CN103739762B - A kind of preparation method of near-ultraviolet polystyrene copolymerization fluorescence microsphere - Google Patents
A kind of preparation method of near-ultraviolet polystyrene copolymerization fluorescence microsphere Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of near-ultraviolet polystyrene copolymerization fluorescence microsphere; that initiator Diisopropyl azodicarboxylate, polyethylene of dispersing agent pyrrolidone are placed in dehydrated alcohol and obtain clear transparent solutions; add vinylbenzene and N-allyl carbazole in solution simultaneously; copolyreaction is carried out under nitrogen protection; obtain polystyrene copolymerization fluorescent microsphere; introduce sulfonic group or oh group respectively at microsphere surface again, make functional near-ultraviolet polystyrene copolymerization fluorescence microsphere.The present invention adopts dispersion polymerization processes, and the near-ultraviolet polystyrene copolymerization fluorescence microsphere prepared has good monodispersity and stable fluorescence property.
Description
Technical field
The present invention relates to a kind of preparation method of fluorescent microsphere, particularly relate to the preparation method of the styrene copolymerized fluorescent microsphere of a kind of near ultraviolet functional polyalkylene.
Background technology
Fluorescent microsphere has stable morphological structure and efficient luminous efficiency, less than pure fluorescent chemicals by the impact of ambient conditions as solvent, heat, electricity, magnetic etc., especially biomedical sector has extremely important application in a lot of fields, as the detection, gene studies, the quality control of susceptibility diagnostic reagent etc. of the detection of immunodetection, cell marking and high-flux medicaments sifting, immobilized enzyme, cell-surface antigens, degenerative neuropathy tracer, phagocytic function.Wherein fluorescent microsphere (1-10 μm) application of mono dispersed micrograde widely, the application particularly in flow cytometer.
CN1278534A discloses fluorescently-labeled polymer microsphere and preparation method thereof, first obtains nano level or micron-sized polymer microsphere by Polymer Synthesizing method, and prepares fluorescent microsphere with its absorption or bonding fluorescence molecule or fluorescent probe.In absorption fluorescent microsphere prepared by the method fluorescence dye easily leak, cancellation, test time can cause sample contamination.
Document (DyesandPigments, 2009,82,134-141) report with N-allyl group naphthalimide and vinylbenzene as raw material, adopt the method for emulsifier-free emulsion polymerization to prepare fluorescent microsphere, but this fluorescent microsphere surface lack functional group, the research of the aspects such as inconvenient subsequent biological.
As everyone knows, polystyrene microsphere has that size is controlled, good dispersity, specific surface area are large, have biologically inert, do not dissolved by common solvent or swelling, adsorptivity is strong, coherency good, and the specific physique such as surface reaction activity is high, to the binding ability that the materials such as such as protein, dyestuff, close ligand have had, be well suited for the carrier as fluorescent substance in bioanalysis.Polystyrene microsphere is combined with the fluorescence dye with double bond, its stable morphological structure and stable and efficient luminous efficiency, organism is marked, detect and the application of the aspect such as screening a lot of.
But the fluorescence dye used in existing report is mostly glow or the fluorescent material of green glow, does not use the fluorescent material of blue light-emitting.In addition, according to document (JournalofMaterialsChemistry, 2009,19,2018-2025) report, because the luminescent dye molecule with double bond is larger, what exist to a certain degree in polymerization process is sterically hindered, have from inhibition, the double bond fluorescence dye simultaneously added can destroy the polymerizing condition of blank polymeric microspheres stabilize originally, not easily forms the polystyrene copolymerization fluorescent microsphere of uniform particle diameter.
Summary of the invention
The object of this invention is to provide and a kind ofly there is good monodispersity, the preparation method of the near-ultraviolet polystyrene copolymerization fluorescence microsphere with functional group that fluorescence property is good and stable.
