CN102675501A - Method for preparing monodisperse polystyrene microspheres with controllable particle size - Google Patents
Method for preparing monodisperse polystyrene microspheres with controllable particle size Download PDFInfo
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- CN102675501A CN102675501A CN2012101893762A CN201210189376A CN102675501A CN 102675501 A CN102675501 A CN 102675501A CN 2012101893762 A CN2012101893762 A CN 2012101893762A CN 201210189376 A CN201210189376 A CN 201210189376A CN 102675501 A CN102675501 A CN 102675501A
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Abstract
The invention belongs to the field of biomedicine and particularly discloses a method for preparing monodisperse polystyrene microspheres with a controllable particle size. The method is characterized by comprising the following steps of: adding water and emulsifier into a three-necked flask, stirring a solution until the solution is clarified, introducing nitrogen to replace air in the reaction system, adding a certain amount of monomers, emulsifying for 0.5 to 2.5 hours, heating to reaction temperature of between 65 and 90 DEG C, stirring again, dripping an initiating agent under the protection of nitrogen, and performing polymerization reaction for 12 to 48 hours; and stopping reaction to obtain emulsion particles, performing centrifugal sedimentation by using an ultracentrifuge, discarding supernate, adding absolute ethanol, performing ultrasonic dispersion, repeating the steps for 3 to 4 times, pouring washed microspheres into culture dish, putting in a vacuum drying oven, and drying to obtain polymer microspheres. Compared with the prior art, the method for preparing the monodisperse polystyrene microspheres with the controllable particle size has the advantages that raw materials are low in cost and can be obtained easily; the process is simple; and the prepared monodisperse polystyrene microspheres with the controllable particle size can be applied to the field of biomedicine, micro electronic techniques and the like well.
Description
Technical field
The invention belongs to biomedical sector, the preparation method of the controlled monodisperse polystyrene microsphere of a kind of specifically particle diameter.
Background technology
Along with of the application of monodisperse polymer microballoon in fields such as biomedicine, analytical chemistry, chromatographic technique, microelectronicss; In decades in the past; Investigators have done a lot of researchs to obtaining the controlled monodisperse polymer microballoon of particle diameter both at home and abroad, have wherein also obtained a lot of achievements.
For example: some science households use 2, and 2-azo (2-methyl-propyl amidine) dihydrochloride is made initiator, has obtained the top condition of polyreaction through the consumption of monomeric consumption, initiator, the potential of hydrogen of reaction system.Some scientists join a kind of amphoterics dimethyl-dodecyl ammonium inner salt in the reaction system of vinylbenzene, Potassium Persulphate, water in initial reaction stage, and the result prepares that median size reaches 3.4um and size distribution is relatively poor.
USP, publication number: US5006617, open 1991 04 month 09 date; Proposed to prepare the method for emulsion particle with alkene class base unsaturated monomer through emulsifier-free emulsion polymerization, the latex distribution of sizes of preparation is between 0.02um-5um.It is the monodisperse cross-linked phenylethylene micro ball of 4-7um that thereby some scientists use two step of seed swelling technology to prepare particle diameter.Also have some scientists to utilize the distillation precipitation polymerization method to prepare the monodisperse cross-linked polystyrene microsphere of particle diameter for 2-3um.Also having some scientists is dispersion agent with the polyvinyl pyrrolidone; Diisopropyl azodicarboxylate is an initiator; Alcohol, water mixture are dispersion medium; Prepare PS with dispersion copolymerization method, studied initial monomer concentration, dispersant dosage, initiator concentration, dispersion medium is formed and the influence of reaction conditions resulting polymers microspherulite diameter such as temperature of reaction and size distribution comprehensively.
And above method concrete operations more complicated, the prices of raw and semifnished materials are expensive, to having relatively high expectations of some instrument, for common biological pharmaceutical manufacturer, can't promote the use of.
[summary of the invention]
The present invention provides the preparation method of the controlled monodisperse polystyrene microsphere of a kind of particle diameter in order to overcome the deficiency of prior art.
