CN103265657A - Method for preparing monodisperse polymer microspheres by photo-initiation precipitation polymerization - Google Patents
Method for preparing monodisperse polymer microspheres by photo-initiation precipitation polymerization Download PDFInfo
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Abstract
The invention discloses a method for preparing monodisperse polymer microspheres by photo-initiation precipitation polymerization. The method comprises the following steps of: adding a cross-linking agent and a comonomer in a 50 ml quartz reaction bottle respectively, adding a solvent, and then adding a photoinitiator in the reaction bottle; manually oscillating at room temperature until the mixture in the reaction bottle is completely dissolved; charging nitrogen in the reaction bottle to remove oxygen for 5 minutes, and then sealing the opening of the reaction bottle; fixing the reaction bottle on a rotating instrument, and irradiating the reaction bottle for 70-120 hours via a collecting lens; and centrifugally separating the mixed solution in the reaction bottle, washing the solid polymer obtained by centrifuging by acetone, tetrahydrofuran and ethanol, and then drying the solid polymer in an oven at 100 DEG C for 6 hours to obtain the monodisperse polymer microspheres having a particle size of 2-5 microns. The preparation method can be used for preparing monodisperse polymer microspheres with pure surfaces, without the need of a surfactant or a stabilizer.
Description
Technical field
The present invention relates to a kind of functional polymer microsphere preparation technology, especially light-initiated precipitation polymerization prepares the method for mono-disperse polymer microspheres.
Background technology
As everyone knows, monodisperse polymer micro-sphere is that a kind of particle diameter is in micron order, uniform spherical polymer.This type of microballoon can be widely used in fields such as fixing, the albumen sepn of chromatograph packing material, medicine controlled releasing, enzyme and standard metering, because its extensive prospect in association areas such as biology, medical science, cause lot of domestic and foreign experts and scholars' extensive concern, also obtained great progress.For example, abroad the someone has proposed to need not the precipitation polymerization process that tensio-active agent and stablizer prepare mono-dispersion microballoon, with Diisopropyl azodicarboxylate make initiator, acetonitrile is made solvent and be warming up to 70 ℃ of initiated polymerizations in airtight reaction flask, prepared the polydivinylbenezene mono-dispersion microballoon, and by copolymerization such as Vinylstyrene and acrylate and styrene monomers mono-dispersion microballoon.It is the precipitation polymerization that solvent has carried out DVB that domestic also someone proposes with acetic acid, and their result of study shows that further there is remarkably influenced in temperature of reaction to the microballoon form, can obtain spheroidal particle during 80 ℃ of polymerizations, then obtains the microballoon of pumpkin-shaped during 60 ℃ of polymerizations.In addition, also have Many researchers to utilize diverse ways also all to synthesize mono-disperse polymer microspheres, but still have some problems not solve.In recent years, along with the progressively enhancing of health of people environmental consciousness, the use of toxic chemicals more and more is restricted, and can become the bottleneck that precipitation polymerization is applied if continue the use toxic solvents after the scale production.And the confined reaction system of thermal initiation is adopted in present research more, studies show that, temperature of reaction seriously influences structure and the pattern existence of microballoon, and preparation mono-disperse polymer microspheres equipment is had higher requirement, and is unfavorable for the preparation of mono-disperse polymer microspheres.The investigator is also arranged in addition, the reaction method for preparing mono-disperse polymer microspheres with a kind of uv-light polymerization, though the advantage that this method has safety, can prepare at ambient temperature, but, need to add more stablizer in this reaction, after the reaction, microballoon is difficult to be purified, make that microsphere surface purity is lower, do not reach desirable requirement.
Summary of the invention
In order to overcome the in-problem deficiency of prior art, the invention provides the method that a kind of light-initiated precipitation polymerization prepares mono-disperse polymer microspheres.The method of this light-initiated precipitation polymerization need not tensio-active agent or stablizer, can prepare the pure mono-disperse polymer microspheres in surface.Can use hypotoxic ethanol to substitute toxic organic solvent and prepare monodisperse polymer micro-sphere.
The technical solution adopted for the present invention to solve the technical problems is: light-initiated precipitation polymerization prepares the method for mono-disperse polymer microspheres, and its needed raw material has:
Linking agent comprises Vinylstyrene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethyl-acrylate, and wherein one or both are compound.
Comonomer comprises: vinylbenzene, maleic anhydride, methacrylic ester, methacrylic acid and acrylamide, wherein one or both are compound.
Solvent comprises distilled water, ethanol, acetonitrile, toluene, butanone, normal hexane, tetrahydrofuran (THF), and wherein one or both are compound.
