CN101362068B - Precipitation polymerization preparation method of crosslinked polystyrene microspheres - Google Patents
Precipitation polymerization preparation method of crosslinked polystyrene microspheres Download PDFInfo
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- CN101362068B CN101362068B CN2008101659114A CN200810165911A CN101362068B CN 101362068 B CN101362068 B CN 101362068B CN 2008101659114 A CN2008101659114 A CN 2008101659114A CN 200810165911 A CN200810165911 A CN 200810165911A CN 101362068 B CN101362068 B CN 101362068B
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Abstract
The invention discloses a preparation method of monodisperse micron-scale crosslinked polystyrene microspheres. The preparation method is characterized in that: monomer styrene, divinyl benzene and zaodiisobutyronitrile as an initiator are dissolved in a mixed solvent formed by acetonitrile and butanol; nitrogen gas is fed into the obtained mixture to remove oxygen for 15 minutes; reaction is carried out with oscillation under stable temperature; the polymerization product is centrifugally separated, washed by anhydrous alcohol and dried till the weight is stable. The crosslinked polystyrene microspheres with good monodisperse performance, crosslinked degree reaching 64 percent and grain sizes arranging from 1 micron to 4 microns can be obtained by the preparation method disclosed by the invention. The preparation method is applicable to the fields, such as biological medication, electronic information, chromatographic separation, cosmetic and coatings.
Description
Technical field
The present invention relates to a kind of preparation method of mono dispersed micrograde high-crosslinking-degree polystyrene microsphere, belong to field of polymer microsphere materials.
Background technology
It is big that the monodisperse micron crosslinked polystyrene microballoon has specific area, adsorptivity is strong, the mechanical strength height, surface reaction activity is good, hydrophobicity, biodegradable is ungood, and the controllability of particle size is good, is not dissolved or swelling by common solvent, be convenient to use and plurality of advantages such as recovery, thereby in the application in fields such as standard metering, biomedicine, analytical chemistry, information, chemical industry and microelectronics more and more widely.In recent years, the preparation of monodisperse cross-linked polymer microspheres had become a focus in the polymer science field.
The conventional method of preparation polymer microballoon is suspension polymerization, emulsion polymerization and dispersion copolymerization method, and suspension polymerization generally is used for the bigger microballoon of preparation size, and product condenses easily, microspherulite diameter is distributed broaden; The microspherulite diameter that emulsion polymerization makes has an emulsifying agent less than residual in 0.5 micron and the product that obtains, and the use of emulsifying agent simultaneously can cause environmental pollution; The dispersion copolymerization method production technology is simple relatively, and adaptability is strong, and product cut size is controlled, and the particle diameter narrow distribution still, uses dispersion copolymerization method to be difficult to obtain the polymer microballoon of stable high-crosslinking-degree.The seed swelling method also is a kind of more common method for preparing microballoon, but seed swelling method complex steps, condition harshness, consuming time tediously long, application is narrower.
Precipitation polymerization method can prepare single polymer microballoon that disperses high-crosslinking-degree, and this method to have reaction system simple, emulsifier free or stabilizing agent, instrument and equipment is simple, operating condition is easily controlled, many advantages such as the pure and post processing of product is easy, thus precipitation polymerization method in recent years extremely people pay close attention to.But in common precipitation polymerization method, used solvent is an acetonitrile, and acetonitrile meets the requirement of precipitation polymerization method, is the single good solvent that disperses the high-crosslinking-degree polymer microballoon of preparation.But the toxicity of acetonitrile is big, and too much use meeting causes very big pollution to environment.In reaction system, add the toxicity that cosolvent can reduce solvent for use, reduce environmental pollution.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, and a kind of method for preparing the monodisperse micron crosslinked polystyrene microballoon in the less relatively mixed solvent of being made up of acetonitrile and n-butanol of toxicity is provided.
Purpose of the present invention can reach by following measure: a kind of preparation method of monodisperse micron crosslinked polystyrene microballoon, it is characterized in that: with monomer styrene and divinylbenzene, the initator azodiisobutyronitrile is dissolved in the mixed solvent of acetonitrile and n-butanol composition, wherein, the consumption of styrene and divinylbenzene is 0.5～4% of a mixed solvent cumulative volume, the divinylbenzene consumption is 20～90% of a monomer cumulative volume, initiator amount is 0.5～4% of a monomer gross mass, and the volume of n-butanol is 5～40% of a solvent cumulative volume.Logical then nitrogen deoxygenation 15 minutes, the vibration heating at 60～80 degrees centigrade, under 20～120 rev/mins of frequencies of oscillation, was reacted 12～28 hours, and polymerizate is through centrifugation, and absolute ethanol washing is dried to constant weight.
