CN102358783B - Preparation method of polystyrene/gold composite microspheres - Google Patents
Preparation method of polystyrene/gold composite microspheres Download PDFInfo
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- CN102358783B CN102358783B CN2011102120409A CN201110212040A CN102358783B CN 102358783 B CN102358783 B CN 102358783B CN 2011102120409 A CN2011102120409 A CN 2011102120409A CN 201110212040 A CN201110212040 A CN 201110212040A CN 102358783 B CN102358783 B CN 102358783B
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Abstract
The invention relates to a preparation method of polystyrene/gold composite microspheres, which comprises the following steps: modifying polystyrene microspheres with a silane coupling agent, mixing with a chloroauric acid solution, and heating to carry out ionic selfassembly, wherein gold ions are fixed to the surface of the polystyrene microspheres through gold-nitrogen bonds; and after the solution is boiling, adding trisodium citrate to reduce the gold ions adsorbed onto the amino group in situ, thereby generating the core-shell structure in which a gold nanoparticle is coated on each polystyrene microsphere. The size of the gold particles and the coverage percentage of the gold particles on the polystyrene microspheres are controllable to some extent.
Description
Technical field
The invention belongs to the nano-functional material technical field, be specifically related to a kind of preparation method of polystyrene/Au complex microsphere.
Background technology
Composite nano materials not only has the characteristic of each composition material, also has new performance, has enlarged the range of application of material.Wherein concrete unique pattern, structure and physicochemical characteristic of the polystyrene/Au complex microsphere of nucleocapsid structure is expected to be used widely at aspects such as catalysis, photosensor, TEMP, surface enhanced Raman scattering effect, immunodetection.Therefore, the research to its preparation, performance and application always is one of problem that the material scholars make earnest efforts.The preparation method of polystyrene/Au complex microsphere directly affects the performance of complex microsphere, generally adopts self-assembly method, local reduction way etc.
Self-assembly method is at the polyelectrolyte or the molecular radical of the outside of polystyrene microsphere absorption one deck band xenogenesis electric charge, utilizes static or specific chemical bond, and the surface that gold nano grain is fixed to polystyrene microsphere forms nucleocapsid structure.To gather 4-SSS (PSS) like F. Caruso etc. combines with polymine (PEI) and forms the multilayer tamanori of polyelectrolyte (PE); Controlled polystyrene/Au complex microsphere (reference 1:Chem. Mater, 2003. 15 (16): p. 3176-3183) of preparation shell.Jiang etc. have synthesized a kind of dendritic tensio-active agent C18N3; This tensio-active agent has a plurality of amine; Utilize the mutual electrostatic force of hydrophobic group of hydrophilic radical and carbochain, can be self-assembled into vesicle, around polystyrene microsphere, form bilayer structure (reference 2:J. Phys. Chem. B; 2008. 112 (5): p. 1409-1413); It is come bonding gold grain and polystyrene microsphere as tamanori and tensio-active agent, form PSC18N3Au (reference 3:Nanotechnology, 2010. 21:p. 085501).Shi, W etc. modify carboxylic acid terminated polystyrene microsphere with 2-aminoothyl mercaptan hydrochloride (AET), form peptide bond on the polystyrene microsphere surface with hydroxy-acid group, finally stop with mercaptan.Gold nano grain and sulfydryl attract each other, and are deposited on (reference 4:Langmuir, 2005. 21 (4): p. 1610-1617) on the polystyrene microsphere.
In addition, Wang Zhaoqun etc. have proposed a kind of literalness construction from part, and the polystyrene microsphere that directly will not carry out any modification joins in the ebullient aqueous solution of chloraurate, adds reductive agent again, and the gold grain of generation just is assembled into the surface of polystyrene microsphere.This method has been avoided the finishing of p-poly-phenyl ethene microballoon, has simplified preparation process (reference 5: one Chinese patent application number 201010018270.7).