The preparation method of near-ultraviolet polystyrene copolymerization fluorescence microsphere provided by the invention is that copolymerization obtains fluorescent microsphere, then introduces sulfonic group or oh group respectively at microsphere surface with vinylbenzene and N-allyl carbazole for raw material.
Its concrete preparation method comprises the following steps:
1), initiator Diisopropyl azodicarboxylate, polyethylene of dispersing agent pyrrolidone are placed in dehydrated alcohol and obtain clear transparent solutions, add vinylbenzene and N-allyl carbazole in solution simultaneously, under nitrogen protection, in 65 ~ 70 DEG C of copolyreaction 12 ~ 24h, obtain polystyrene copolymerization fluorescent microsphere; Wherein, the add-on of described N-allyl carbazole is 0.4 ~ 0.9% of vinylbenzene quality.
2), get above-mentioned polystyrene copolymerization fluorescent microsphere and be scattered in the vitriol oil, 40 ~ 60 DEG C of reaction 6 ~ 8h, be washed to neutrality, drying obtains the functional near-ultraviolet polystyrene copolymerization fluorescence microsphere of sulfonic group; Or above-mentioned polystyrene copolymerization fluorescent microsphere, Diisopropyl azodicarboxylate and γ-methacryloxypropyl trimethoxy silane are scattered in aqueous ethanolic solution; 65 ~ 70 DEG C of reaction 24 ~ 36h under nitrogen protection, washing drying obtains hydroxy-functional near-ultraviolet polystyrene copolymerization fluorescence microsphere.
Above-mentioned steps 1) copolyreaction in, the consumption of described initiator Diisopropyl azodicarboxylate is 1.8 ~ 2.3% of vinylbenzene quality; The consumption of polyethylene of dispersing agent pyrrolidone is 4.6 ~ 6.2% of vinylbenzene quality.
Above-mentioned steps 2) in hydroxy-functional near-ultraviolet polystyrene copolymerization fluorescence microsphere preparation in, the consumption of described γ-methacryloxypropyl trimethoxy silane is 2 ~ 7 times of polystyrene copolymerization fluorescent microsphere quality, the consumption of Diisopropyl azodicarboxylate is 0.24 ~ 0.48 times of polystyrene copolymerization fluorescent microsphere quality, the solution that described aqueous ethanolic solution preferred alcohol and water are mixed to get according to 5: 1.
The polystyrene copolymerization fluorescent microsphere priority deionized water that above-mentioned preparation method obtains by the present invention and ethanol repetitive scrubbing, until after washings no longer detects fluorescence, obtain final fluorescent microsphere product in 50 DEG C of vacuum-dryings.And adopt use the same method washing and drying obtain sulfonic group or hydroxy-functional near-ultraviolet polystyrene copolymerization fluorescence microsphere.
The present invention adopts diffuse-aggregate method, the vinylbenzene and N-allyl carbazole two kinds of monomers with double bond are carried out copolymerization, prepared polystyrene copolymerization fluorescent microsphere, and and then to its modifying surface, obtain functional near-ultraviolet polystyrene copolymerization fluorescence microsphere.
Compared with prior art, the present invention has the following advantages: the fluorescence dye N-allyl carbazole that 1, the present invention adopts is a kind of near ultraviolet or mazarine fluorescence material, should be used for saying for multi-wavelength fluorometric analyses such as comprising immunofluorescence, nucleic acid and protein chip, this short wavelength's blue light can provide contrasting colour, can be easier to distinguish from the fluorescent probe of other longwave transmissions.2, adopt allyl carbazole and vinylbenzene direct polymerization, fluorescence dye is evenly distributed in microballoon, thus ensure that higher microballoon whole lighting efficiency, fluorescence dye stable existence, in microballoon, is not easy leakage, cancellation, can not causes test sample contamination.3, adopt dispersion copolymerization method to prepare fluorescent microsphere, the fluorescent microsphere uniform particle diameter (about 2.5 μm) prepared, there is good monodispersity.4, sulfonic group or hydroxyl functional groups is introduced by two kinds of approach on fluorescent microsphere surface, particularly by microsphere surface residual double bonds, polymerization is adopted to be combined with silane coupling agent KH570, thus introduce silicone hydroxyl at microsphere surface, as a kind of platform, more multiple other specific function group that can combine with biomolecules can be introduced.5, the present invention adopts one kettle way to prepare fluorescent microsphere, makes to prepare the easy and simple to handle of fluorescent microsphere.6, the present invention uses micro-reaction to prepare fluorescent microsphere, makes to prepare the with low cost of fluorescent microsphere.
