CN102504077A - Preparation method of quantum dot polymer microspheres - Google Patents
Preparation method of quantum dot polymer microspheres Download PDFInfo
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Abstract
The invention discloses a preparation method of quantum dot polymer microspheres, which comprises the following steps that: hydrophobic monomer, oil soluble quantum dot and oil soluble initiator are fully mixed to form uniformly scattered oil phase fluid; jet-flow suspension polymerization is adopted to break and scatter the oil phase fluid into oil drops with uniform sizes, and O/W type suspension liquid forming in the water phase is subjected to polymerization at the constant temperature to form quantum dot polymer microspheres with uniform sizes. The quantum dot polymer microspheres prepared by the method is uniform in grain sizes, controllable in the sizes of the microspheres, high in fluorescence efficiency and stable in chemical properties, thereby having potential application values in the field of biological tests and medical science.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of preparation method of quanta polymer microballoon.
Background technology
Fluorescence is meant a kind of chemiluminescence phenomenon of pl-.When of incident light (normally ultraviolet ray or the X ray) irradiation of certain normal temperature material through certain wavelength; Absorb that luminous energy is laggard goes into excited state; And the emergent light longer than incident light wavelength (wavelength is at visible light wave range usually) sent out and sent to de excitation immediately; In a single day and stopping incident light, luminescence phenomenon also disappears thereupon immediately.Emergent light with this character just is referred to as fluorescence.In recent years; Fluorescent microsphere is as one type of new-type functional material; With its special morphological structure and luminous efficiency efficiently; In biomedical sectors such as fluoroimmunoassay, biosensor and high-flux medicaments sifting, playing an important role, is current research exploitation and one of hot subject of using.But now general organic dye fluorescent reagent exists that fluorescence intensity is little, excitation spectrum is narrow, be easy to by shortcomings such as photobleachings, has seriously restricted its application.
Quantum dot is made up of a spot of atom, and diameter can be accepted the semiconductor nanoparticle of excitation light generation fluorescence between 1-100nm.Quantum dot has special and good visible region fluorescent emission character; Its fluorescence intensity is strong, bleaching speed is slow, fluorescence spectrum is narrow, highly sensitive; And the PLE continuous distribution, fluorescence spectra can be regulated and control through the size that changes quantum dot, therefore; As a kind of novel fluorescent marker, show application prospects based on the fluorescent microsphere of quantum dot in biomolecules identification and in detecting.
CN 100497515C disclose a kind of in mesoporous silicon oxide the method for assembling quantum dot, this method comprises: with mesoporous silicon oxide (SBA-15) is template, TSL 8330 is modified mesoporous silicon oxide, adds cadmium acetate, utilizes amino complexing Cd
2+, Cd
2+Be adsorbed in the inner positively charged ion precursor solution that forms in duct, again with trioctylphosphine oxide, Se or Te ion source pyroreaction, inner synthesizing CdSe or cadmium telluride quantum dot form the quantum dot silicon dioxide microsphere in the duct.
CN 102115508A discloses the diffuse-aggregate method of a kind of utilization quantum dot has been coated in the polymkeric substance micron ball, can obtain the fluorescent microsphere of 1～10 μ m.Concrete grammar is: quantum dot is added in the styrene solution shake up, be added to then in the solution of PVP K120 and absolute ethyl alcohol, the intensification polymerization obtains the quantum dot polystyrene microsphere.
Suspension polymerization is the simplest method of current synthetic quantum dot polymer microballoon.This method is that the monomer that is dissolved with initiator is mixed with quantum dot, under the effect of violent stirring and dispersion agent, with droplet-like be suspended in the water and the polymerisation process that carries out (referring to document J.Mater.Chem.2005,15,1238-1243).But the quanta polymer microspherulite diameter of suspension polymerization preparation is big and distribution is very inhomogeneous, in application process, receives very big restriction.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is to provide a kind of all methods of grain quanta polymer microballoon of jet flow suspension polymerization preparation that adopt.