To achieve these goals, the present invention has designed the preparation method of the controlled monodisperse polystyrene microsphere of a kind of particle diameter, it is characterized in that: comprise the steps; Add entry and emulsifying agent in the there-necked flask, stirred solution to solution is clarified, and feeds the air of nitrogen replacement reaction system; The monomer that adds certain amount again emulsification 0.5-2.5 hour, rises to temperature of reaction 65-90 ℃; Restir, and under protection of nitrogen gas, drip initiator, polyreaction 12-48 hour;
Termination reaction promptly gets emulsion particle, ultracentrifuge centrifugal settling, and abandoning supernatant adds the absolute ethyl alcohol ultrasonic dispersing, and preceding road step repeats 3-4 time, pours the microballoon after the washing in petridish vacuum drying oven oven dry, promptly gets polymer microballoon.
The particle size distribution range of described polymer microballoon 50 to 300nm.
Described monomer is 100g, and its composition is the mixture of vinylbenzene or vinylbenzene and other comonomer.
Described emulsifying agent is one or more mixtures in sodium lauryl sulphate, PS pyrrolidone, the oleic acid.
Described initiator is 0.5g, and its composition is a kind of in persulphate and the Diisopropyl azodicarboxylate.
The existence form of described polymer microballoon is that latex disperses or pressed powder in deionized water.
The present invention compares with prior art, has following characteristics:
1, can obtain the controlled monodisperse polystyrene microsphere of particle diameter simply through regulating monomer concentration, emulsifying agent consumption, temperature of reaction, emulsification times, initiator amount, reaction times, prepare particle size distribution range between 50-300nm.
2, this preparing method's raw material cheap, be easy to get, technology is simple, plant and instrument is required low, cost is low, the controlled monodisperse polystyrene microsphere of the particle diameter of preparation can be good at being applied to fields such as biomedicine, analytical chemistry, chromatographic technique, microelectronics.
[embodiment]
Further describe in the face of the present invention down.
Embodiment one:
In there-necked flask, add 1000ml water and 150mg emulsifying agent, stirred solution to solution is clarified, and feeds the air of nitrogen replacement reaction system; The monomer that adds 200g again, this monomer staple are the mixture of vinylbenzene or vinylbenzene and other comonomer, and this interpolymer is one or more mixtures in vinylformic acid, methylacrylic acid, ester OH, sodium sulfonate, the propenal; Emulsification 0.5-2.5 hour; Rise to temperature of reaction 65-90 ℃, stirring, and under protection of nitrogen gas, dripping the 1.0g initiator; This initiator staple is persulphate or Diisopropyl azodicarboxylate, polyreaction 12-48 hour.Termination reaction promptly gets emulsion particle.
Through ultracentrifuge centrifugal settling, abandoning supernatant adds the absolute ethyl alcohol ultrasonic dispersing again, repeats above-mentioned steps 3 to 4 times.Pour the microballoon after the washing in petridish vacuum drying oven oven dry, promptly get polymer microballoon.Better through microballoon ball-type property in the projection electron microscopic observation emulsion, present good monodispersity.Measure microspherulite diameter through the size distribution appearance and distribute, median size is at 302nm, and CV is 8.9%.
Embodiment two:
In there-necked flask, add 1000ml water and 180mg emulsifying agent, stirred solution to solution is clarified, and feeds the air of nitrogen replacement reaction system; The monomer that adds 150g again, this monomer staple are the mixture of vinylbenzene or vinylbenzene and other comonomer, and this interpolymer is one or more mixtures in vinylformic acid, methylacrylic acid, ester OH, sodium sulfonate, the propenal; Emulsification 0.5-2.5 hour, rise to temperature of reaction 65-90 ℃, restir; And under protection of nitrogen gas, drip the 0.8g initiator; This initiator staple is persulphate or Diisopropyl azodicarboxylate, and polyreaction 12-48 hour, termination reaction promptly got emulsion particle.
Through ultracentrifuge centrifugal settling, abandoning supernatant adds the absolute ethyl alcohol ultrasonic dispersing again, after above step repeats 3 to 4 times, pours the microballoon after the washing in petridish vacuum drying oven oven dry, promptly gets polymer microballoon.Better through microballoon ball-type property in the projection electron microscopic observation emulsion, present good monodispersity.Measure microspherulite diameter through the size distribution appearance and distribute, median size is at 147nm, and CV is 6.2%.
