CN102115508A - Synthetic method for micro-size polymer fluorescent microspheres - Google Patents
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Abstract
The invention relates to a synthetic method for micro-size polymer fluorescent microspheres and aims to solve the problem of limited application range since the size of fluorescent microspheres is only defined between nanometer and submicron. The synthetic method comprises the following steps: firstly, synthesizing Na2SeSO3 solution; secondly, synthesizing quantum dots QDs1 with high quality; thirdly, preparing pure quantum dots QDs2; fourthly, adding the quantum dots QDs2 in styrene solution for shaking; fifthly, adding polyvinylpyrrolidone and absolute ethyl alcohol in a four-necked flask, then feeding N2 into the four-necked flask, and dripping the styrene solution to obtain an emulsion sample after polyreaction; and sixthly, performing centrifugal settling, washing and drying to the emulsion sample to obtain polystyrene microspheres. The quantum dots are wrapped in the polymer microspheres by the dispersion polymerization method to obtain 1-10 mu.m fluorescent microspheres, the fluorescent microspheres can be applied to the field of biomarkers, coating fillers, optical encoders and the like, and the method can be used for the synthesis of fluorescent microspheres.
Description
Technical field
The present invention relates to a kind of synthetic method of micrograde polymer fluorescent microsphere.
Background technology
Dispersion copolymerization method is a kind of polymerization process that grows up the beginning of the seventies, because have advantage simple and easy to do, that product property is good, over 30 years, dispersion copolymerization method has obtained sufficient development.When the research polymerizing condition, carry out the research of dispersion polymerization mechanism synchronously, and obtained huge achievement, Tseng, Lok, Lu, people such as Pr ochazka and Paine have made initiative contribution.Progressively perfect along with the ripe gradually and polymerization mechanism of dispersion polymerization processes, dispersion polymerization not only is confined to the preparation of single variety polymer microballoon, but develops to multi-functional, polymorphic, many kind.Nowadays, based on this method, successfully developed the crosslinking structure functional microsphere, the hollow porous microsphere is examined a shell structure functional microballoon, magnetic microsphere, and novel kind such as temperature-sensitive microballoon also is applied to many fields, particularly biomedical sector.
Fluorescent microsphere (Fluorescent microspheres) be meant diameter at nano level to the micron order scope, load has fluorescent substance, stimulated by outside energy to inspire the solia particle of fluorescence, its profile can be arbitrary shape, representative configuration be a sphere.The carrier of fluorescent microsphere mostly is the organic or inorganic polymer materials, and it has metastable morphological structure with the exciting light behavior, is subjected to the influence of ambient conditions such as solvent, heat, electricity, magnetic etc. littler than pure fluorescent chemicals.It has been widely used in biomedical sector as a kind of novel solid support material, carries medical emulsion reagent, biomolecular labeling and spike, the mark of immunodetection, cell marking, nucleic acid hybridization etc. as the medicine of biological chemistry and biomedical aspect is directed.
The preparation method of existing fluorescent microsphere mainly contains: 1, be main raw with the fluorescence quantum, and surface coverage certain protection layer or further introduce modification group; 2, fluorescence dye is introduced in the polymer or the microballoon of silicon-dioxide; But, make their application in some aspects be subjected to certain restriction because the size of microballoon only limits to nanometer and submicron.
Summary of the invention
The present invention develops a kind of method of new synthetic polymer micron ball, solve that the fluorescent microsphere size lacks micron order and the limited problem of range of application that causes, and the synthetic method of a kind of micrograde polymer fluorescent microsphere that provides.