The preparation method of quanta polymer microballoon provided by the present invention may further comprise the steps:
(1) hydrophobic monomer, oil soluble quantum dot are mixed with oil-soluble initiator, fully stir, form homodisperse oil phase fluid;
(2) in reaction kettle, add stablizer and water, dispersed with stirring forms uniform aqueous phase solution;
(3) pressurization makes said oil phase fluid disperse to get into and forms O/W type suspension-s in the said aqueous phase solution;
(4) constant temperature polyreaction obtains the quanta polymer microballoon after separation, washing, the drying.
As optimal technical scheme, wherein, the class of the preferred hydrophobicity alkene of hydrophobic monomer described in the step (1) is preferably vinylbenzene, divinylbenzene, TEB 3K, methyl acrylate, vinyl acetate, SY-Monomer G or derivatives thereof.
The oil soluble quantum dot is selected from a kind of or two or more at least mixture among CdSe, CdTe, InP, InAs, CdSe/CdS, CdSe/ZnSe, the CdTe/ZnS described in the step (1).Said two or more mixture comprises two kinds mixture, and like the mixing of CdSe and CdTe or the mixing of CdTe and InP, the perhaps mixture more than three kinds or three kinds is like the mixture of InAs, CdSe/CdS and CdSe/ZnSe.
Oil-soluble initiator is organo-peroxide or azo-initiator described in the step (1), further is preferably Lucidol or Diisopropyl azodicarboxylate or its mixture.Initiator is claimed radical initiator again, refers to that one type of easy decomposes becomes the compound of radical (being elementary radical), can be used for causing alkene class, the monomeric radical polymerization of diene class and copolymerization.Different polymerization methods, different technological conditions, the Different products purposes should be selected different initiators.Preparing method of the present invention is jet flow suspension polymerization, therefore, selects and the mutual dissolved oil-soluble initiator of organic monomer, like Lucidol or Diisopropyl azodicarboxylate or its mixture.
Mix and be stirred in the oil phase storage tank described in the step (1) and accomplish.
As optimal technical scheme, wherein, reaction kettle is the stirring-type polymerization reaction kettle described in the step (2).The stirring-type polymerization reaction kettle helps forming homodisperse solution system.
Stablizer is a tensio-active agent described in the step (2), includes but not limited to a kind of or two or more at least mixture in Z 150PH, Vinylpyrrolidone polymer, Mierocrystalline cellulose, the HPMC.Said two or more mixture comprises two kinds mixture, like the mixture of Z 150PH and Vinylpyrrolidone polymer, or the mixture more than three kinds or three kinds, like the mixture of Vinylpyrrolidone polymer, Mierocrystalline cellulose and HPMC.
As optimal technical scheme, wherein, pressure is 0.05～0.2MPa described in the step (3), is preferably 0.1～0.2MPa; Preferably; Described dispersion makes the oil phase fluid carry out through nozzle through jet flow suspension polymerization device; Said jet flow suspension polymerization device comprises polymerization reaction kettle, oil phase storage tank and nozzle; Oil phase storage tank upper end links to each other with nitrogengas cylinder through first variable valve, and links to each other through the nozzle of second variable valve with the polymerization reaction kettle upper end; Oil phase storage tank upper end is equipped with tensimeter and motor, and the paddle agitator by driven by motor is installed in the polymerization reaction kettle.Utilize jet flow suspension polymerization device to make the oil phase fluid disperse to get into aqueous phase solution, can make the oil phase fluid in storage tank, remain homodisperse, the microballoon size homogeneous that makes, adjustable grain, chemicalstability is good.
As optimal technical scheme, wherein, the temperature of polyreaction is 60～100 ℃ described in the step (4), is preferably 70～90 ℃, further is preferably 80 ℃; The time of constant temperature polyreaction is not less than 1h, preferably is not less than 2h, further is preferably 3h.