The volume fraction that the styrene among the present invention and the consumption of divinylbenzene account for the mixed solvent cumulative volume preferably 1～3%.
The volume fraction that the consumption of the monomer divinylbenzene among the present invention accounts for the monomer cumulative volume preferably 30～80%.
The mass fraction that initiator amount among the present invention accounts for the monomer gross mass preferably 1～3%.
The volume fraction that the volume of the n-butanol among the present invention accounts for the solvent cumulative volume preferably 5～30%.
Preferably 65～75 degrees centigrade of polymeric reaction temperatures among the present invention.
Preferably 40～100 rev/mins of frequencies of oscillation among the present invention.
Preferably 16～24 hours reaction time among the present invention.
Compared with the prior art the present invention has following advantage: preparation method provided by the invention is simple and easy to do, do not need to add any emulsifying agent and stabilizing agent in the reaction system, only need simple vibration heating, by one-step method, can obtain the mono dispersed micrograde high-crosslinking-degree polystyrene microsphere in the appropriate particle size scope.Under the prerequisite that keeps the particle diameter monodispersity, introduce the cosolvent n-butanol, reduced the consumption of acetonitrile, reduced the toxicity of solvent for use.
Description of drawings
Fig. 1 is the electron scanning micrograph of the crosslinked polystyrene microsphere of embodiment 1.
Fig. 2 is the electron scanning micrograph of the crosslinked polystyrene microsphere of embodiment 2.
The specific embodiment
Describe the present invention below in detail and provide several embodiment:
Embodiment 1
With 47.5 milliliters of acetonitriles, 2.5 milliliters of n-butanols, 0.35 milliliter of styrene, 0.15 milliliter of divinylbenzene and azodiisobutyronitrile 0.0136 gram mix, logical nitrogen deoxygenation 15 minutes, 40 rev/mins of constant oscillation frequency, 65 degrees centigrade were reacted 16 hours.Polymerizate is through centrifugation, and absolute ethanol washing is dried to constant weight.
Gained polystyrene microsphere average grain diameter is 1.22 microns, and the degree of cross linking is 24%, and monodispersity is good, and its electron scanning micrograph as shown in Figure 1.
Embodiment 2
With 45 milliliters of acetonitriles, 5 milliliters of n-butanols, 0.25 milliliter of styrene, 0.25 milliliter of divinylbenzene and azodiisobutyronitrile 0.0048 gram mix, logical nitrogen deoxygenation 15 minutes, 70 rev/mins of constant oscillation frequency, 70 degrees centigrade were reacted 24 hours.Polymerizate is through centrifugation, and absolute ethanol washing is dried to constant weight.
Gained polystyrene microsphere average grain diameter is 1.67 microns, and the degree of cross linking is 40%, and monodispersity is good, and its electron scanning micrograph as shown in Figure 2.
Embodiment 3
With 47.5 milliliters of acetonitriles, 2.5 milliliters of n-butanols, 1.05 milliliters of styrene, 0.45 milliliter of divinylbenzene and azodiisobutyronitrile 0.0135 gram mix, logical nitrogen deoxygenation 15 minutes, 100 rev/mins of constant oscillation frequency, 75 degrees centigrade were reacted 24 hours.Polymerizate is through centrifugation, and absolute ethanol washing is dried to constant weight.
Gained polystyrene microsphere average grain diameter is 2.20 microns, and the degree of cross linking is 24%, and monodispersity is good.
Embodiment 4
With 35 milliliters of acetonitriles, 15 milliliters of n-butanols, 0.3 milliliter of styrene, 1.2 milliliters of divinylbenzenes and azodiisobutyronitrile 0.0133 gram mix, logical nitrogen deoxygenation 15 minutes, 100 rev/mins of constant oscillation frequency, 75 degrees centigrade were reacted 24 hours.Polymerizate is through centrifugation, and absolute ethanol washing is dried to constant weight.
