CN103694392A - Method for preparing carboxyl polystyrene copolymerized fluorescent microsphere - Google Patents
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Abstract
The invention discloses a method for preparing a carboxyl polystyrene copolymerized fluorescent microsphere. The method comprises steps of putting absolute ethyl alcohol, initiator azodiisobutyronitrile and dispersing agent polyvinylpyrrolidone into water so as to obtain clear transparent solution, adding styrene, acrylic acid and allyl fluorescent dyes into the solution simultaneously, and copolymerizing under nitrogen protection so as to obtain the carboxyl polystyrene copolymerized fluorescent microsphere. The method adopts a dispersion polymerization manner; the prepared carboxyl polystyrene copolymerized fluorescent microsphere has good monodispersity and stable fluorescence.
Description
Technical field
The present invention relates to a kind of preparation method of fluorescent microsphere, particularly relate to a kind of preparation method of carboxyl polystyrene copolymerization fluorescent microsphere.
Background technology
Fluorescent microsphere has a good application prospect.Research shows, it can be widely used in the determination and analysis aspect of correction, biomolecules and the synthetic molecules of fluorescent instrument, especially surface-functionalized fluorescent microsphere, at biomedicine field, there is potential using value, as gene sequencing and expression, protein sequencing, medical diagnosis on disease and drug screening etc.Meanwhile, at aspects such as environmental monitoring and food test, also fluorescent microsphere is had to a large amount of demands.
CN 102115508A discloses a kind of synthetic method of micro-size polymer fluorescent microspheres, first it prepare high-quality quantum dot, adopt again diffuse-aggregate method, quantum dot is coated in polystyrene micron ball, can obtain the fluorescent microsphere of 1-10 μ m.Yet quantum dot easily leaks in fluorescent microsphere prepared by the method, can cause in use the pollution of sample.
Document (Materials Letters, 2008,62,2603-2606) report, take vinylcarbazole, dansyl chloride allylamine and vinylbenzene as raw material, adopt diffuse-aggregate method can prepare fluorescent microsphere, yet this fluorescent microsphere does not have functional group, be difficult for being combined with follow-up biology.
As everyone knows, polystyrene microsphere have good dispersity, specific surface area large, have biologically inert, by common solvent, do not dissolved or swelling, and there are specific physiques such as surface reaction ability, the binding ability that the materials such as protein, dyestuff, close ligand have been had, is suitable as the carrier of fluorescent substance in bioanalysis.By vinylbenzene and the fluorescence dye copolymerization with two keys, can prepare polystyrene fluorescence polymer material, the morphological structure that it is stable and stable and efficient luminous efficiency, the application of organism being carried out to the aspects such as mark, detection and screening is a lot of.But, according to document [Journal of Materials Chemistry, 2009,19,2018-2025] report, the luminescent dye molecule with two keys is larger, in polymerization process, there is to a certain degree sterically hindered, have from inhibition, the two key fluorescence dyes that simultaneously add can destroy the polymerizing condition of blank polymeric microspheres stabilize originally, are difficult for forming the microballoon of uniform particle diameter.
Summary of the invention
The object of this invention is to provide a kind of preparation method with carboxyl function group, carboxyl polystyrene copolymerization fluorescent microsphere that good monodispersity, fluorescence property is good and stable.
The preparation method of carboxyl polystyrene copolymerization fluorescent microsphere provided by the invention obtains fluorescent microsphere by vinylbenzene, vinylformic acid and the copolymerization of allyl group fluorescence dye, its concrete preparation method is: dehydrated alcohol, initiator Diisopropyl azodicarboxylate, polyethylene of dispersing agent pyrrolidone are placed in to water and obtain clear solution, in solution, add vinylbenzene, vinylformic acid and allyl group fluorescence dye simultaneously, under nitrogen protection, carry out copolyreaction, obtain carboxyl polystyrene copolymerization fluorescent microsphere; Wherein, described allyl group fluorescence dye comprises allyl group rhodamine B, allyl group fluorescein or allyl group Nile red, and the add-on of allyl group fluorescence dye is 0.25～0.8% of vinylbenzene quality.
