CN103788526A - Preparation method of silver-loaded polymer microspheres - Google Patents
Preparation method of silver-loaded polymer microspheres Download PDFInfo
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- CN103788526A CN103788526A CN201410016060.2A CN201410016060A CN103788526A CN 103788526 A CN103788526 A CN 103788526A CN 201410016060 A CN201410016060 A CN 201410016060A CN 103788526 A CN103788526 A CN 103788526A
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Abstract
The invention belongs to the technical field of preparing composite materials, and concretely relates to a preparation method of silver-loaded polymer microspheres. The preparation method comprises the following steps: polymerizing a soap-free emulsion by a redox initiator to produce amino-containing polystyrene core-shell microspheres; adding AgNO3 solution into the microsphere solution, wherein silver ions are coordinated with amino groups on the surfaces of the microspheres, NaBH4 is in-situ reduced into silver nano particles, so as to obtain the silver-loaded polymer microspheres. The preparation method of the silver-loaded polymer microspheres is simple, the reaction condition is gentle, the stability of the microspheres is good, the size of the microspheres is controllable and in the range of 0.4-1.0 micron, and the particle size distribution of the microspheres is relatively uniform. The prepared polymer microspheres have high silver-carrying content in the range of 2.35-39.2%. The silver-loaded polymer microspheres can also be applied to bio-medical field and catalyst fields.
Description
Technical field
The invention belongs to matrix material preparing technical field, be specifically related to the preparation method of a kind of year silver-colored polymer microballoon.
Background technology
Complex microsphere refers to diameter at nano level to the coccoid between micron order, and the compound heterogeneous structure being made up of two or more material respectively interconnects by physics or chemical action between mutually.Complex microsphere is because the controllability of its form and structure composition has larger application development potentiality.Can be divided into organic-organic composite microspheres, organic-inorganic composite microballoons and inorganic-inorganic complex microsphere several types according to the difference of composition material.Nano silver grain has higher surfactivity and inhales the premium propertiess such as ripple, therefore have more wide application prospect in recent years in fields such as catalyzer, antibacterial, self-cleaning, pharmaceutical carrier, antistatic and absorbing materials, its preparation method and application have become the focus of research.Nano silver grain is loaded to polymer microballoon surface, obtain organic-inorganic composite microballoons, can strengthen stability and the dispersiveness of Nano silver grain.Thereby, carry the premium properties that silver-colored polymer composite microsphere has polymkeric substance and metallics simultaneously.
Nucleocapsid structure complex microsphere is to form respectively kernel and shell by two or more material, interconnects the compound heterogeneous structure of composition by physics or chemical action.The shell of core-shell material not only can be adjusted the surface property of particle, change its surface charge density, surfactivity, biocompatibility, stable and dispersed, can also pass through special gradient-structure, give interior karyomicrosome by distinctive outer shell particles catalytic activity, electric property, biological medicine performance and optical property etc. simultaneously.In the shell of microballoon, introduce functional group, as amido, utilize the coordination between functional group and silver atoms, can greatly improve the carrying capacity of microballoon to Nano silver grain, increase the stability of carrying silver-colored microballoon.Nucleocapsid structure carries silver-colored complex microsphere and has broad application prospects in fields such as biological medicine, assembled material, catalysis.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of year silver-colored polymer microballoon.
A preparation method for year silver-colored polymer microballoon, comprises the following steps:
1) polystyrene seed emulsion that is 10～15% by every 30～50g massfraction is mixed with functional monomer, the Vinylstyrene of 0.05～0.15g and the distilled water of 100ml of the vinylbenzene of 5.0～12.0g, 1.0～3.0g, stirring mixes it, mixing speed is 200～400r/min, then adds 1.0～3.0 × 10
-3the initiator of mol, logical nitrogen protection is reacted 2～6h, the cooling polystyrene core-shell microsphere obtaining with functional amido in the water bath with thermostatic control of 30～60 ℃;
2) get the above-mentioned microballoon of 5～20g, adding 5～10mL concentration is the AgNO of 5mM
3solution, stirs 8～16h under room temperature, stirring velocity 280r/min, and then adding 10～20mL concentration is the NaBH of 5mM
4solution, stirring reaction 1～3h, suction filtration, washing, dry, obtain carrying silver-colored polymer microballoon.
In step 1), the preparation of polystyrene seed emulsion adopts emulsifier-free emulsion polymerization method, and concrete steps are as follows:
The acrylamide of every 0.75～1.50g is mixed with the distilled water of 150mL; add the vinylbenzene of 10.5～20.5g; rapid stirring 10～30min; logical nitrogen protection; adding 5～10mL mass concentration is 5% Potassium Persulphate and sodium sulfite aqueous solution; in 60 ℃ of waters bath with thermostatic control, react 3h, obtain polystyrene seed emulsion.