Embodiment three:
In there-necked flask, add 1000ml water and 220mg emulsifying agent, stirred solution to solution is clarified, and feeds the air of nitrogen replacement reaction system; The monomer that adds 120g again, this monomer staple are the mixture of vinylbenzene or vinylbenzene and other comonomer, and this interpolymer is one or more mixtures in vinylformic acid, methylacrylic acid, ester OH, sodium sulfonate, the propenal; Emulsification 0.5-2.5 hour, rise to temperature of reaction 65-90 ℃, stirring; And under protection of nitrogen gas, drip the 0.5g initiator; This initiator staple is persulphate or Diisopropyl azodicarboxylate, and polyreaction 12-48 hour, termination reaction promptly got emulsion particle.
Through ultracentrifuge centrifugal settling, abandoning supernatant adds the absolute ethyl alcohol ultrasonic dispersing again, and centrifugal again washing more so repeats 3 to 4 times, pours the microballoon after the washing in petridish vacuum drying oven oven dry, promptly gets polymer microballoon.Better through microballoon ball-type property in the projection electron microscopic observation emulsion, present good monodispersity.Measure microspherulite diameter through the size distribution appearance and distribute, median size is at 98nm, and CV is 10.4%.
Embodiment four:
In there-necked flask, add 1000ml water and 240mg emulsifying agent, stirred solution to solution is clarified, and feeds the air of nitrogen replacement reaction system; The monomer that adds 100g again, monomer whose staple are the mixture of vinylbenzene or vinylbenzene and other comonomer, and this interpolymer is one or more mixtures in vinylformic acid, methylacrylic acid, ester OH, sodium sulfonate, the propenal; Emulsification 0.5-2.5 hour; Rise to temperature of reaction 65-90 ℃, under stirring and protection of nitrogen gas, drip the 0.5g initiator, this initiator staple is persulphate or Diisopropyl azodicarboxylate; Polyreaction 12-48 hour, termination reaction promptly got emulsion particle.
Through ultracentrifuge centrifugal settling, abandoning supernatant adds the absolute ethyl alcohol ultrasonic dispersing again, after above step repeats 3 to 4 times, pours the microballoon after the washing in petridish vacuum drying oven oven dry, promptly gets polymer microballoon.Better through microballoon ball-type property in the projection electron microscopic observation emulsion, present good monodispersity.Measure microspherulite diameter through the size distribution appearance and distribute, median size is at 52nm, and CV is 8.6%.
Claims (7)
1. the preparation method of the controlled monodisperse polystyrene microsphere of particle diameter is characterized in that: comprise the steps, add entry and emulsifying agent in the there-necked flask; Stirred solution to solution is clarified, and feeds the air of nitrogen replacement reaction system, adds the monomer of certain amount again; Emulsification 0.5-2.5 hour, rise to temperature of reaction 65-90 ℃, restir; And under protection of nitrogen gas, drip initiator, polyreaction 12-48 hour;
Termination reaction promptly gets emulsion particle, ultracentrifuge centrifugal settling, and abandoning supernatant adds the absolute ethyl alcohol ultrasonic dispersing, and preceding road step repeats 3-4 time, pours the microballoon after the washing in petridish vacuum drying oven oven dry, promptly gets polymer microballoon.
2. the preparation method of the controlled monodisperse polystyrene microsphere of a kind of particle diameter according to claim 1 is characterized in that: the particle size distribution range of described polymer microballoon is 50 to 300nm.
3. the preparation method of the controlled monodisperse polystyrene microsphere of a kind of particle diameter according to claim 1 and 2 is characterized in that: described monomer is 100g, and its composition is the mixture of vinylbenzene or vinylbenzene and other comonomer.
4. the preparation method of the controlled monodisperse polystyrene microsphere of a kind of particle diameter according to claim 3 is characterized in that: described comonomer is one or more mixtures in vinylformic acid, methylacrylic acid, ester OH, sodium sulfonate, the propenal.
5. the preparation method of the controlled monodisperse polystyrene microsphere of a kind of particle diameter according to claim 1 and 2 is characterized in that: described emulsifying agent is one or more mixtures in sodium lauryl sulphate, PS pyrrolidone, the oleic acid.
