
(3) synthetic ZnO nanoparticle in the polymeric media system makes synthetic ZnO surface have polymeric groups;
(4) will prepare the raw material of ZnO nanoparticle and the raw material of preparation polymkeric substance and mix, single step reaction synthesizes ZnO-polyalcohol nucleocapsid type nanoparticle.
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| TWI506064B (en) * | 2012-07-23 | 2015-11-01 | Innocom Tech Shenzhen Co Ltd | Quantum dots/polymer composite films and method for manufacturing the same |
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| CN101275073B (en) * | 2007-09-26 | 2010-07-21 | 浙江大学 | Preparation for ZnO quantum dot |
| CN101220128B (en) * | 2008-01-31 | 2011-04-06 | 复旦大学 | Polymethyl methacrylate composite microsphere, preparation method and application thereof |
| JP5392697B2 (en) * | 2008-02-07 | 2014-01-22 | 独立行政法人産業技術総合研究所 | Core-shell type zinc oxide fine particles or dispersion containing the same, their production method and use |
| WO2009106810A1 (en) * | 2008-02-25 | 2009-09-03 | Nanoco Technologies Limited | Semiconductor nanoparticle capping agents |
| US20120175585A1 (en) * | 2009-09-17 | 2012-07-12 | Yissum Research Development Company Of The Hebrew University Of Jerusalem, Ltd., | Cage nanostructures and prepartion thereof |
| CN102321469A (en) * | 2011-05-30 | 2012-01-18 | 复旦大学 | ZnO luminous nanoparticles synthesized in polyethylene glycol and preparation method thereof |
| CN102964506B (en) * | 2012-12-05 | 2015-03-11 | 山东世拓高分子材料股份有限公司 | Nano zinc dioxide impact-resistant modified acrylate polymer and preparation method thereof |
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| CN107157951B (en) * | 2017-05-16 | 2019-11-12 | 复旦大学 | Nano zine oxide medicine-carrying capsule of self assembly and its preparation method and application |
| CN109233166A (en) * | 2017-07-10 | 2019-01-18 | 合肥杰事杰新材料股份有限公司 | A kind of Zinc oxide quantum dot in-situ polymerization polymethyl methacrylate nano composite material and preparation method |
| CN113130779B (en) * | 2019-12-30 | 2022-08-02 | Tcl科技集团股份有限公司 | Nano material, preparation method thereof and quantum dot light-emitting diode |
| CN113809272A (en) * | 2020-06-16 | 2021-12-17 | Tcl科技集团股份有限公司 | Zinc oxide nano material, preparation method, electron transmission film and light emitting diode |
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