Preferably, functional monomer described in step 1) is selected from the one in acrylamide, Methacrylamide, N methacrylamide, N-ethyl acrylamide.
Preferably, initiator described in step 1) is selected from the one in redox initiator Potassium Persulphate/S-WAT, ammonium persulphate/S-WAT, Potassium Persulphate/sodium bisulfite, Potassium Persulphate/Sulfothiorine.
What the preparation method of provided by the present invention year silver-colored polymer microballoon prepared carries silver-colored polymer microballoon, and the particle diameter of described year silver-colored polymer microballoon is between 0.4～1.0 micron, and size distribution is more even.
What the preparation method of provided by the present invention year silver-colored polymer microballoon prepared carries silver-colored polymer microballoon, and the silver content of described year silver-colored polymer microballoon is between 2.35～39.2%.
Year silver-colored polymer microballoon technique prepared by the present invention is simple, reaction conditions gentleness, and polymeric microspheres stabilize performance is good, and size is controlled, and particle diameter is between 0.4～1.0 micron, and size distribution is more even; Polymer microballoon silver carrying amount prepared by the present invention is high, and according to reaction conditions difference, microballoon sphere silver-carrying amount is between 2.35～39.2%; A year silver-colored polymer microballoon prepared by the present invention can be used for biomedical sector and catalytic field.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph that carries silver-colored polymer microballoon.
Embodiment
Below principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
The preparation of polystyrene seed emulsion: 0.78g acrylamide, 150mL distilled water are joined in the there-necked flask that agitator, reflux condensing tube and thermometer are housed; stirring at room temperature makes its dissolving; add 12.6g vinylbenzene; rapid stirring 20min; respectively adding 5mL mass concentration is 5% Potassium Persulphate and sodium sulfite aqueous solution; logical nitrogen protection, reacts 3h in 60 ℃ of waters bath with thermostatic control, obtains polystyrene seed emulsion.
Take the above-mentioned polystyrene seed emulsion of 30g, 7.5g vinylbenzene, 1.5g acrylamide and 0.1g Vinylstyrene, 100mL distilled water adds in there-necked flask, stir 10min, mixing speed is 380r/min, then adds 1.0 × 10
-3potassium Persulphate/S-WAT of mol, logical nitrogen protection, reacts 4h in 30 ℃ of waters bath with thermostatic control, stops heating, obtains the polystyrene core-shell microsphere with amido.
Take the above-mentioned microspheres solution of 20g, adding 5mL concentration is the AgNO of 5mM
3solution, stirs 16h under room temperature, stirring velocity 280r/min, and then adding 10mL concentration is the NaBH of 5mM
4, stirring reaction 2h, suction filtration, washing, dry, obtain carrying silver-colored polymer microballoon.
Fig. 1 is the stereoscan photograph that carries silver-colored polymer microballoon, as can be seen from the figure, the well-regulated globosity of complex microsphere tool, size distribution is more even.The median size that laser particle analyzer is measured polymer microballoon is 560nm, and size distribution index is 1.27.It is 10.2% that energy spectrum analysis obtains microsphere surface silver content.
Embodiment 2
Take the polystyrene seed emulsion 40g of the first step gained in routine l, 1.5 × 10
-3potassium Persulphate/Sulfothiorine of mol and 100mL distilled water join in 250mL there-necked flask; stir 10min; mixing speed is 350r/min; add Methacrylamide and the 0.12g Vinylstyrene of 9.0g vinylbenzene, 1.5g; logical nitrogen protection; in 50 ℃ of waters bath with thermostatic control, react 5h, stop heating, obtain the polystyrene core-shell microsphere with amido.
Take the above-mentioned polystyrene microsphere solution of 20g, adding 5mL concentration is the AgNO of 5mM
3solution, stirs 12h under room temperature, stirring velocity 280r/min, and then adding 10mL concentration is the NaBH of 5mM
4, stirring reaction 2h, suction filtration, washing, dry, obtain carrying silver-colored polymer microballoon.
The median size of polymer microballoon is 720nm, and size distribution index is 1.32.It is 15.2% that energy spectrum analysis obtains microsphere surface silver content.