Near-ultraviolet polystyrene copolymerization fluorescence microsphere prepared by the present invention has high-quantum efficiency and wide spectral range, can be applicable to immune labeled context of detection, for the combination with subsequent biological.
Accompanying drawing explanation
Fig. 1 is the fluorescence emission spectrogram of the polystyrene copolymerization fluorescent microsphere that the embodiment of the present invention 1 provides.
Fig. 2 is the infrared absorption spectrum comparison diagram of the polystyrene microsphere that the functional near-ultraviolet polystyrene copolymerization fluorescence microsphere of sulfonic group, polystyrene copolymerization fluorescent microsphere and comparative example 1 that the embodiment of the present invention 1 provides provide.
Fig. 3 is the infrared absorption spectrum comparison diagram of the polystyrene microsphere that hydroxy-functional near-ultraviolet polystyrene copolymerization fluorescence microsphere, polystyrene copolymerization fluorescent microsphere and comparative example 1 that embodiment 2 provides provide.
Fig. 4 is the SEM figure of the blank microballoon that provides of comparative example 1 and embodiment 1 and fluorescent microsphere.
Fig. 5 is the shows fluorescent microscopy images of the fluorescent microsphere that embodiment 1 and embodiment 2 provide.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further elaborated.
Embodiment 1
Get Diisopropyl azodicarboxylate 0.024g, polyvinylpyrrolidone 0.072g respectively, dehydrated alcohol 9.0g is placed in microscale reactor, ultrasonic clear transparent solutions.Add vinylbenzene 1.2g, N-allyl carbazole 7.2mg, letting nitrogen in and deoxidizing, sealing.Be placed in constant temperature oscillator, at 70 DEG C, under 130rpm condition, react 12h.Priority water and ethanol repetitive scrubbing thus obtained microsphere, until after washings no longer detects fluorescence, namely 50 DEG C of vacuum-dryings obtain polystyrene copolymerization fluorescent microsphere.
Take above-mentioned polystyrene copolymerization fluorescent microsphere 1.0g, add vitriol oil 28mL, the ultrasonic fluorescent microsphere that makes disperses in concentrated sulfuric acid, 7h is reacted at 55 DEG C, wash sample with water to neutral, 50 DEG C of vacuum-dryings, obtain the functional near-ultraviolet polystyrene copolymerization fluorescence microsphere of sulfonic group.
Embodiment 2
Get Diisopropyl azodicarboxylate 0.028g, polyvinylpyrrolidone 0.067g respectively, dehydrated alcohol 9.8g is placed in microscale reactor, ultrasonic clear transparent solutions.Add vinylbenzene 1.4g, N-allyl carbazole 11.6mg, letting nitrogen in and deoxidizing, sealing.Be placed in constant temperature oscillator, at 70 DEG C, under 130rpm condition, react 12h.Priority water and ethanol repetitive scrubbing thus obtained microsphere, until after washings no longer detects fluorescence, namely 50 DEG C of vacuum-dryings obtain polystyrene copolymerization fluorescent microsphere.