In above-mentioned copolyreaction, described vinylformic acid consumption is 3.5～5.5% of vinylbenzene quality; The consumption of initiator Diisopropyl azodicarboxylate is 2～2.5% of vinylbenzene quality; The consumption of polyethylene of dispersing agent pyrrolidone is 3.5～7% of vinylbenzene quality; Described copolyreaction is under nitrogen protection, in 65～70 ℃ of reaction 12～24h.
The carboxyl polystyrene copolymerization fluorescent microsphere that the present invention obtains above-mentioned preparation method is successively used deionized water and ethanol repetitive scrubbing, until washings no longer detects after fluorescence, in 50 ℃ of vacuum-dryings, obtains final fluorescent microsphere product.
The present invention adopts diffuse-aggregate method, and styrene monomer, Acrylic Acid Monomer and the allyl group fluorescence dye monomer with two keys are carried out to copolymerization, has prepared carboxyl polystyrene copolymerization fluorescent microsphere.
Compared with prior art, the present invention has the following advantages: 1, adopt allyl group fluorescence dye and vinylbenzene and the vinylformic acid direct polymerization with polymerizable groups, fluorescence dye is evenly distributed in microballoon, thereby has guaranteed higher microballoon whole lighting efficiency; Make fluorescence dye stable existence in microballoon, be not easy leakage, cancellation, can not cause test sample contamination; Make fluorescent microsphere there is carboxyl function group.2, use dispersion copolymerization method to prepare fluorescent microsphere, the fluorescent microsphere uniform particle diameter of therefore preparing (2 μ m left and right), has good monodispersity.3, the present invention adopts one kettle way to prepare fluorescent microsphere, makes to prepare the easy and simple to handle of fluorescent microsphere.4, the present invention uses micro-reaction to prepare fluorescent microsphere, makes to prepare the with low cost of fluorescent microsphere.
Accompanying drawing explanation
Fig. 1 is the fluorescence emission spectrogram of the carboxyl polystyrene copolymerization fluorescent microsphere that provides of the embodiment of the present invention.
Fig. 2 is the carboxyl polystyrene microsphere that provides of the embodiment of the present invention and the infrared absorption spectrum comparison diagram of carboxyl polystyrene copolymerization fluorescent microsphere.
Fig. 3 is the SEM figure of the prepared blank microballoon of the embodiment of the present invention and fluorescent microsphere.
Fig. 4 is the shows fluorescent microscopy images of the prepared fluorescent microsphere of the embodiment of the present invention.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further elaborated.
1, allyl group rhodamine B is synthetic: press document (J. Mater. Chem., 2009,19,2018-2025) method, by rhodamine B 240g, salt of wormwood 0.73g, 3-bromopropylene 2.65g drops in reaction flask, add solvent DMF 50ml, catalyst iodine trace, hydroquinone of polymerization retarder trace, under anhydrous and oxygen-free condition, 71 ℃ of reaction 25h, synthesis of allyl rhodamine B, thick product obtains sterling through column chromatography.
2, the preparation of carboxyl polystyrene copolymerization fluorescent microsphere: get respectively Diisopropyl azodicarboxylate 0.06g, polyvinylpyrrolidone 0.18g, dehydrated alcohol 9.6ml and water 0.4ml, be placed in microscale reactor, the ultrasonic clear solution that obtains.Add vinylbenzene 3.02g, vinylformic acid 0.15g, allyl group rhodamine B 15mg, letting nitrogen in and deoxidizing, sealing.Be placed in constant temperature oscillator, under 70 ℃ of conditions, react 12h.Successively, with deionized water and ethanol repetitive scrubbing thus obtained microsphere, until no longer detect fluorescence in washings, 50 ℃ of vacuum-dryings, obtain carboxyl polystyrene copolymerization fluorescent microsphere.
Comparative example 1
Get Diisopropyl azodicarboxylate 0.06g, polyvinylpyrrolidone 0.18g, dehydrated alcohol 9.6ml and water 0.4ml, be placed in microscale reactor, the ultrasonic clear solution that obtains.Add vinylbenzene 3.02g and vinylformic acid 0.15g, letting nitrogen in and deoxidizing, sealing.Be placed in constant temperature oscillator, under 70 ℃ of conditions, react 12h.Successively, with deionized water and ethanol repetitive scrubbing thus obtained microsphere, 50 ℃ of vacuum-dryings, obtain the blank microballoon of carboxyl polystyrene.