One of the object of the invention also is to provide a kind of and makes the quanta polymer microballoon according to each described method of claim 1～9.
The preparation method of a kind of quanta polymer microballoon provided by the invention adopts jet flow to disperse to substitute mechanical stirring and disperses, and oil phase fluid homodisperse and polyreaction are separately carried out.Form stable O/W type suspension-s through the jet flow technology with the even fragmentation of oil phase fluid and at aqueous phase, polyreaction can obtain the quanta polymer microballoon of uniform particle diameter.
The quanta polymer microballoon for preparing with respect to existing suspension polymerization; The polymer microballoon that utilizes preparation method provided by the present invention to make has obtained the new characteristic of quanta polymer microballoon, its uniform particle diameter; Adjustable size, this existing suspension polymerization can't prepare.Therefore, quanta polymer method for preparing microsphere of the present invention can substitute the suspension polymerization of prior art, can be used for the preparation of any suitable quanta polymer microballoon.
Embodiment
The preparation method of quantum dot such as CdSe:
(1) get the 0.09g selenium powder, place the flask that adds the 30ml octadecylene, under nitrogen protection, be heated to 200 ℃, constant temperature 20 minutes is cooled to room temperature, obtains the selenium storing solution;
(2) 0.06g CdO, 0.5g Triple Pressed Stearic Acid and 20ml octadecylene are blended in the beaker, heating is 150 ℃ under nitrogen protection, and constant temperature 20 minutes is cooled to room temperature, obtains the cadmium storing solution;
(3) get the cadmium storing solution of above-mentioned 0.5ml, add 0.25g oxidation tri-n-octyl phosphine and cetylamine, under nitrogen protection, heat 260 ℃, kept for 20 seconds, remove heating unit rapidly and make product be cooled to room temperature.
(4) product adds normal hexane, and is centrifugal, discards post precipitation, adds acetone, leaves standstill to make the product deposition in 10 minutes, and abandoning supernatant obtains the CdSe quantum dot.
Embodiment one
(1) organic phase of 80g vinylbenzene, 10g divinylbenzene, 0.1g CdSe quantum dot and 3g Lucidol being formed adds in the oil phase storage tank, forms uniform oil phase fluid through stirring;
(2) in the stirring-type polymerization reaction kettle, add 1000ml zero(ppm) water and 10g Z 150PH, after 80 ℃ of constant temperature stir 30min, Z 150PH is dissolved fully, keep stirring velocity to 200rpm;
(3) pressurization makes the pressure in the oil phase storage tank keep 0.1MPa, opens second variable valve, and the oil phase fluid forms O/W suspension-s through aqueous phase in the nozzle dispersion entering polymerization reaction kettle, 80 ℃ of reactions of constant temperature 3h;
(4) after the cooling,, can obtain CdSe quantum dot polystyrene microsphere through operations such as spinning, washing, oven dry.
Embodiment two
(1) organic phase of 70g TEB 3K, 5g TGM 1,0.1g CdSe quantum dot and 4g Lucidol being formed adds in the oil phase storage tank, forms uniform oil phase fluid through stirring;
(2) in the stirring-type polymerization reaction kettle, add 1000ml zero(ppm) water and 15g Vinylpyrrolidone polymer, after 80 ℃ of constant temperature stir 30min, Vinylpyrrolidone polymer is dissolved fully, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in the oil phase storage tank keep 0.1MPa, open second variable valve, the oil phase fluid gets into the interior aqueous phase of polymerization reaction kettle through nozzle dispersion and forms O/W suspension-s;
(4) 80 ℃ of following constant temperature polyreaction 3h after the cooling, through operations such as spinning, washing, oven dry, can obtain CdSe quantum dot poly (methyl methacrylate) micro-sphere.