Take 0.064gAIBN, be scattered in the mixed solvent of 25.6mL ethanol/deionized water (5: 1).Taking the above-mentioned polystyrene copolymerization fluorescent microsphere of 0.2g joins in mixed solvent, ultrasonic disperse.Letting nitrogen in and deoxidizing, adds gamma-methyl allyl acyloxypropyl trimethoxysilane 0.832g simultaneously, seals and shakes up.Be placed in constant temperature oscillator, 70 DEG C of violent jolting 30h.After reaction terminates, centrifugal with deionized water and ethanol repetitive scrubbing, 50 DEG C of vacuum-dryings, obtain hydroxy-functional near-ultraviolet polystyrene copolymerization fluorescence microsphere.
Comparative example 1
Get Diisopropyl azodicarboxylate 0.023g, polyvinylpyrrolidone 0.066g respectively, dehydrated alcohol 9.5g is placed in microscale reactor, ultrasonic clear transparent solutions.Add vinylbenzene 1.2g, letting nitrogen in and deoxidizing, sealing.Be placed in constant temperature oscillator, at 70 DEG C, under 130rpm condition, react 12h.Successively with second alcohol and water repetitive scrubbing thus obtained microsphere, namely 50 DEG C of vacuum-dryings obtain polystyrene microsphere.
Fig. 1 is the fluorescence emission spectrogram of polystyrene copolymerization fluorescent microsphere (3% is scattered in ethanol) prepared by embodiment 1, and as can be seen from Figure, under 328nm exciting light, the maximum emission wavelength of fluorescent microsphere is 365nm.
In Fig. 2, curve a is the infrared absorption spectrum of the functional near-ultraviolet polystyrene copolymerization fluorescence microsphere of sulfonic group prepared by embodiment 1, curve b is the infrared absorption spectrum of polystyrene copolymerization fluorescent microsphere prepared by embodiment 1, and curve c is the infrared absorption spectrum of polystyrene microsphere prepared by comparative example 1.Can be observed by curve a, 3446cm
-1it is the stretching vibration characteristic peak of O-H in sulfonic group; 3026cm
-1one group of obvious absorption peaks of left and right is the stretching vibration absorption peak of C-H on phenyl ring; 1169cm
-1, 1070cm
-1, 620cm
-1near have sulfonic charateristic avsorption band, prove sulfonic existence in sample; At fingerprint region 835cm
-1have the absorption peak of the last one, illustrate phenyl ring has di-substituted, 530cm
-1near absorption peak have obvious reinforcement, above-mentioned absorption peak describe effectively sulfonic group with phenyl ring generation chemical reaction, be bonded on polystyrene copolymerization fluorescent microsphere.Comparison curves b and c, the two is substantially the same, and this is that infrared spectrum can not symbolize the characteristic peak of fluorescence dye because in fluorescent microsphere, fluorescence dye content is few.
In Fig. 3, curve a is the infrared absorption spectrum of hydroxy-functional near-ultraviolet polystyrene copolymerization fluorescence microsphere prepared by embodiment 2, curve b is the infrared absorption spectrum of polystyrene copolymerization fluorescent microsphere prepared by embodiment 2, and curve c is the infrared absorption spectrum of polystyrene microsphere prepared by comparative example 1.Can be observed by curve a, 3026cm
-1the obvious absorption peak in one group, left and right is the stretching vibration absorption peak of C-H on phenyl ring; At 3458-3311cm
-1having the peak that is wide and weak, is the stretching vibration characteristic peak of O-H; 2924 and 2840cm
-1absorption peak be-CH
2stretching vibration characteristic absorbance; 1236-1182cm
-1then belong to Si-C, Si-O stretching vibration, these changes have absolutely proved on microsphere surface bonding gamma-methyl allyl acyloxypropyl trimethoxysilane (KH570).Comparison curves b and c, the two is substantially the same, and this is that infrared spectrum can not symbolize the characteristic peak of fluorescence dye because in fluorescent microsphere, fluorescence dye content is few.