Embodiment 3
Take the polystyrene seed emulsion 40g of the first step gained in routine l, 2.0 × 10
-3potassium Persulphate/Sulfothiorine of mol and 100mL distilled water join in 250mL there-necked flask; stir 10min; mixing speed is 300r/min; add N methacrylamide and the 0.12g Vinylstyrene of 12.0g vinylbenzene, 2.0g; logical nitrogen protection; in 60 ℃ of waters bath with thermostatic control, react 5h, stop heating, obtain the polystyrene core-shell microsphere with amido.
Take the above-mentioned microspheres solution of 30g, adding 10mL concentration is the AgNO of 5mM
3solution, stirs 16h under room temperature, stirring velocity 280r/min, and then adding 20mL concentration is the NaBH of 5mM
4, stirring reaction 2h, suction filtration, washing, dry, obtain carrying silver-colored polymer microballoon.
The median size of polymer microballoon is 780nm, and size distribution index is 1.54.It is 28.6% that energy spectrum analysis obtains microsphere surface silver content.
Embodiment 4
Take the polystyrene seed emulsion 50g of the first step gained in routine l, 3.0 × 10
-3ammonium persulphate/S-WAT of mol and 100mL distilled water join in 250mL there-necked flask; stir 10min; mixing speed is 380r/min; add the N-ethyl acrylamide of 12.0g vinylbenzene, 3.0g and the Vinylstyrene of 0.15g; logical nitrogen protection; in 60 ℃ of waters bath with thermostatic control, react 5h, stop heating, obtain the polystyrene core-shell microsphere with amido.
Take the above-mentioned microspheres solution of 30g, adding 10mL concentration is the AgNO of 5mM
3solution, stirs 16h under room temperature, stirring velocity 280r/min, and then adding 20mL concentration is the NaBH of 5mM
4, stirring reaction 2h, suction filtration, washing, dry, obtain carrying silver-colored polymer microballoon.
The median size of polymer microballoon is 842nm, and size distribution index is 1.44.It is 39.2% that energy spectrum analysis obtains microsphere surface silver content.
The foregoing is only preferred embodiments of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (5)
1. a preparation method of carrying silver-colored polymer microballoon, comprises the following steps:
1) polystyrene seed emulsion that is 10～15% by the massfraction of every 30～50g is mixed with functional monomer, the Vinylstyrene of 0.05～0.15g and the distilled water of 100ml of the vinylbenzene of 5.0～12.0g, 1.0～3.0g, stirring mixes it, mixing speed is 200～400r/min, then adds 1.0～3.0 × 10
-3the initiator of mol, logical nitrogen protection is reacted 2～6h, the cooling polystyrene core-shell microsphere obtaining with functional amido in the water bath with thermostatic control of 30～60 ℃;
2) get described polystyrene core-shell microsphere, in polystyrene core-shell microsphere, adding 5～10mL concentration described in every 5～20g is the AgNO of 5mM
3solution, stirs 8～16h under room temperature, stirring velocity 280r/min, and then adding 10～20mL concentration is the NaBH of 5mM
4solution, stirring reaction 1～3h, suction filtration, washing, dry, obtain carrying silver-colored polymer microballoon.
2. the preparation method of according to claim 1 year silver-colored polymer microballoon, is characterized in that: functional monomer described in step 1) is selected from the one in acrylamide, Methacrylamide, N methacrylamide, N-ethyl acrylamide.
3. the preparation method of according to claim 1 year silver-colored polymer microballoon, is characterized in that: initiator described in step 1) is selected from the one in redox initiator Potassium Persulphate/S-WAT, ammonium persulphate/S-WAT, Potassium Persulphate/sodium bisulfite, Potassium Persulphate/Sulfothiorine.
4. year silver-colored polymer microballoon preparing according to the arbitrary described preparation method of carrying silver-colored polymer microballoon of claims 1 to 3, is characterized in that: the particle diameter of described year silver-colored polymer microballoon is between 0.4～1.0 micron, and size distribution is more even.