Embodiment three
(1) organic phase of 70g vinyl acetate, 4g divinylbenzene, 0.1g CdSe quantum dot and 4g Lucidol composition adds in the oil phase storage tank, forms uniform oil phase fluid through stirring;
(2) in the stirring-type polymerization reaction kettle, add 1000ml zero(ppm) water and 15g Z 150PH, after 80 ℃ of constant temperature stir 30min, Z 150PH is dissolved fully, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in the oil phase storage tank keep 0.05MPa, open second variable valve, the oil phase fluid gets into the interior aqueous phase of polymerization reaction kettle through nozzle dispersion and forms O/W suspension-s;
(4) 85 ℃ of following constant temperature polyreaction 2h after the cooling, through operations such as spinning, washing, oven dry, can obtain 0.1g CdSe quantum dot Vinyl Acetate Copolymer ester microsphere.
Embodiment four
(1) organic phase of 70g methyl acrylate, 4g divinylbenzene, 0.1g CdSe quantum dot and 4g Lucidol composition adds in the oil phase storage tank, forms uniform oil phase fluid through stirring;
(2) in the stirring-type polymerization reaction kettle, add 1000ml zero(ppm) water and 15g Z 150PH, after 80 ℃ of constant temperature stir 30min, Z 150PH is dissolved fully, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in the oil phase storage tank keep 0.2MPa, open second variable valve, the oil phase fluid gets into the interior aqueous phase of polymerization reaction kettle through nozzle dispersion and forms O/W suspension-s;
(4) 90 ℃ of following constant temperature polyreaction 1h after the cooling, through operations such as spinning, washing, oven dry, can obtain CdSe quantum dot polymethyl acrylate microballoon.
Embodiment five
(1) organic phase of 80g SY-Monomer G, 4g TGM 1,0.1g CdSe quantum dot and 3g Lucidol composition adds in the oil phase storage tank, forms uniform oil phase fluid through stirring;
(2) in the stirring-type polymerization reaction kettle, add 1000ml zero(ppm) water and 20g Z 150PH, after 80 ℃ of constant temperature stir 30min, Z 150PH is dissolved fully, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in the oil phase storage tank keep 0.1MPa, open second variable valve, the oil phase fluid gets into the interior aqueous phase of polymerization reaction kettle through nozzle dispersion and forms O/W suspension-s;
(4) 75 ℃ of following constant temperature polyreaction 4h after the cooling, through operations such as spinning, washing, oven dry, can obtain CdSe quantum dot poly (glycidyl methacrylate) microballoon.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technical process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technical process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technical process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the preparation method of a quanta polymer microballoon may further comprise the steps:
(1) hydrophobic monomer, oil soluble quantum dot are mixed with oil-soluble initiator, fully stir, form homodisperse oil phase fluid;
(2) in reaction kettle, add stablizer and water, dispersed with stirring forms uniform aqueous phase solution;
(3) pressurization makes said oil phase fluid disperse to get into and forms O/W type suspension-s in the said aqueous phase solution;
(4) constant temperature polyreaction obtains the quanta polymer microballoon after separation, washing, the drying.
2. the method for claim 1; It is characterized in that; The class of the preferred hydrophobicity alkene of hydrophobic monomer described in the step (1) is preferably vinylbenzene, divinylbenzene, TEB 3K, methyl acrylate, vinyl acetate, SY-Monomer G or derivatives thereof.
3. the method for claim 1 is characterized in that, the oil soluble quantum dot is selected from a kind of or two or more at least mixture among CdSe, CdTe, InP, InAs, CdSe/CdS, CdSe/ZnSe, the CdTe/ZnS described in the step (1).
4. the method for claim 1 is characterized in that, oil-soluble initiator is organo-peroxide or azo-initiator described in the step (1), further is preferably Lucidol or Diisopropyl azodicarboxylate or its mixture.
5. like each described method of claim 1～4, it is characterized in that, mix and be stirred in the oil phase storage tank described in the step (1) and accomplish.
