CN1298751C - Process for synthesis of monodisperse micron crosslinked polystyrene copolymerization microsphere - Google Patents
Process for synthesis of monodisperse micron crosslinked polystyrene copolymerization microsphere Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 32
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 12
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 12
- 238000007334 copolymerization reaction Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 title abstract description 7
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002612 dispersion medium Substances 0.000 claims abstract description 4
- 238000012674 dispersion polymerization Methods 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 8
- 238000006392 deoxygenation reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 5
- 230000006641 stabilisation Effects 0.000 claims description 4
- 238000011105 stabilization Methods 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 238000005304 joining Methods 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229960003511 macrogol Drugs 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 4
- 239000003381 stabilizer Substances 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002307 Dextran Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- MWRBNPKJOOWZPW-GPADLTIESA-N 1,2-di-[(9E)-octadecenoyl]-sn-glycero-3-phosphoethanolamine Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OC[C@H](COP(O)(=O)OCCN)OC(=O)CCCCCCC\C=C\CCCCCCCC MWRBNPKJOOWZPW-GPADLTIESA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- -1 alkyl (methyl) acrylate Chemical compound 0.000 description 1
- QDHUQRBYCVAWEN-UHFFFAOYSA-N amino prop-2-enoate Chemical class NOC(=O)C=C QDHUQRBYCVAWEN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
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Abstract
The present invention discloses a synthesizing method of a monodisperse crosslinked polystyrene copolymerized microsphere, which belongs to the range of the preparation technology of new high molecular materials. Azodiisobutyronitrile (AIBN) as an initiator and polyethylene glycol 200 dimethacrylae (PEG200DMA) as a crosslinking agent are dissolved in a styrene monomer; polyvinylpyrrolidone (PVP) as a stabilizing agent is dissolved in ethanol as a dispersion medium so as to carry out dispersion polymerization; crosslinked powder is obtained after separation and drying. The crosslinking agent of PEG20DMA is used to replace a common crosslinking agent, namely DVB, which improves the stability of a reaction system. The function of the stabilizing agent is favorable for forming the monodisperse crosslinked microsphere. When the content of the crosslinking agent reaches 2.5% of the monomer, the functional group of the PEG200DMA enriches on the surface of the microsphere so as to obtain a uniform monodisperse crosslinked functional microsphere in a petal shape. The microsphere can be widely used as a catalyst carrier in medical and medicine fields, biochemistry fields and fields of electronic message materials.
Description
Technical field
The invention belongs to the novel high polymer material preparation field, particularly a kind of synthetic method of monodisperse cross-linked polystyrene copolymerization microsphere.
Technical background
Specific physiques such as polymer microsphere has good sphericity, size is little, specific surface area is big, adsorptivity reaches functional group by force at surface enrichment, and the surface reaction ability is strong.Polymer microsphere can be applied to high sophisticated technology field, as medical treatment and field of medicaments, and biochemical field, electronic information material field etc.Solvent resistance, the thermotolerance of common polymer microsphere are low, have limited its application aspect a lot.How preparing crosslinked mono-disperse polymer microspheres becomes the focus of research and development.The seed swelling method is the common methods of preparation microballoon, but this method needs polystep reaction, and the time cycle is long, and preparation process is loaded down with trivial details.Therefore people attempt introducing cross-linking monomer in reaction system, and the method that adopts a step dispersion copolymerization to close prepares crosslinked microsphere.
Disclose at present the patented technologies such as preparation method, new system of many polymer crosslinked microspheres, in US5714237, adopted polycomponent C4-C14 alkyl (methyl) acrylate and some function monomer copolymerization, prepared partial cross-linked high polymer elastic microballoon.In JP2286729, will be scattered in the magnetic particle pre-emulsification in the aqueous solution in vinyl-arene and the crosslinked Emulgating polymers earlier, repolymerization can obtain a kind of magnetic core, and the composite macromolecule microsphere of hydrophobicity cross-linked polymer shell can be applicable to biological field.In US487394, by selecting appropriate solvent, polymerization reaction take place in containing the solution of at least a cross-linking monomer is prepared crosslink macromolecule microsphere.J.W.Kim is at document " Colloid polymer Sic; 1998; 276:870-878 " in addition. deliver the polymer microsphere research that is entitled as " High monodisperse crosslinked polystyrene microparticles bydispersion polymerization ", this article utilizes amino acrylates to make linking agent, makes crosslinked polystyrene microsphere by dispersion copolymerization method.Wu Qiye etc. are at " plastics industry; 2000; 28 (3): 21-23 " report " the emulsifier-free emulsion polymerization method is synthesized monodisperse cross-linked P S Nano microsphere ", and this article has synthesized nano-level crosslinked microballoon by the emulsifier-free emulsion polymerization method, and has studied the influence factor of particle diameter and polymolecularity.Guo Yuhan etc. deliver the article that is entitled as " the synthetic and sign of the monodisperse cross-linked P MM of surface hydrophilicity granularity A resin " on " polymer journal; 2000,5:641-643 ", this article seed swelling polymerization process has synthesized the monodispersed crosslinked polymethylmethacrylaparticles microballoon of granularity.With microballoon by hydrolysis, make it be converted into the resin of surface band carboxyl, with compound of polysaccharide Dextran and DEAE Dextran coating is carried out on the hydrolytic resin surface respectively, carry out crosslinkedly then with n-butyleneglycol DEPE respectively, prepare two kinds of surfaces and be with the tectal resin of high cross-linked polysaccharides.