Light trigger comprises Diisopropyl azodicarboxylate, benzoyl peroxide, ammonium persulphate, and is wherein a kind of as light trigger.
The preparation method:
A, in 50ml quartz reaction bottle, add linking agent and comonomer respectively.The dosage of crosslinking agent scope is 1%-6%; The comonomer amount ranges is 1%-6%.
Also need add total amount is the 31.5-39.5g solvent, and keeping the concentration of monomer in solvent is 2%-8%.
In reaction flask, add the light trigger that concentration is 0.06%-0.40% more then.
B, at room temperature vibrate manually that mixture dissolves fully to the reaction flask.With reaction flask letting nitrogen in and deoxidizing sealed reaction bottleneck after 5 minutes, above-mentioned reaction flask is fixed on the gyroscope.Open gyroscope, the 150w xenon lamp shone reaction flask 70-120 hour by condensor under the room temperature.
C, stop irradiation after, with mixed solution centrifugation in the reaction flask, use acetone, tetrahydrofuran (THF) and the centrifugal gained solid polymer of washing with alcohol, be placed on then in 100 ℃ of baking ovens dry 6 hours, get the monodisperse polymer micro-sphere that particle diameter is 2-5 μ m.
The invention has the beneficial effects as follows that this light-initiated precipitation polymerization prepares the method for mono-disperse polymer microspheres, can use hypotoxic ethanol to substitute toxic organic solvent and prepare monodisperse polymer micro-sphere; In addition, for traditional thermal initiation technology, precipitation polymerization prepares mono-dispersion microballoon under the room temperature mild conditions with light-initiated technology generation, and this method can improve the above high yield mono-dispersion microballoon that obtains of monomer concentration to 6%, helps to promote large-scale production; The particularly important is, a kind of method of light-initiated precipitation polymerization is provided, need not tensio-active agent or stablizer, can prepare the pure mono-disperse polymer microspheres in surface.
Embodiment
Embodiment 1
A, in 50ml quartz reaction bottle, add weight 0.40g Vinylstyrene and etc. the maleic anhydride of weight, add the 32.20g butanone again, manually vibration at room temperature is to dissolving, and then with 7.648g butanone dissolving 0.016g light trigger Diisopropyl azodicarboxylate, join at last in the 50ml reaction flask.
B, at room temperature vibrate manually that mixture dissolves fully to the reaction flask.With reaction flask letting nitrogen in and deoxidizing sealed reaction bottleneck after 5 minutes, above-mentioned reaction flask is fixed on the gyroscope.Open gyroscope, the 150w xenon lamp shone reaction flask 120 hours by condensor under the room temperature.
C, stop the irradiation after, with mixed solution centrifugation in the reaction flask, use acetone, tetrahydrofuran (THF) and the centrifugal gained solid polymer of washing with alcohol, be placed on then in 100 ℃ of baking ovens dry 6 hours, getting particle diameter is the monodisperse polymer micro-sphere of 0.6 μ m, and its productive rate is 21%.
Embodiment 2
A, in 50ml quartz reaction bottle, add weight 0.80g trimethylolpropane trimethacrylate and etc. the vinylbenzene of weight, add 31.56g ethanol again, manually vibration at room temperature is to dissolving, and then with 7.496g dissolve with ethanol 0.032g light trigger Diisopropyl azodicarboxylate, all join in the 50ml reaction flask at last.
B, at room temperature vibrate manually that mixture dissolves fully to the reaction flask.With reaction flask letting nitrogen in and deoxidizing sealed reaction bottleneck after 5 minutes, above-mentioned reaction flask is fixed on the gyroscope.Open gyroscope, the 150w xenon lamp shone reaction flask 120 hours by condensor under the room temperature.
C, stop the irradiation after, with mixed solution centrifugation in the reaction flask, use acetone, tetrahydrofuran (THF) and the centrifugal gained solid polymer of washing with alcohol, be placed on then in 100 ℃ of baking ovens dry 6 hours, getting particle diameter is the monodisperse polymer micro-sphere of 1.2 μ m, and its productive rate is 70%.
Claims (2)
1. a light-initiated precipitation polymerization prepares the method for mono-disperse polymer microspheres, it is characterized in that: needed raw material has: linking agent comprises Vinylstyrene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethyl-acrylate, wherein one or both are compound, comonomer comprises: vinylbenzene, maleic anhydride, methacrylic ester, methacrylic acid and acrylamide, wherein one or both are compound, solvent comprises distilled water, ethanol, acetonitrile, toluene, butanone, normal hexane, tetrahydrofuran (THF), wherein one or both are compound, light trigger comprises Diisopropyl azodicarboxylate, benzoyl peroxide, ammonium persulphate, wherein a kind of as light trigger.