The synthetic method of a kind of micrograde polymer fluorescent microsphere of the present invention is carried out according to following steps: one, with Na
2SO
3Join in the deionized water, obtain the Na that concentration is 7.5g/L~23.5g/L
2SO
3Solution adds the Se powder again, and the concentration that makes Se in the solution is 4.4g/L~10.9g/L, and 55 ℃~65 ℃ oil baths feed nitrogen purge oxygen 2h~5h, synthetic Na
2SeSO
3Solution; Two, NaOH is joined in the deionized water, obtain the NaOH solution of 1.2mol/L~2.25mol/L, the volume ratio of adding and NaOH solution is 2~5: 1 dehydrated alcohol again, stir, the volume ratio of adding of dissolving back and NaOH solution is 2~4.5: 5 oleic acid, adds Cd (AC) 2H of 20g/L~30g/L again
2O, concentration is 2.5g/L~6.5g/L, obtains mixed solution, with step 1 synthetic Na
2SeSO
3Solution joins in this mixed solution, and concentration is 0.01mol/L~0.022mol/L, and gained solution moves in the autoclave again, in 40~150 ℃ of temperature ranges, and reaction 0.5~24h, synthetic high-quality quantum dot QDs1; Three, in step 2 synthetic quantum dot QDs1, add 50~80mL normal hexane, 4500r/min~5500r/min centrifugation, absolute ethanol washing, repeated multiple times obtains purified quantum dot QDs2; Four, step 3 synthetic quantum dot QDs2 is joined in 15%~35% the styrene solution, shake up, quantum dot is dispersed in the vinylbenzene uniformly, obtain the styrene solution of quantum dot; Five, 1%~5% Polyvinylpyrolidone (PVP) (PVP) and dehydrated alcohol are joined in the four-necked bottle, stir form homogeneous system after, feed N
2Emptying, and the slow vinylbenzene that is dissolved with Diisopropyl azodicarboxylate (AIBN) and CdSe quantum dot that drips of beginning are after monomer dropping finishes, keep nitrogen atmosphere and stirring and evenly mixing, at 50 ℃~85 ℃ following polyreaction 20h~27h, obtain the polystyrene microsphere samples of latex, this polymerization belongs to dispersion polymerization; Six, step 5 synthetic samples of latex is used hypervelocity 4500r/min~5500r/min centrifugal settling, discard supernatant liquid, with absolute ethanol washing lower floor microballoon, 4500r/min~5500r/min is centrifugal again, washing so repeats repeatedly again, and the microballoon after the washing is poured in the culture dish, dry 20h~30h in 50 ℃~68 ℃ vacuum drying ovens promptly gets polystyrene microsphere.
The present invention uses diffuse-aggregate method that quantum dot is coated in the polymkeric substance micron ball, can obtain 1~10um fluorescent microsphere, this microballoon can be applied to fields such as biomarker, paint filler, optical encoding, for other traditional testing method, present method range of application is expanded greatly.
Description of drawings
Fig. 1 is CdSe quantum dot suspension fluorescence spectrum figure; Fig. 2 is the polymer fluorescent microspheres electron scanning micrograph; Fig. 3 is the fluorescence spectrum figure of microballoon dissolving back quantum dot suspension.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the synthetic method of a kind of micrograde polymer fluorescent microsphere of present embodiment is carried out according to the following steps: one, with Na
2SO
3Join in the deionized water, configuration concentration is the Na of 7.5g/L~23.5g/L
2SO
3Solution adds the Se powder again, and the concentration that makes Se in the solution is 4.4g/L~10.9g/L, and 55 ℃~65 ℃ oil baths feed nitrogen purge oxygen 2h~5h, synthetic Na
2SeSO
3Solution.Two, NaOH is joined in the deionized water, obtain the NaOH solution of 1.2mol/L~2.25mol/L, the volume ratio of adding and NaOH solution is 2~5: 1 dehydrated alcohol again, stirs, and the volume ratio of adding of dissolving back and NaOH solution is 2~4.5: 5 oleic acid.Cd (AC) 2H that adds 20g/L~30g/L again
2O, concentration is 2.5g/L~6.5g/L, obtains mixed solution.With step 1 synthetic Na
2SeSO