Gold nano grain in the local reduction way does not prepare in advance, but in-situ reducing generates in reaction.PS can prepare in advance, also can in recombination process, form.Behind polystyrene microsphere and gold ion chelating, reduce gold ion with reductive agent, just can make matrix material.Chang for example, C etc. use vinylbenzene, Potassium Persulphate, water (St/KPS/H
2O) carry out the letex polymerization of surfactant-free, prepare with sulfate radical terminated polystyrene microsphere.The sulfate radical on polystyrene microsphere surface both can be used as the reduction of metal ion agent, was again the stablizer of metallic colloid; Avoid use (reference 6:Colloid & Polymer Science, 2010. 288 (4): p. 395-403) of other reductive agents dexterously.
Above-mentioned traditional preparation method has their own characteristics each, but also exists certain shortcoming.Self-assembly method (LbL) can obtain the polyelectrolyte of single or multiple lift layer by layer, and fraction of coverage is high, simple to operate, but pilot process need be wasted time and energy repeatedly.Reference 5 literalness polystyrene microsphere surface-assembled gold grains though simplify step, will inevitably influence homogeneity and controllability that gold grain distributes on polystyrene microsphere.And the associativity of local reduction way gold grain and polystyrene microsphere is poor, fraction of coverage is low, greatly affects pattern, structure and the characteristic of polystyrene/Au complex microsphere.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of a kind of fraction of coverage polystyrene/Au complex microsphere high, simultaneously easy and simple to handle.
The present invention has developed a kind of preparation method of polystyrene/Au complex microsphere on self-assembly method and local reduction way basis, process is: the amino or the sulfydryl modification of (1) p-poly-phenyl ethene microsphere surface; (2) the coordination chemistry effect through taking place and be adsorbed on polystyrene microsphere surface (self assembling process) with the functional group of modifying in gold ion; (3) the in-situ reducing gold ion forms golden shell.The particle diameter of gold nano grain and coating degree have certain controllability.
Core technology thought of the present invention is: avoided gold grain to be assembled on the polystyrene microsphere through static or the chemical bonding effect of classics; Adopted the chemical coordination under the ionic condition, make gold ion more rapidly, more firmly with modify after polystyrene microsphere combine; Guarantee reaction uniformity, controllability.In addition, can also control accurately, realize further regulation and control the complex microsphere pattern to the particle diameter and the coating degree of gold nano grain.
Preparing method's concrete steps of polystyrene/Au complex microsphere proposed by the invention are following:
1, polystyrene microsphere can adopt the emulsion polymerization preparation; With alcohol-water mixed solution is medium, and sodium lauryl sulphate is an emulsifying agent, and Potassium Persulphate is an initiator; Under stirring and argon shield condition, be the controlled monodispersed polystyrene microsphere of surface cleaning, particle diameter with monomer polymerization.Also can prepare polystyrene microsphere with other ordinary method.Polystyrene microsphere is dispersed in the ethanol of volume(tric)fraction 70 ~ 98% after cleaning, and is made into the emulsion of PS;
2, be that the methoxy silane of amino or sulfydryl or the ethanolic soln of Ethoxysilane coupling agent are added drop-wise in the polystyrene emulsion with functional end-group; Stirring at room is reacted more than 2 h, guarantees that modification reaction fully carries out; After centrifugal and cleaning, in the aqueous solution, disperse then;
3, in the PS aqueous solution of finishing, drip chlorauric acid solution, stir, be warming up to the solution boiling again, add the reductive agent of gold ion rapidly, react more than 30 min, then through centrifugal, clean back acquisition polystyrene/Au complex microsphere.
Through test of many times, the optimum condition of discovery is:
The polystyrene microsphere particle diameter that is used for preparing polystyrene emulsion is less than 500 nm.
The concentration of polystyrene emulsion is 1 mg/ml, and as the volumes of aqueous ethanol fractional bits 70% ~ 98% of solvent, preferably 95%.Silane coupling agent can with the water hydrolytic reactions, generate corresponding silanol.Here adopt the ethanol of this scope water cut, for the hydrolysis of silane suitable condition is provided exactly.But also to consider that the dispersiveness of PS and solvent cannot destroy PS pattern, structure.
Among the present invention, the silane coupling agent volume(tric)fraction is 2% ethanolic soln, and solution usage is 0.4 ml/20 mg polystyrene microsphere.