6. the method for claim 1 is characterized in that, reaction kettle is the stirring-type polymerization reaction kettle described in the step (2).
7. the method for claim 1 is characterized in that, stablizer is a tensio-active agent described in the step (2), is preferably a kind of or two or more at least mixture in Z 150PH, Vinylpyrrolidone polymer, Mierocrystalline cellulose, the HPMC.
8. the method for claim 1 is characterized in that, pressure is 0.05～0.2MPa described in the step (3), is preferably 0.1～0.2MPa;
Preferably; Described dispersion makes the oil phase fluid carry out through nozzle through jet flow suspension polymerization device; Said jet flow suspension polymerization device comprises polymerization reaction kettle, oil phase storage tank and nozzle; Oil phase storage tank upper end links to each other with nitrogengas cylinder through first variable valve, and links to each other through the nozzle of second variable valve with the polymerization reaction kettle upper end; Oil phase storage tank upper end is equipped with tensimeter and motor, and the paddle agitator by driven by motor is installed in the polymerization reaction kettle.
9. the method for claim 1 is characterized in that, the temperature of polyreaction is 60～100 ℃ described in the step (4), is preferably 70～90 ℃, further is preferably 80 ℃; The time of constant temperature polyreaction is not less than 1h, preferably is not less than 2h, further is preferably 3h.
10. a quanta polymer microballoon is characterized in that, makes according to each described method of claim 1～9.
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| CN102936015A (en) * | 2012-11-23 | 2013-02-20 | 苏州知益微球科技有限公司 | Preparation method of silica gel microspheres |
| CN107722158A (en) * | 2017-10-10 | 2018-02-23 | 成都爱兴生物科技有限公司 | Monodisperse carboxyl modification quantum dot complex microsphere, its preparation method and application |
| CN108546314A (en) * | 2018-05-08 | 2018-09-18 | 纳晶科技股份有限公司 | Quantum dot dispersion resin formed body, preparation method and quantum dot dispersion |
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| CN102936015A (en) * | 2012-11-23 | 2013-02-20 | 苏州知益微球科技有限公司 | Preparation method of silica gel microspheres |
| CN107722158A (en) * | 2017-10-10 | 2018-02-23 | 成都爱兴生物科技有限公司 | Monodisperse carboxyl modification quantum dot complex microsphere, its preparation method and application |
| CN108546314A (en) * | 2018-05-08 | 2018-09-18 | 纳晶科技股份有限公司 | Quantum dot dispersion resin formed body, preparation method and quantum dot dispersion |
| CN110713754B (en) * | 2018-07-11 | 2022-05-31 | Tcl科技集团股份有限公司 | Block copolymer, composite particle, printing ink and preparation method and application thereof |
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| CN113234201A (en) * | 2021-04-23 | 2021-08-10 | 武汉珈源同创科技有限公司 | Multilayer coated quantum dot fluorescent coding microsphere and preparation method thereof |
| CN113619204A (en) * | 2021-08-04 | 2021-11-09 | 南京贝迪新材料科技股份有限公司 | Novel barrier-free quantum dot film and preparation method thereof |
| CN114181341A (en) * | 2021-12-30 | 2022-03-15 | 广东粤港澳大湾区国家纳米科技创新研究院 | Method for preparing quantum dot fluorescent microspheres by ultrasonic initiation |
| CN114181341B (en) * | 2021-12-30 | 2024-01-19 | 朱小波 | Method for preparing quantum dot fluorescent microspheres by ultrasonic initiation |
| CN115626840A (en) * | 2022-09-08 | 2023-01-20 | 重庆锦弘新材料技术工程有限公司 | Concrete durability protection material for sewage treatment plant and application thereof |
| CN115626840B (en) * | 2022-09-08 | 2024-01-12 | 重庆锦弘新材料技术工程有限公司 | Concrete durability protection material for sewage treatment plant and application thereof |
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Application publication date: 20120620 |