6. the preparation method of the controlled monodisperse polystyrene microsphere of a kind of particle diameter according to claim 1 and 2 is characterized in that: described initiator is 0.5g, and its composition is a kind of in persulphate and the Diisopropyl azodicarboxylate.
7. the preparation method of the controlled monodisperse polystyrene microsphere of a kind of particle diameter according to claim 1 and 2 is characterized in that: the existence form of described polymer microballoon is that latex disperses or pressed powder in deionized water.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628922A (en) * | 2014-09-30 | 2015-05-20 | 青岛科技大学 | Preparation method of ultra-high molecular weight polystyrene used for selective laser sintering rapid formation |
| CN105384856A (en) * | 2015-12-10 | 2016-03-09 | 重庆三零三科技有限公司 | Preparation method of polystyrene microsphere |
| CN106947026A (en) * | 2017-03-31 | 2017-07-14 | 中国科学院宁波材料技术与工程研究所 | A kind of method that utilization Dual Surfactants prepare monodisperse polystyrene microsphere |
| CN107936167A (en) * | 2017-12-21 | 2018-04-20 | 苏州希尔盖森新材料有限公司 | One kind has hydrophilic polystyrene microsphere |
| CN108072688A (en) * | 2017-12-22 | 2018-05-25 | 扬州大学 | A kind of preparation method of the biosensor of protein Sensitive Detection |
| CN108132351A (en) * | 2017-12-22 | 2018-06-08 | 扬州大学 | A kind of nano-probe device of Raman enhancing protein detection and preparation method thereof |
| CN109988333A (en) * | 2019-04-04 | 2019-07-09 | 成都爱兴生物科技有限公司 | A kind of polystyrene microsphere |
| CN110357999A (en) * | 2019-06-26 | 2019-10-22 | 华南理工大学 | A kind of nano carboxy polystyrene microsphere and its preparation method and application |
| CN114773515A (en) * | 2022-03-29 | 2022-07-22 | 中触媒新材料股份有限公司 | Preparation method of submicron carboxyl functionalized polystyrene microspheres |
| CN114923837A (en) * | 2015-02-09 | 2022-08-19 | 弹弓生物科学公司 | Hydrogel particles with tunable optical properties and methods of using the same |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628922A (en) * | 2014-09-30 | 2015-05-20 | 青岛科技大学 | Preparation method of ultra-high molecular weight polystyrene used for selective laser sintering rapid formation |
| CN114923837A (en) * | 2015-02-09 | 2022-08-19 | 弹弓生物科学公司 | Hydrogel particles with tunable optical properties and methods of using the same |
| CN105384856A (en) * | 2015-12-10 | 2016-03-09 | 重庆三零三科技有限公司 | Preparation method of polystyrene microsphere |
| CN106947026A (en) * | 2017-03-31 | 2017-07-14 | 中国科学院宁波材料技术与工程研究所 | A kind of method that utilization Dual Surfactants prepare monodisperse polystyrene microsphere |
| CN107936167A (en) * | 2017-12-21 | 2018-04-20 | 苏州希尔盖森新材料有限公司 | One kind has hydrophilic polystyrene microsphere |
| CN108072688A (en) * | 2017-12-22 | 2018-05-25 | 扬州大学 | A kind of preparation method of the biosensor of protein Sensitive Detection |
| CN108132351A (en) * | 2017-12-22 | 2018-06-08 | 扬州大学 | A kind of nano-probe device of Raman enhancing protein detection and preparation method thereof |
| CN108132351B (en) * | 2017-12-22 | 2020-05-15 | 扬州大学 | Nano probe device for Raman enhanced protein detection and preparation method thereof |
| CN109988333A (en) * | 2019-04-04 | 2019-07-09 | 成都爱兴生物科技有限公司 | A kind of polystyrene microsphere |
| CN110357999A (en) * | 2019-06-26 | 2019-10-22 | 华南理工大学 | A kind of nano carboxy polystyrene microsphere and its preparation method and application |
| CN114773515A (en) * | 2022-03-29 | 2022-07-22 | 中触媒新材料股份有限公司 | Preparation method of submicron carboxyl functionalized polystyrene microspheres |
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