3Solution joins in this mixed solution, and concentration is 0.01mol/L~0.022mol/L.Gained solution moves in the autoclave again, in 40~150 ℃ of temperature ranges, and reaction 0.5~24h, synthetic high-quality quantum dot QDs1.Three, in step 2 synthetic quantum dot QDs1, add 50~80mL normal hexane, 4500r/min~5500r/min centrifugation, absolute ethanol washing, repeated multiple times obtains purified quantum dot QDs2.Four, step 3 synthetic quantum dot QDs2 is joined in 15%~35% the styrene solution, shake up, quantum dot is dispersed in the vinylbenzene uniformly, obtain the styrene solution of quantum dot.Five, 1%~5% Polyvinylpyrolidone (PVP) (PVP) and dehydrated alcohol are joined in the four-necked bottle, stir form homogeneous system after, feed N
2Emptying, and beginning slowly drips the vinylbenzene that is dissolved with Diisopropyl azodicarboxylate (AIBN) and CdSe quantum dot.After monomer dropping finishes, keep nitrogen atmosphere and stirring and evenly mixing,, obtain the polystyrene microsphere samples of latex at 50 ℃~85 ℃ following polyreaction 20h~27h.This polymerization belongs to dispersion polymerization.Six, with step 5 synthetic samples of latex 4500r/min~5500r/min centrifugal settling, discard supernatant liquid, with absolute ethanol washing lower floor microballoon, 4500r/min~5500r/min is centrifugal again, and washing so repeats repeatedly again.Microballoon after the washing is poured in the culture dish, and dry 20h~30h in 50 ℃~68 ℃ vacuum drying ovens promptly gets polystyrene microsphere.
Embodiment two: what present embodiment and embodiment one were different is: the Na that disposes in the step 1
2SO
3Strength of solution is 10.5g/L~17.5g/L, and the concentration of Se is 6.4g/L~9.9g/L in the solution, and 58 ℃~62 ℃ oil baths feed nitrogen purge oxygen 2.5h~4h, and other is identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is: the Na that disposes in the step 1
2SO
3Strength of solution is 16.5g/L, and the concentration of Se is 8.5g/L in the solution, and 60 ℃ of oil baths feed nitrogen purge oxygen 3.5h, and other is identical with embodiment one.
Embodiment four: what present embodiment and embodiment one to three were different is: dispose in the step 2 the NaOH strength of solution be 1.4mol/L~2.05mol/L, the volume ratio of adding and NaOH solution is 2.5~4: 1 dehydrated alcohol again, stir, the volume ratio of adding of dissolving back and NaOH solution is 2.8~4.2: 5 oleic acid.Cd (AC) 2H that adds 22g/L~28g/L again
2O, concentration is 3.5g/L~5.5g/L, obtains mixed solution.With step 1 synthetic Na
2SeSO
3Solution joins in this mixed solution, and concentration is 0.012mol/L~0.019mol/L.Gained solution moves in the autoclave again, in 40~150 ℃ of temperature ranges, and reaction 0.5~24h, synthetic high-quality quantum dot QDs1.Other is identical with embodiment one to three.
Embodiment five: what present embodiment and embodiment one to three were different is: dispose in the step 2 the NaOH strength of solution be 1.95mol/L, the volume ratio of adding and NaOH solution is 3.9: 1 a dehydrated alcohol again, stir, the volume ratio of adding of dissolving back and NaOH solution is 3: 5 a oleic acid.Cd (AC) 2H that adds 26.6g/L again
2O, concentration is 5.4g/L, obtains mixed solution.With step 1 synthetic Na
2SeSO
3Solution joins in this mixed solution, and concentration is 0.013mol/L.Gained solution moves in the autoclave again, in 80 ℃ of temperature ranges, and reaction 10h, synthetic high-quality quantum dot QDs1.Other is identical with embodiment one to three
Embodiment six: what present embodiment and embodiment one to five were different is: cinnamic concentration is 20%~30% in the step 4, and other is identical with embodiment one to five.
Embodiment seven: what present embodiment and embodiment one to five were different is: cinnamic concentration is 25% in the step 4, and other is identical with embodiment one to five.