1, allyl group fluorescein is synthetic: press document (J. Mater. Chem., 2009,19,2018-2025) method, by fluorescein 2.00g, 3-bromopropylene 2.42g and Anhydrous potassium carbonate 4.97g drop in reaction flask, add solvent DMF 50ml, catalyst iodine trace, hydroquinone of polymerization retarder trace, under anhydrous and oxygen-free condition, 71 ℃ of reaction 25h, obtain the yellow crude product of allyl group fluorescein, after Gossypol recrystallized from chloroform, through column chromatography, obtain sterling.
2, the preparation of carboxyl polystyrene copolymerization fluorescent microsphere: get respectively Diisopropyl azodicarboxylate 0.07g, polyvinylpyrrolidone 0.21g, dehydrated alcohol 9ml and water 1.2ml, be placed in microscale reactor, the ultrasonic clear solution that obtains.Add vinylbenzene 3.0g, vinylformic acid 0.11g, allyl group fluorescein 9mg, letting nitrogen in and deoxidizing, sealing.Be placed in constant temperature oscillator, under 70 ℃ of conditions, react 12h.Successively, with deionized water and ethanol repetitive scrubbing thus obtained microsphere, until no longer detect fluorescence in washings, 50 ℃ of vacuum-dryings, obtain carboxyl polystyrene copolymerization fluorescent microsphere.
Embodiment 3
1, allyl group Nile red is synthetic: press document (J. Mater. Chem., 2009,19,2018-2025) method, N between inciting somebody to action, N-diethylaminophenol 1.65g, concentrated hydrochloric acid 3.40ml and water 1.70ml drop in reaction flask, under ice bath, be stirred to dissolving, control temperature at 0 ℃, slowly drip wherein sodium nitrite in aqueous solution (NaNO
20.78g, H
2o 5.9mL), 30min adds, and 0～5 ℃ of reaction 4h, filters to obtain crude salt hydrochlorate product, vacuum-drying 8h at 50 ℃.Thick product is dissolved in the ethanol of 25ml boiling, is cooled to 40 ℃, slowly add ether until there is crystallization to occur, mixture is placed refrigerator 24h, filters to obtain khaki color needle-like crystal 5-(diethylin)-2-nitrosophenol.
By 5-(diethylin)-2-nitrosophenol 0.50g, 1,6-dihydroxy naphthlene 0.33g and dry DMF 40ml drop in reaction flask, are heated with stirring to backflow, and pressure reducing and steaming DMF after reaction 4h, obtains crude product 1.24g.Column chromatography separating-purifying obtains sterling 9-(diethylin)-2-hydroxyl-5H-benzo [a] phenoxazine-5-ketone.
By 9-(diethylin)-2-hydroxyl-5H-benzo [a] phenoxazine-5-ketone 0.26g, 3-bromopropylene 0.28g, Anhydrous potassium carbonate 0.54g and methyl alcohol 7.30ml drop in reaction flask, be heated with stirring to backflow, reaction 48h obtains crude product, and dry method loading obtains sterling allyl group Nile red through column chromatography separating-purifying.
2, the preparation of carboxyl polystyrene copolymerization fluorescent microsphere: get respectively Diisopropyl azodicarboxylate 0.057g, polyvinylpyrrolidone 0.17g, dehydrated alcohol 8.4ml and water 1.1ml, be placed in microscale reactor, the ultrasonic clear solution that obtains.Add vinylbenzene 2.85g, vinylformic acid 0.11g, allyl group Nile red 18mg, letting nitrogen in and deoxidizing, sealing.Be placed in constant temperature oscillator, under 70 ℃ of conditions, react 12h.Successively, with deionized water and ethanol repetitive scrubbing thus obtained microsphere, until no longer detect fluorescence in washings, 50 ℃ of vacuum-dryings, obtain carboxyl polystyrene copolymerization fluorescent microsphere.