2. light-initiated precipitation polymerization according to claim 1 prepares the method for mono-disperse polymer microspheres, and its preparation method is:
A, in 50ml quartz reaction bottle, add linking agent and comonomer respectively, the dosage of crosslinking agent scope is 1%-6%; The comonomer amount ranges is 1%-6%, and adding total amount is the 31.5-39.5g solvent, and keeping the concentration of monomer in solvent is 2%-8%, adds the light trigger that concentration is 0.06%-0.40% more then in reaction flask,
B, at room temperature vibrate manually that mixture dissolves fully to the reaction flask, with reaction flask letting nitrogen in and deoxidizing sealed reaction bottleneck after 5 minutes, above-mentioned reaction flask is fixed on the gyroscope, open gyroscope, the 150w xenon lamp shone reaction flask 70-120 hour by condensor under the room temperature
C, stop irradiation after, with mixed solution centrifugation in the reaction flask, use acetone, tetrahydrofuran (THF) and the centrifugal gained solid polymer of washing with alcohol, be placed on then in 100 ℃ of baking ovens dry 6 hours, get the monodisperse polymer micro-sphere that particle diameter is 2-5 μ m.
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Cited By (7)
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| CN103435424A (en) * | 2013-09-02 | 2013-12-11 | 济宁道淼新材料科技有限公司 | Controlled release coating material containing polymer micro nanoparticles |
| CN104829770A (en) * | 2015-05-12 | 2015-08-12 | 天津大学 | Preparation method of crosslinked polystyrene |
| CN106432564A (en) * | 2016-09-13 | 2017-02-22 | 中国科学院过程工程研究所 | Method for preparing functional monodisperse polymer microsphere |
| CN108892747A (en) * | 2018-07-25 | 2018-11-27 | 重庆工程职业技术学院 | A kind of preparation method of poly-dopamine Methacrylamide microballoon |
| CN109134754A (en) * | 2018-07-25 | 2019-01-04 | 重庆工程职业技术学院 | A kind of antibacterial micro-nano particle and its preparation method and application having adhesive function |
| CN112877034A (en) * | 2021-01-25 | 2021-06-01 | 贝荣佳 | Environment-friendly flame-retardant composite material and preparation method thereof |
| CN113402663A (en) * | 2021-07-26 | 2021-09-17 | 上海微陌新材料科技有限公司 | Preparation method of maleic anhydride-styrene-alpha-methylstyrene-vinyl acetate copolymer |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435424A (en) * | 2013-09-02 | 2013-12-11 | 济宁道淼新材料科技有限公司 | Controlled release coating material containing polymer micro nanoparticles |
| CN103435424B (en) * | 2013-09-02 | 2016-03-30 | 济宁道淼新材料科技有限公司 | A kind of slow controlled release coated fertilizer of the pbz polymer micro-nano grain of rice |
| CN104829770A (en) * | 2015-05-12 | 2015-08-12 | 天津大学 | Preparation method of crosslinked polystyrene |
| CN106432564A (en) * | 2016-09-13 | 2017-02-22 | 中国科学院过程工程研究所 | Method for preparing functional monodisperse polymer microsphere |
| CN106432564B (en) * | 2016-09-13 | 2019-03-12 | 中国科学院过程工程研究所 | A method of preparing functionalization monodisperse polymer micro-sphere |
| CN108892747A (en) * | 2018-07-25 | 2018-11-27 | 重庆工程职业技术学院 | A kind of preparation method of poly-dopamine Methacrylamide microballoon |
| CN109134754A (en) * | 2018-07-25 | 2019-01-04 | 重庆工程职业技术学院 | A kind of antibacterial micro-nano particle and its preparation method and application having adhesive function |
| CN108892747B (en) * | 2018-07-25 | 2020-06-05 | 重庆工程职业技术学院 | Preparation method of polydopamine methacrylamide microsphere |
| CN109134754B (en) * | 2018-07-25 | 2020-06-05 | 重庆工程职业技术学院 | Antibacterial micro-nano particles with adhesion function and preparation method and application thereof |
| CN112877034A (en) * | 2021-01-25 | 2021-06-01 | 贝荣佳 | Environment-friendly flame-retardant composite material and preparation method thereof |
| CN112877034B (en) * | 2021-01-25 | 2023-12-01 | 山西大秦天创科技有限公司 | Environment-friendly flame-retardant composite material and preparation method thereof |
| CN113402663A (en) * | 2021-07-26 | 2021-09-17 | 上海微陌新材料科技有限公司 | Preparation method of maleic anhydride-styrene-alpha-methylstyrene-vinyl acetate copolymer |
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Application publication date: 20130828 |