Summary of the invention
Purpose of the present invention provides a kind of synthetic method of monodisperse cross-linked polystyrene copolymerization microsphere, it is characterized in that: adopt linking agent Macrogol 200 dimethyl double methacrylate PEG200DMA to replace common linking agent divinylbenzene DVB, improved the stability of reaction system, because it helps stabilization, helps forming mono-dispersion microballoon.Initiator Diisopropyl azodicarboxylate AIBN, linking agent PEG200DMA are dissolved in the monomer styrene, stablizer polyvinylpyrrolidone PVP are dissolved in carry out dispersion polymerization in the dispersion medium ethanol.After separating, drying, promptly obtain micron-sized monodisperse polystyrene microsphere powder; Its processing step is:
1) remove stopper in the styrene monomer: with 10wt%NaOH solution with equal-volume than joining in the separating funnel that fills styrene monomer, wash styrene monomer, the vibration precipitation discards lower floor's liquid, repeats 2 times, washes with water 3-4 time again; Complete with anhydrous sodium sulfate drying then, make water content to 0.5wt%;
2) the stablizer polyvinylpyrrolidone that takes by weighing the 7wt%-12wt% of styrene monomer is dissolved in the 75wt% ethanol, take by weighing the initiator Diisopropyl azodicarboxylate of the 1wt%-3wt% of styrene monomer, the 1wt%-3wt% linking agent PEG200DMA of styrene monomer is dissolved in the styrene monomer of 25wt%, above liquid mixes respectively, and is stand-by;
3) ethanolic soln of PVP is transferred to 250ml and is equipped with in the four-hole boiling flask of thermometer, mechanical stirrer and prolong, feed Ar gas, flow 16ml/min-20ml/min, deoxygenation 30min.
4) be warming up to 60-80 ℃ then,, begin reaction by constant pressure funnel drip styrene monomer solution.
5) reaction finished in 16-20 hour, and the gained emulsion is separated with whizzer, removes the upper strata stillness of night, adds ethanol and water washing again, and 3-5 time repeatedly, oven drying at low temperature in 40 ℃ of baking ovens makes water content to 0.5wt%, and sub-microballoon powder can secure satisfactory grades.
Beneficial effect of the present invention: adopt linking agent PEG200DMA to replace common linking agent DVB, improved the stability of reaction system,, help forming monodisperse cross-linked microballoon because it helps stabilization.In addition, after its content is to monomeric 2.5%, can obtain " petal-shaped " microballoon of homogeneous, the microballoon of this special appearance then is the result of the functional group of PEG200DMA in the microsphere surface enrichment.So, can make a kind of monodisperse cross-linked functional microsphere by adding linking agent PEG200DMA.
Description of drawings
The cross-linked styrene microsphere particle surface topography (SEM) of Fig. 1 for obtaining in the example 1.
The cross-linked styrene microsphere particle surface topography (SEM) of Fig. 2 for obtaining in the example 3.
Embodiment
Purpose of the present invention provides a kind of synthetic method of monodisperse cross-linked polystyrene copolymerization microsphere, it is characterized in that: adopt linking agent PEG200DMA to replace common linking agent DVB, improved the stability of reaction system,, helped forming mono-dispersion microballoon because it helps stabilization.Initiator A IBN, linking agent PEG200DMA are dissolved in the monomer styrene, the stablizer polyvinylpyrrolidone are dissolved in carry out dispersion polymerization in the dispersion medium ethanol.After separating, drying, promptly obtain micron-sized monodisperse polystyrene microsphere powder; Its processing step is:
1) remove stopper in the styrene monomer: with 10wt%NaOH solution with equal-volume than joining in the separating funnel that fills styrene monomer, wash styrene monomer, the vibration precipitation discards lower floor's liquid, repeats 2 times, washes with water 3-4 time again; Complete with anhydrous sodium sulfate drying then, make water content to 0.5wt%;
2) the stablizer polyvinylpyrrolidone that takes by weighing the 7wt%-12wt% of styrene monomer is dissolved in the 75wt% ethanol, take by weighing the initiator Diisopropyl azodicarboxylate of the 1wt%-3wt% of styrene monomer, the 1wt%-3wt% linking agent PEG200DMA of styrene monomer is dissolved in the styrene monomer of 25wt%, above liquid mixes respectively, and is stand-by;
3) ethanolic soln of PVP is transferred to 250ml and is equipped with in the four-hole boiling flask of thermometer, mechanical stirrer and prolong, feed Ar gas, flow 16ml/min-20ml/min, deoxygenation 30min.;
4) be warming up to 60-80 ℃ then,, begin reaction by constant pressure funnel drip styrene monomer solution.