Embodiment eight: what present embodiment and embodiment one to seven were different is: the concentration of Polyvinylpyrolidone (PVP) in the step 5 (PVP) is 1.5%~4.5%, polymeric reaction condition is 52 ℃~80 ℃, 19h~26h, other is identical with embodiment one to seven.
Embodiment nine: what present embodiment and embodiment one to seven were different is: the concentration of Polyvinylpyrolidone (PVP) in the step 5 (PVP) is 2%, and polymeric reaction condition is 60 ℃, 20h, and other is identical with embodiment one to seven.
Embodiment ten: what present embodiment and embodiment one to nine were different is: drying conditions is dry 22h~28h in 55 ℃~66 ℃ vacuum drying ovens in the step 6, and other is identical with embodiment one to nine.
Embodiment 11: what present embodiment and embodiment one to nine were different is: the two times centrifugal condition is 5000r/min in the step 6, and drying conditions is dry 27h in 65 ℃ of vacuum drying ovens, and other is identical with embodiment one to nine.
Claims (10)
1. the synthetic method of a micrograde polymer fluorescent microsphere is characterized in that a kind of synthetic method of micrograde polymer fluorescent microsphere is carried out according to the following steps: one, with Na
2SO
3Join in the deionized water, obtain the Na that concentration is 7.5g/L~23.5g/L
2SO
3Solution adds the Se powder again, and the concentration that makes Se in the solution is 4.4g/L~10.9g/L, and 55 ℃~65 ℃ oil baths feed nitrogen purge oxygen 2h~5h, synthetic Na
2SeSO
3Solution; Two, NaOH is joined in the deionized water, obtain the NaOH solution of 1.2mol/L~2.25mol/L, the volume ratio of adding and NaOH solution is 2~5: 1 dehydrated alcohol again, stir, the volume ratio of adding of dissolving back and NaOH solution is 2~4.5: 5 oleic acid,, add Cd (AC) 2H of 20g/L~30g/L again
2O, concentration is 2.5g/L~6.5g/L, obtains mixed solution, with step 1 synthetic Na
2SeSO
3Solution joins in this mixed solution, and concentration is 0.01mol/L~0.022mol/L, and gained solution moves in the autoclave again, in 40~150 ℃ of temperature ranges, and reaction 0.5~24h, synthetic high-quality quantum dot QDs1; Three, in step 2 synthetic quantum dot QDs1, add 50~80mL normal hexane, 4500r/min~5500r/min centrifugation, absolute ethanol washing, repeated multiple times obtains purified quantum dot QDs2; Four, step 3 synthetic quantum dot QDs2 is joined in 15%~35% the styrene solution, shake up, quantum dot is dispersed in the vinylbenzene uniformly, obtain the styrene solution of quantum dot; Five, 1%~5% Polyvinylpyrolidone (PVP) (PVP) and dehydrated alcohol are joined in the four-necked bottle, stir form homogeneous system after, feed N
2Emptying, and the slow vinylbenzene that is dissolved with Diisopropyl azodicarboxylate (AIBN) and CdSe quantum dot that drips of beginning are after monomer dropping finishes, keep nitrogen atmosphere and stirring and evenly mixing, at 50 ℃~85 ℃ following polyreaction 20h~27h, obtain the polystyrene microsphere samples of latex, this polymerization belongs to dispersion polymerization; Six, step 5 synthetic samples of latex is used hypervelocity 4500r/min~5500r/min centrifugal settling, discard supernatant liquid, with absolute ethanol washing lower floor microballoon, 4500r/min~5500r/min is centrifugal again, washing so repeats repeatedly again, and the microballoon after the washing is poured in the culture dish, dry 20h~30h in 50 ℃~68 ℃ vacuum drying ovens promptly gets polystyrene microsphere.