Fig. 1 is the fluorescence emission spectrogram of carboxyl polystyrene copolymerization fluorescent microsphere 3% alcohol dispersion liquid of embodiment 1,2,3 preparations, by Fig. 1 a (embodiment 1), can be found out, under 556nm exciting light, the maximum emission wavelength of this fluorescent microsphere is 575nm; By Fig. 1 b (embodiment 2), can be found out, under 457nm exciting light, the maximum emission wavelength of this fluorescent microsphere is 526nm; By Fig. 1 c (embodiment 3), can be found out, under 547nm exciting light, the maximum emission wavelength of this fluorescent microsphere is 596nm.
In Fig. 2, figure a is the infrared absorpting light spectra of the blank microballoon of reference examples 1 carboxyl polystyrene, and figure b is the infrared absorpting light spectra of embodiment 1 carboxyl polystyrene copolymerization fluorescent microsphere.From figure a, can observe 1702cm
-1place is the stretching vibration peak of C=O base, 3446cm
-1for the stretching vibration peak of hydroxyl in carboxylic acid, the existence of microsphere surface carboxyl is described; 1489cm
-1and 1448cm
-1place is the C-C stretching vibration peak on phenyl ring, 700cm
-1and 758cm
-1for the out-of-plane deformation vibration peak of c h bond on phenyl ring, 3019,3060 and 2921cm
-1stretching vibration peak for unsaturated c h bond on phenyl ring.The provable blank microballoon of carboxyl polystyrene of successfully having prepared of above-mentioned figure a.Compare the infrared spectrogram b of carboxyl polystyrene copolymerization fluorescent microsphere and the infrared spectrogram a of the blank microballoon of carboxyl polystyrene, the two is substantially the same, this is because fluorescence dye content in fluorescent microsphere is few, can not symbolize the characteristic peak of fluorescence dye in infrared spectrum.
Fig. 3 is the SEM figure of the blank microballoon of reference examples 1 carboxyl polystyrene and embodiment 1 carboxyl polystyrene copolymerization fluorescent microsphere.From Fig. 3 a, can find out, the blank microballoon of preparation has good sphericity and monodispersity is good, for preparation copolymerization fluorescent microsphere is laid a good foundation.From Fig. 3 b, can find out, copolymerization fluorescent microsphere and the blank microballoon of preparation have essentially identical particle diameter and dispersiveness.
In Fig. 4, a is that carboxyl polystyrene rhodamine B copolymerization fluorescent microsphere photo, b are that carboxyl polystyrene fluorescein copolymerization fluorescent microsphere photo, c are carboxyl polystyrene Nile red copolymerization fluorescent microsphere photo.
Claims (5)
1. the preparation method of a carboxyl polystyrene copolymerization fluorescent microsphere, to obtain fluorescent microsphere by vinylbenzene, vinylformic acid and the copolymerization of allyl group fluorescence dye, it is characterized in that adopting following method to prepare: dehydrated alcohol, initiator Diisopropyl azodicarboxylate, polyethylene of dispersing agent pyrrolidone to be placed in to water and to obtain clear solution, in solution, add vinylbenzene, vinylformic acid and allyl group fluorescence dye simultaneously, under nitrogen protection, carry out copolyreaction, obtain carboxyl polystyrene copolymerization fluorescent microsphere; Wherein, described allyl group fluorescence dye comprises allyl group rhodamine B, allyl group fluorescein or allyl group Nile red, and the add-on of allyl group fluorescence dye is 0.25～0.8% of vinylbenzene quality.
2. the preparation method of carboxyl polystyrene copolymerization fluorescent microsphere according to claim 1, is characterized in that described vinylformic acid consumption is 3.5～5.5% of vinylbenzene quality.
3. the preparation method of carboxyl polystyrene copolymerization fluorescent microsphere according to claim 1, the consumption that it is characterized in that described initiator Diisopropyl azodicarboxylate is 2～2.5% of vinylbenzene quality.
4. the preparation method of carboxyl polystyrene copolymerization fluorescent microsphere according to claim 1, the consumption that it is characterized in that described polyethylene of dispersing agent pyrrolidone is 3.5～7% of vinylbenzene quality;
According to the preparation method of the carboxyl polystyrene copolymerization fluorescent microsphere described in claim 1,2,3 or 4, it is characterized in that described copolyreaction is under nitrogen protection, in 65～70 ℃ of reaction 12～24h.