The silane coupling agent that p-poly-phenyl ethene microballoon is modified uses the 3-aminopropyl triethoxysilane.
Among the present invention, aqueous solution of chloraurate concentration is 1 wt%, and amount of aqueous solution used is 0.8 ml/20 mg polystyrene microsphere.
Among the present invention, said reductive agent can be trisodium citrate, xitix, Sodium Citrate, tannic acid, oxammonium hydrochloride, boron sodium oxide, Hydrazine Hydrate 80 etc.
Among the present invention, trisodium citrate aqueous solution concentration is 1 wt%, and solution usage is 1 ~ 4 times of aqueous solution of chloraurate.
In the test, the complex microsphere that the electron microscopic observation reaction obtains finds that gold nano grain is evenly attached to the polystyrene microsphere surface.The particle diameter of gold nano grain is 6-10 nm.
Preparing method's of the present invention characteristics are: (1) chlorauric acid solution and amidized polystyrene microsphere thorough mixing, and utilize the coordination between amino and the gold ion to form gold-nitrogen key, make gold ion fully attached to the polystyrene microsphere surface.(2) gold ion is reduced on the surface of polystyrene microsphere, makes firm absorption and equally distributed gold nano grain, has simplified operation steps.(3) have particle diameter and the controllability that coats degree, can be through the consumption of regulating hydrochloro-auric acid, the consumption of reductive agent etc., thus obtain the polystyrene/Au nucleocapsid structure complex microsphere of different-shape and performance.(4) the ammoxidation time whether fully, also directly have influence on the modification situation on polystyrene microsphere surface, thereby influence the pattern of polystyrene/Au nucleocapsid structure complex microsphere.
The inventive method combines the advantage of self-assembly and in-situ reducing method, has proposed amido modified polystyrene microsphere and hydrochloro-auric acid radical ion thorough mixing, reductive preparation method then.Realized self-assembly in the ion aspect, and at security deposit's particle on polystyrene microsphere surface evenly, in fine and close the coating, the particle diameter and the fraction of coverage of gold nano grain are precisely regulated and control.Polystyrene microsphere has more attachment point through amido modified than literalness PS, and the golden stratum nucleare that makes is finer and close, and gold grain is more even.Contrast traditional self-assembly, the method for the direct mixed polystyrene/Au complex microsphere that gets of promptly amidized polystyrene microsphere and gold nano grain need not to prepare in advance gold colloid, greatly simplifies the preparation process, shortens preparation time.
Description of drawings
The transmission electron micrograph of the polystyrene/Au complex microsphere of Fig. 1 embodiment 1 preparation.
The transmission electron micrograph of the polystyrene/Au complex microsphere of Fig. 2 embodiment 2 preparations.
The transmission electron micrograph of the polystyrene/Au complex microsphere of Fig. 3 embodiment 3 preparations.
The transmission electron micrograph of the polystyrene/Au complex microsphere of Fig. 4 embodiment 4 preparations.
The transmission electron micrograph of the polystyrene/Au complex microsphere of Fig. 5 embodiment 5 preparations.
The transmission electron micrograph of the polystyrene/Au complex microsphere of Fig. 6 embodiment 6 (traditional self-assembly method) preparation.
Embodiment
Embodiment 1:
In three-necked flask, 0.0244 g sodium lauryl sulphate and 0.0222 g Potassium Persulphate are dissolved in the mixing solutions of ethanol (95%)/water (50ml:20ml), under argon shield, stir.In solution, drip styrene monomer 1 ml that cleaned by 10% sodium hydroxide solution, be heated to 70 ℃, react 8 h.Reaction finishes the back spinning, cleans 3 times with ethanol; Use volume(tric)fraction 95% ethanol as solvent, be made into the ethanolic soln of the polystyrene microsphere of 1 mg/ml.The particle diameter of the polystyrene microsphere that reaction obtains is about 300 nm.