5. year silver-colored polymer microballoon preparing according to the arbitrary described preparation method of carrying silver-colored polymer microballoon of claims 1 to 3, is characterized in that: the silver content of described year silver-colored polymer microballoon is between 2.35～39.2%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179508A (en) * | 2016-07-05 | 2016-12-07 | 潘江生 | A kind of unglazed according to quick potent decomposing formaldehyde catalysis material and preparation method thereof |
| CN106938194A (en) * | 2017-03-16 | 2017-07-11 | 天津大学 | A kind of synthetic method of single dispersing high catalytic performance solution state silver nano-grain and application |
| CN108704587A (en) * | 2018-05-14 | 2018-10-26 | 苏州知益微球科技有限公司 | A kind of preparation method for the magnetic microsphere that monodisperse is amido modified |
| TWI640565B (en) * | 2015-10-27 | 2018-11-11 | 諾兒朵股份有限公司 | Polymer latex particle composition containing nano silver particles |
| CN110586003A (en) * | 2019-07-30 | 2019-12-20 | 上海匡宇科技股份有限公司 | Composite microsphere and preparation method thereof |
| CN111728892A (en) * | 2020-08-14 | 2020-10-02 | 宋家豪 | Oil-control cosmetic cream for improving oily skin and preparation method thereof |
| CN112480478A (en) * | 2020-10-28 | 2021-03-12 | 厦门大学 | Preparation method and application of silver-loaded polymer microspheres |
| CN112604612A (en) * | 2020-12-03 | 2021-04-06 | 广东省科学院生物工程研究所 | Organic-inorganic raspberry-shaped structure microsphere and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6337131B1 (en) * | 1998-05-04 | 2002-01-08 | Basf Aktiengesellschaft | Core-shell particles and preparation and use thereof |
| DE19834194B4 (en) * | 1998-07-29 | 2009-03-05 | Basf Se | Colorant-containing dispersions of core / shell particles and core / shell particles |
| CN102165960A (en) * | 2010-11-29 | 2011-08-31 | 南开大学 | Preparation method of nano silver antibacterial mother liquor through two-step polymerization |
| CN102444027A (en) * | 2011-08-24 | 2012-05-09 | 翔瑞（泉州）纳米科技有限公司 | Antimicrobial fabric supported with nano silver core-shell polymer microsphere and preparation method thereof |
| CN103464203A (en) * | 2013-08-26 | 2013-12-25 | 陕西师范大学 | Preparation method of thermosensitive microgel asymmetric supported nano silver catalyst |
-
2014
- 2014-01-14 CN CN201410016060.2A patent/CN103788526B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6337131B1 (en) * | 1998-05-04 | 2002-01-08 | Basf Aktiengesellschaft | Core-shell particles and preparation and use thereof |
| DE19834194B4 (en) * | 1998-07-29 | 2009-03-05 | Basf Se | Colorant-containing dispersions of core / shell particles and core / shell particles |
| CN102165960A (en) * | 2010-11-29 | 2011-08-31 | 南开大学 | Preparation method of nano silver antibacterial mother liquor through two-step polymerization |
| CN102444027A (en) * | 2011-08-24 | 2012-05-09 | 翔瑞（泉州）纳米科技有限公司 | Antimicrobial fabric supported with nano silver core-shell polymer microsphere and preparation method thereof |
| CN103464203A (en) * | 2013-08-26 | 2013-12-25 | 陕西师范大学 | Preparation method of thermosensitive microgel asymmetric supported nano silver catalyst |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI640565B (en) * | 2015-10-27 | 2018-11-11 | 諾兒朵股份有限公司 | Polymer latex particle composition containing nano silver particles |
| CN106179508A (en) * | 2016-07-05 | 2016-12-07 | 潘江生 | A kind of unglazed according to quick potent decomposing formaldehyde catalysis material and preparation method thereof |
| CN106179508B (en) * | 2016-07-05 | 2018-09-07 | 甘肃润康药业有限公司 | A kind of quick potent decomposing formaldehyde catalysis material and preparation method thereof of no light |
| CN106938194A (en) * | 2017-03-16 | 2017-07-11 | 天津大学 | A kind of synthetic method of single dispersing high catalytic performance solution state silver nano-grain and application |
| CN106938194B (en) * | 2017-03-16 | 2020-03-27 | 天津大学 | Synthesis method and application of monodisperse high-catalytic-performance solution-state silver nanoparticles |
| CN108704587A (en) * | 2018-05-14 | 2018-10-26 | 苏州知益微球科技有限公司 | A kind of preparation method for the magnetic microsphere that monodisperse is amido modified |
| CN110586003A (en) * | 2019-07-30 | 2019-12-20 | 上海匡宇科技股份有限公司 | Composite microsphere and preparation method thereof |
| CN111728892A (en) * | 2020-08-14 | 2020-10-02 | 宋家豪 | Oil-control cosmetic cream for improving oily skin and preparation method thereof |
| CN112480478A (en) * | 2020-10-28 | 2021-03-12 | 厦门大学 | Preparation method and application of silver-loaded polymer microspheres |
| CN112604612A (en) * | 2020-12-03 | 2021-04-06 | 广东省科学院生物工程研究所 | Organic-inorganic raspberry-shaped structure microsphere and preparation method and application thereof |
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