5. according to the preparation method of the carboxyl polystyrene copolymerization fluorescent microsphere described in claim 1,2,3 or 4, it is characterized in that the described carboxyl polystyrene copolymerization fluorescent microsphere obtaining successively to use deionized water and ethanol repetitive scrubbing, until washings no longer detects fluorescence, 50 ℃ of vacuum-dryings.
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Cited By (10)
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| CN104910301A (en) * | 2015-07-07 | 2015-09-16 | 南京工业大学 | Polystyrene microsphere with fluorescent response to pH value and preparation method thereof |
| CN108084316A (en) * | 2017-12-15 | 2018-05-29 | 中北大学 | A kind of preparation method of carboxylated porous crosslinked polystyrene copolymerization fluorescent microsphere |
| CN108129595A (en) * | 2017-12-28 | 2018-06-08 | 湖南辰砾新材料有限公司 | A kind of fluorescent copolymer microballoon and preparation method thereof |
| CN108129594A (en) * | 2017-12-20 | 2018-06-08 | 英德科迪颜料技术有限公司 | A kind of fluorescent copolymer microballoon and preparation method thereof |
| CN108264601A (en) * | 2018-01-23 | 2018-07-10 | 湖北新纵科病毒疾病工程技术有限公司 | A kind of preparation method and applications of carboxylic polystyrene microsphere |
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| CN114456326A (en) * | 2022-02-17 | 2022-05-10 | 武汉纺织大学 | Carboxylated polystyrene nano-microsphere and preparation method and application thereof |
| CN115109580A (en) * | 2022-05-11 | 2022-09-27 | 上海大学 | Polystyrene AIE dye fluorescence encoding microsphere material with carboxyl coated on outer layer, and preparation method and application thereof |
| CN115746825A (en) * | 2022-10-26 | 2023-03-07 | 苏州星烁纳米科技有限公司 | Water-soluble fluorescent material-resin compound, preparation method thereof and tracer prepared from compound |
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| CN104910301A (en) * | 2015-07-07 | 2015-09-16 | 南京工业大学 | Polystyrene microsphere with fluorescent response to pH value and preparation method thereof |
| CN108084316A (en) * | 2017-12-15 | 2018-05-29 | 中北大学 | A kind of preparation method of carboxylated porous crosslinked polystyrene copolymerization fluorescent microsphere |
| CN108129594A (en) * | 2017-12-20 | 2018-06-08 | 英德科迪颜料技术有限公司 | A kind of fluorescent copolymer microballoon and preparation method thereof |
| CN108129594B (en) * | 2017-12-20 | 2020-06-19 | 英德科迪颜料技术有限公司 | Fluorescent copolymer microsphere and preparation method thereof |
| CN108129595A (en) * | 2017-12-28 | 2018-06-08 | 湖南辰砾新材料有限公司 | A kind of fluorescent copolymer microballoon and preparation method thereof |
| CN108264601A (en) * | 2018-01-23 | 2018-07-10 | 湖北新纵科病毒疾病工程技术有限公司 | A kind of preparation method and applications of carboxylic polystyrene microsphere |
| CN111116813A (en) * | 2019-12-30 | 2020-05-08 | 河北工业大学 | Preparation method of fluorescent microspheres based on crosslinked polymer |
| CN112851846A (en) * | 2021-01-28 | 2021-05-28 | 浙江大学 | Method for preparing surface carboxylation nano fluorescent microspheres by soap-free emulsion polymerization |
| CN112851846B (en) * | 2021-01-28 | 2022-04-01 | 浙江大学 | Method for preparing surface carboxylation nano fluorescent microspheres by soap-free emulsion polymerization |
| CN114456326A (en) * | 2022-02-17 | 2022-05-10 | 武汉纺织大学 | Carboxylated polystyrene nano-microsphere and preparation method and application thereof |
| CN115109580A (en) * | 2022-05-11 | 2022-09-27 | 上海大学 | Polystyrene AIE dye fluorescence encoding microsphere material with carboxyl coated on outer layer, and preparation method and application thereof |
| CN115746825A (en) * | 2022-10-26 | 2023-03-07 | 苏州星烁纳米科技有限公司 | Water-soluble fluorescent material-resin compound, preparation method thereof and tracer prepared from compound |
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