Under the room temperature, be in the PS ethanolic soln of the ethanolic soln of the 3-aminopropyl triethoxysilane of 1:49 1 mg/ml that joins 20 ml with the volume ratio of 0.4 ml.Magnetic agitation is reacted 2 h.Amidized polystyrene microsphere is dispersed in the distilled water after repeatedly cleaning through spinning and with ethanol, is made in the aqueous solution of 1 mg/ml, leaves standstill 25h, fully disperses.
Under the room temperature, the aqueous solution of chloraurate of 1 wt% of 0.8 ml is added drop-wise in the amidized PS aqueous solution, magnetic agitation is warming up to boiling, adds the trisodium citrate aqueous solution of 1 wt% of 3.2 ml, reacts 30 min, and reacted system is a grape.The polystyrene/Au complex microsphere repeatedly cleans through spinning and with distilled water.Transmission electron microscope show product be gold nano grain evenly, densely attached to the polystyrene microsphere surface, the median size of gold nano grain is 10.9 ± 2.1 nm; And the gold colloid particles number of single polystyrene microsphere surface adsorption is about 312.
Embodiment 2:
Adopt the 300 nm polystyrene emulsion and the amidized PS aqueous solution among the embodiment 1, leave standstill 13h, fully disperse.
Under the room temperature, the aqueous solution of chloraurate of 1 wt% of 0.6 ml is added drop-wise in the amidized PS aqueous solution, magnetic agitation is warming up to boiling, adds the trisodium citrate aqueous solution of 1 wt% of 2.4 ml, reacts 30 min, and reacted system is a grape.The polystyrene/Au complex microsphere repeatedly cleans through spinning and with distilled water.Transmission electron microscope show product be gold nano grain evenly, densely attached to the polystyrene microsphere surface, the median size of gold nano grain is 8.0 ± 2.0 nm.And the gold colloid particles number of single polystyrene microsphere surface adsorption is about 413.
Embodiment 3:
Adopt the 300 nm polystyrene emulsion and the amidized PS aqueous solution among the embodiment 1, leave standstill 22h, fully disperse.
Under the room temperature, the aqueous solution of chloraurate of 1 wt% of 0.2 ml is added drop-wise in the amidized PS aqueous solution, magnetic agitation is warming up to boiling, adds the trisodium citrate aqueous solution of 1 wt% of 0.8 ml, reacts 30 min, and reacted system is a red-purple.The polystyrene/Au complex microsphere repeatedly cleans through spinning and with distilled water.Transmission electron microscope shows that product is that gold nano grain is surperficial attached to polystyrene microsphere equably, and the median size of gold nano grain is 6.5 ± 1.8 nm.And the gold colloid particles number of single polystyrene microsphere surface adsorption is about 140.
Embodiment 4:
Adopt 300 nm polystyrene microspheres of preparation among the embodiment 1,, leave standstill 24 h, fully disperse its aqueous solution that is made into the PS of 1 mg/ml.
Under the room temperature; 1% the aqueous solution of chloraurate of 0.8 ml is added drop-wise in the not amidized PS aqueous solution of 20 ml, and magnetic agitation is warming up to boiling, adds the trisodium citrate aqueous solution of 1 wt% of 3.2 ml; React 30 min, reacted system color is that watermelon is red.The polystyrene/Au complex microsphere repeatedly cleans through spinning and with distilled water.Transmission electron microscope shows that product is not of uniform size, the out-of-shape of gold nano grain, sparsely attached to the polystyrene microsphere surface.
Embodiment 5:
Adopt 300 nm polystyrene microspheres of preparation among the embodiment 1, use volume(tric)fraction 95% ethanol, be made into the ethanolic soln of the polystyrene microsphere of 1 mg/ml as solvent.
Under the room temperature, be in the PS ethanolic soln of the ethanolic soln of the 3-aminopropyl triethoxysilane of 1:49 1 mg/ml that joins 20 ml with the volume ratio of 0.4 ml.Magnetic agitation is reacted 30 min.Amidized polystyrene microsphere is dispersed in the distilled water after repeatedly cleaning through spinning and with ethanol, is made in the aqueous solution of 1 mg/ml, leaves standstill 20 h, fully disperses.