Gained polystyrene microsphere average grain diameter is 2.54 microns, and the degree of cross linking is 64%, and monodispersity is good.
Embodiment 5
With 45 milliliters of acetonitriles, 5 milliliters of n-butanols, 0.375 milliliter of styrene, 0.375 milliliter of divinylbenzene and azodiisobutyronitrile 0.0101 gram mix, logical nitrogen deoxygenation 15 minutes, 70 rev/mins of constant oscillation frequency, 70 degrees centigrade were reacted 20 hours.Polymerizate is through centrifugation, and absolute ethanol washing is dried to constant weight.
Gained polystyrene microsphere average grain diameter is 1.56 microns, and the degree of cross linking is 40%, and monodispersity is good.
Embodiment 6
With 35 milliliters of acetonitriles, 15 milliliters of n-butanols, 0.1 milliliter of styrene, 0.4 milliliter of divinylbenzene and azodiisobutyronitrile 0.0139 gram mix, logical nitrogen deoxygenation 15 minutes, 40 rev/mins of constant oscillation frequency, 65 degrees centigrade were reacted 16 hours.Polymerizate is through centrifugation, and absolute ethanol washing is dried to constant weight.
Gained polystyrene microsphere average grain diameter is 2.14 microns, and the degree of cross linking is 64%, and monodispersity is good.
Claims (8)
1. the preparation method of a monodisperse micron crosslinked polystyrene microballoon, it is characterized in that: with monomer styrene and divinylbenzene, the initator azodiisobutyronitrile is dissolved in the mixed solvent of acetonitrile and n-butanol composition, wherein, the consumption of styrene and divinylbenzene is 0.5～4% of a mixed solvent cumulative volume, the divinylbenzene consumption is 20～90% of a monomer cumulative volume, initiator amount is 0.5～4% of a monomer gross mass, the volume of n-butanol is 5～40% of a solvent cumulative volume, logical nitrogen deoxygenation 15 minutes, the vibration heating, polymeric reaction temperature is 60～80 degrees centigrade, frequency of oscillation is 20～120 rev/mins, reaction time is 12～28 hours, polymerizate is through centrifugation, and absolute ethanol washing is dried to constant weight.
2. the preparation method of a kind of monodisperse micron crosslinked polystyrene microballoon according to claim 1 is characterized in that: the consumption of described monomer styrene and divinylbenzene is 1～3% of a mixed solvent cumulative volume.
3. the preparation method of a kind of monodisperse micron crosslinked polystyrene microballoon according to claim 1 is characterized in that: the consumption of divinylbenzene is 30～80% of a monomer cumulative volume.
4. the preparation method of a kind of monodisperse micron crosslinked polystyrene microballoon according to claim 1 is characterized in that: initiator amount is 1～3% of a monomer gross mass.
5. the preparation method of a kind of monodisperse micron crosslinked polystyrene microballoon according to claim 1 is characterized in that: the volume of n-butanol is 5～30% of a solvent cumulative volume.
6. the preparation method of a kind of monodisperse micron crosslinked polystyrene microballoon according to claim 1 is characterized in that: polymeric reaction temperature is 65～75 degrees centigrade.
7. the preparation method of a kind of monodisperse micron crosslinked polystyrene microballoon according to claim 1 is characterized in that: frequency of oscillation is 40～100 rev/mins.
8. the preparation method of a kind of monodisperse micron crosslinked polystyrene microballoon according to claim 1 is characterized in that: the reaction time is 16～24 hours.
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| CN102898572B (en) * | 2012-10-31 | 2014-03-19 | 济南大学 | Preparation method of high-crosslinking monodisperse poly divinylbenzene microspheres |
| CN104250327A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Method for preparing particle size-controllable high-crosslinked monodispersed polydivinylbenzene microspheres |
| CN106478857A (en) * | 2016-10-14 | 2017-03-08 | 北京海岸鸿蒙标准物质技术有限责任公司 | For calibrating standard substance of airborne particle counter and preparation method thereof |
| CN112724295B (en) * | 2020-12-28 | 2022-07-19 | 济南国科医工科技发展有限公司 | Synthesis method of micron-sized polystyrene microspheres |
| CN114591460B (en) * | 2022-03-26 | 2023-09-26 | 浙江工业大学 | Method for preparing carboxylated crosslinked polystyrene based on precipitation polymerization |
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