2. the synthetic method of a kind of micrograde polymer fluorescent microsphere according to claim 1 is characterized in that the Na that disposes in the step 1
2SO
3Strength of solution is 10.5g/L~17.5g/L, and the concentration of Se is 6.4g/L~9.9g/L in the solution, and 58 ℃~62 ℃ oil baths feed nitrogen purge oxygen 2.5h~4h.
3. the synthetic method of a kind of micrograde polymer fluorescent microsphere according to claim 1 is characterized in that the Na that disposes in the step 1
2SO
3Strength of solution is 16.5g/L, and the concentration of Se is 8.5g/L in the solution, and 60 ℃ of oil baths feed nitrogen purge oxygen 3.5h.
4. according to the synthetic method of claim 1,2 or 3 described a kind of micrograde polymer fluorescent microspheres, it is characterized in that the NaOH strength of solution is 1.4mol/L~2.05mol/L in the step 2, the volume ratio of dehydrated alcohol and NaOH solution is 2.5~4: 1, the volume ratio of oleic acid and NaOH solution is 2.8~4.2: 5, the Cd of 22g/L~28g/L (AC) 2H
2O concentration is 3.5g/L~5.5g/L, step 1 synthetic Na
2SeSO
3The solution addition is concentration 0.012mol/L~0.019mol/L, and reaction conditions is 40~150 ℃ of temperature in the autoclave, time 0.5~24h.
5. according to the synthetic method of claim 1,2 or 3 described a kind of micrograde polymer fluorescent microspheres, it is characterized in that the NaOH strength of solution is 1.95mol/L in the step 2, the volume ratio of dehydrated alcohol and NaOH solution is 3.9: 1, the volume ratio of oleic acid and NaOH solution is 3: 5, the Cd of 26.6g/L (AC) 2H
2O concentration is 5.4g/L, step 1 synthetic Na
2SeSO
3The solution addition is concentration 0.013mol/L, and reaction conditions is 80 ℃ of temperature in the autoclave, time 10h.
6. according to the synthetic method of claim 1,2 or 3 described a kind of micrograde polymer fluorescent microspheres, it is characterized in that cinnamic concentration is 20%~30% in the step 4.
7. according to the synthetic method of claim 1,2 or 3 described a kind of micrograde polymer fluorescent microspheres, it is characterized in that cinnamic concentration is 25% in the step 4.
8. according to the synthetic method of claim 1,2 or 3 described a kind of micrograde polymer fluorescent microspheres, the concentration that it is characterized in that Polyvinylpyrolidone (PVP) in the step 5 (PVP) is 1.5%~4.5%, and polymeric reaction condition is 52 ℃~80 ℃, 19h~26h.
9. according to the synthetic method of claim 1,2 or 3 described a kind of micrograde polymer fluorescent microspheres, the concentration that it is characterized in that Polyvinylpyrolidone (PVP) in the step 5 (PVP) is 2%, and polymeric reaction condition is 60 ℃, 20h.
10. according to the synthetic method of claim 1,2 or 3 described a kind of micrograde polymer fluorescent microspheres, it is characterized in that the two times centrifugal condition is 5000r/min in the step 6, drying conditions is dry 22h~28h in 55 ℃~66 ℃ vacuum drying ovens.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1539913A (en) * | 2003-10-29 | 2004-10-27 | 武汉大学 | Multifunctional fluorescent, magnetic Nano material and preparation method |
CN1560633A (en) * | 2004-02-19 | 2005-01-05 | 上海交通大学 | Preparation method of quantum point microspheric for bio-medical fluorescence probe |
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-
2010
- 2010-12-03 CN CN2010105722608A patent/CN102115508B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1539913A (en) * | 2003-10-29 | 2004-10-27 | 武汉大学 | Multifunctional fluorescent, magnetic Nano material and preparation method |
CN1560633A (en) * | 2004-02-19 | 2005-01-05 | 上海交通大学 | Preparation method of quantum point microspheric for bio-medical fluorescence probe |
CN101012312A (en) * | 2007-02-08 | 2007-08-08 | 上海交通大学 | Method of preparing multifunctional macromolecule-inorganic composite microsphere |
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