Under the room temperature, the aqueous solution of chloraurate of the 1wt% of 0.8 ml is added drop-wise in the amidized PS aqueous solution, magnetic agitation is warming up to boiling, adds the trisodium citrate aqueous solution of 1 wt% of 3.2 ml, reacts 30 min, and reacted system is a wine red.The polystyrene/Au complex microsphere repeatedly cleans through spinning and with distilled water.Transmission electron microscope shows that product differs greatly for the gold nano grain size, and shape is very irregular, more thick and fast attached to the polystyrene microsphere surface.
Embodiment 6:
Polystyrene microsphere 40 mg of the particle diameter that makes 500 nm are dispersed in volume(tric)fraction 95% ethanol, are made into the solution of 1 mg/ml.The ethanolic soln (1:49) of the 3-aminopropyl triethoxysilane of 0.2 ml is added drop-wise in the ethanolic soln of polystyrene microsphere magnetic agitation 40 min.
Measure 50 ml distilled waters and add in the flask, add the aqueous solution of chloraurate of 1 wt% of 0.5 ml.Stir, during the solution boiling, add sodium citrate soln 2 ml of 1 wt% rapidly.Keep boiling 30 min.Reaction system is a red-purple.Through transmission electron microscope observation, gold colloid is spherical, and particle diameter is between 6.5-8 nm.
Get the amidized polystyrene microsphere ball aqueous solution 5 ml and mix, shake up 10 min with the gold colloid of 15 ml.Through transmission electron microscope observation,, there is not unnecessary gold to be scattered though gold grain all is adsorbed on the polystyrene microsphere; But the distribution of gold colloid on polystyrene microsphere is very inhomogeneous, and gold grain is easy on the polystyrene microsphere surface reunite, and the degree of absorption on the different polystyrene microspheres is also different.
Claims (8)
1. the preparation method of a polystyrene/Au complex microsphere is characterized in that comprising the steps:
1) polystyrene microsphere is dispersed in the ethanol of volume(tric)fraction 70 ~ 98%, is made into the emulsion of PS;
2) be that the methoxy silane of amino or sulfydryl or the ethanolic soln of Ethoxysilane coupling agent are added drop-wise in the polystyrene emulsion with functional end-group, stirring at room is reacted more than 2 h, after centrifugal and cleaning, in the aqueous solution, disperses then;
3) in the PS aqueous solution of finishing, drip chlorauric acid solution, stir, be warming up to the solution boiling again, add the reductive agent of gold ion, react more than 30 min, then through centrifugal, clean back acquisition polystyrene/Au complex microsphere.
2. preparation method according to claim 1, the polystyrene microsphere particle diameter that it is characterized in that being used for preparing polystyrene emulsion is less than 500 nm.
3. preparation method according to claim 1 and 2, the concentration that it is characterized in that polystyrene emulsion is 1 mg/ml.
4. preparation method according to claim 1 and 2 is characterized in that silane coupler solution is volume ratio 2% ethanolic soln, and solution usage is 0.4 ml/20 mg polystyrene microsphere.
5. preparation method according to claim 1 and 2 is characterized in that the silane coupling agent that p-poly-phenyl ethene microballoon is modified, and uses the 3-aminopropyl triethoxysilane.
6. preparation method according to claim 1 and 2 is characterized in that aqueous solution of chloraurate concentration is 1 wt%, and solution usage is 0.8 ml/20 mg polystyrene microsphere.
7. preparation method according to claim 1 and 2 is characterized in that said reductive agent is trisodium citrate, xitix, tannic acid, oxammonium hydrochloride, boron sodium oxide, Hydrazine Hydrate 80.
8. preparation method according to claim 7 is characterized in that trisodium citrate aqueous solution concentration is 1 wt%, and solution usage is 1 ~ 4 times of aqueous solution of chloraurate.
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| CN108676365A (en) * | 2018-04-09 | 2018-10-19 | 南京捷纳思新材料有限公司 | A kind of synthetic method of the polymer microballoon of nanogold doping |
| CN111732739B (en) * | 2020-07-02 | 2022-04-01 | 长春工业大学 | Preparation method of monodisperse polymer metal composite conductive microspheres |
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