In Fig. 4, A is the blank microballoon that comparative example 1 provides, and as seen from the figure, the blank microballoon of preparation has good sphericity and monodispersity is good, for preparation copolymerization fluorescent microsphere is laid a good foundation.Fig. 4 B is the fluorescent microsphere that embodiment 1 provides, and as can be seen from figure A and B, copolymerization fluorescent microsphere has substantially identical particle diameter and dispersiveness with blank microballoon.
In Fig. 5, A and B is the shows fluorescent microscopy images of the copolymerization fluorescent microsphere that embodiment 1 and embodiment 2 provide respectively.As seen from the figure, fluorescent microsphere has uniform luminescence feature, good sphericity and monodispersity, shows N-allyl carbazole and evenly styrene copolymerized, good stability.
Claims (4)
1. a preparation method for near-ultraviolet polystyrene copolymerization fluorescence microsphere, is obtain fluorescent microsphere by vinylbenzene and the copolymerization of N-allyl carbazole, then introduces sulfonic group or oh group respectively at microsphere surface, it is characterized in that adopting following method to prepare:
1), initiator Diisopropyl azodicarboxylate, polyethylene of dispersing agent pyrrolidone are placed in dehydrated alcohol and obtain clear transparent solutions, add vinylbenzene and N-allyl carbazole in solution simultaneously, under nitrogen protection, in 65 ~ 70 DEG C of copolyreaction 12 ~ 24h, obtain polystyrene copolymerization fluorescent microsphere; Wherein, the add-on of described N-allyl carbazole is 0.4 ~ 0.9% of vinylbenzene quality, and the consumption of initiator Diisopropyl azodicarboxylate is 1.8 ~ 2.3% of vinylbenzene quality, and the consumption of polyethylene of dispersing agent pyrrolidone is 4.6 ~ 6.2% of vinylbenzene quality;
2), get above-mentioned polystyrene copolymerization fluorescent microsphere and be scattered in the vitriol oil, 40 ~ 60 DEG C of reaction 6 ~ 8h, be washed to neutrality, drying obtains the functional near-ultraviolet polystyrene copolymerization fluorescence microsphere of sulfonic group; Or above-mentioned polystyrene copolymerization fluorescent microsphere, Diisopropyl azodicarboxylate and γ-methacryloxypropyl trimethoxy silane are scattered in aqueous ethanolic solution; 65 ~ 70 DEG C of reaction 24 ~ 36h under nitrogen protection, washing drying obtains hydroxy-functional near-ultraviolet polystyrene copolymerization fluorescence microsphere.
2. the preparation method of near-ultraviolet polystyrene copolymerization fluorescence microsphere according to claim 1, it is characterized in that described step 2) in hydroxy-functional near-ultraviolet polystyrene copolymerization fluorescence microsphere preparation in, the consumption of described γ-methacryloxypropyl trimethoxy silane is 2 ~ 7 times of polystyrene copolymerization fluorescent microsphere quality.
3. the preparation method of near-ultraviolet polystyrene copolymerization fluorescence microsphere according to claim 1, it is characterized in that described step 2) in hydroxy-functional near-ultraviolet polystyrene copolymerization fluorescence microsphere preparation in, the consumption of Diisopropyl azodicarboxylate is 0.24 ~ 0.48 times of polystyrene copolymerization fluorescent microsphere quality.
4. the preparation method of near-ultraviolet polystyrene copolymerization fluorescence microsphere according to claim 1, it is characterized in that described step 2) in hydroxy-functional near-ultraviolet polystyrene copolymerization fluorescence microsphere preparation in, described aqueous ethanolic solution be ethanol and water according to 5: 1 the solution that is mixed to get of volume ratio.
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Inventor after: Liu Qinghao Inventor after: Wang Yi Inventor after: Guo Jinchun Inventor after: Liu Hongyan Inventor after: Wang Junmei Inventor before: Liu Qinghao Inventor before: Guo Jinchun Inventor before: Liu Hongyan Inventor before: Wang Junmei |
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