5) reaction finished in 16-20 hour, and the gained emulsion is separated with whizzer, removes the upper strata stillness of night, adds ethanol and water washing again, and 3-5 time repeatedly, oven drying at low temperature in 40 ℃ of baking ovens makes water content to 0.5wt%, and sub-microballoon powder can secure satisfactory grades.
Lifting specific embodiment is below again further specified the present invention.
Embodiment 1
Styrene monomer 25g, ethanol 75g, polyvinylpyrrolidone 2.5g, Diisopropyl azodicarboxylate 0.25g, linking agent PEG200DMA 0.25g feeds Ar deoxygenation 30min in ethanolic soln, be warming up to 70 ℃,, begin reaction by constant pressure funnel drip styrene monomer solution.React end in 18 hours, can obtain the crosslinked microsphere of median size 3.15 μ m, wherein the dispersion coefficient of particle diameter is 0.025, and monodispersity is good.
Embodiment 2
Styrene monomer 25g, ethanol 75g, polyvinylpyrrolidone 2.5g, Diisopropyl azodicarboxylate 0.25g, linking agent PEG200DMA 0.38g feeds Ar deoxygenation 30min in ethanolic soln, be warming up to 70 ℃,, begin reaction by constant pressure funnel drip styrene monomer solution.React end in 18 hours, can obtain the crosslinked microsphere of median size 3.26 μ m, wherein the dispersion coefficient of particle diameter is 0.026, and monodispersity is good.
Embodiment 3
Styrene monomer 25g, ethanol 75g, polyvinylpyrrolidone 2.5g, Diisopropyl azodicarboxylate 0.25g, linking agent PEG200DMA 0.63g feeds Ar deoxygenation 30min in ethanolic soln, be warming up to 60 ℃,, begin reaction by constant pressure funnel drip styrene monomer solution.React end in 20 hours, can obtain " petal-shaped " monodisperse cross-linked functional microsphere of median size 3.74 μ m.Wherein the dispersion coefficient of particle diameter is 0.031, and microballoon is single dispersion.
Claims (1)
1. the synthetic method of a monodisperse cross-linked polystyrene copolymerization microsphere, it is characterized in that: adopt linking agent Macrogol 200 dimethyl double methacrylate PEG200DMA to replace common linking agent divinylbenzene DVB, improved the stability of reaction system, because it helps stabilization, help forming mono-dispersion microballoon, with initiator Diisopropyl azodicarboxylate AIBN, linking agent PEG200DMA is dissolved in the monomer styrene, stablizer PVP polyvinylpyrrolidone is dissolved in carries out dispersion polymerization in the dispersion medium ethanol, through separating, promptly obtain micron-sized monodisperse polystyrene microsphere powder after the oven dry; Its processing step is:
1) remove stopper in the styrene monomer: with 10wt%NaOH solution with equal-volume than joining in the separating funnel that fills styrene monomer, wash styrene monomer, the vibration precipitation discards lower floor's liquid, repeats 2 times, washes with water 3-4 time again; Complete with anhydrous sodium sulfate drying then, make water content to 0.5wt%;
2) the stablizer polyvinylpyrrolidone that takes by weighing the 7wt%-12wt% of styrene monomer is dissolved in the 75wt% ethanol, take by weighing the initiator Diisopropyl azodicarboxylate of the 1wt%-3wt% of styrene monomer, the 1wt%-3wt% linking agent PEG200DMA of styrene monomer is dissolved in the styrene monomer of 25wt%, above liquid mixes respectively, and is stand-by;
3) ethanolic soln of PVP is transferred to 250ml and is equipped with in the four-hole boiling flask of thermometer, mechanical stirrer and prolong, feed Ar gas, flow 16ml/min-20ml/min, deoxygenation 30min;
4) be warming up to 60-80 ℃ then,, begin reaction, react end in 16-20 hour by constant pressure funnel drip styrene monomer solution;
5) the gained emulsion is separated with whizzer, remove the upper strata stillness of night, add ethanol and water washing again, 3-5 time repeatedly, oven drying at low temperature in 40 ℃ of baking ovens makes water content to 0.5wt%, and sub-microballoon powder can secure satisfactory grades.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102005021335A1 (en) * | 2005-05-04 | 2006-11-09 | Röhm Gmbh | Process for the preparation of bead polymers having a mean particle size in the range of 1 .mu.m to 40 .mu.m, and molding compositions and moldings comprising bead polymer |
| CN100503664C (en) * | 2005-08-15 | 2009-06-24 | 中国科学院理化技术研究所 | Method for preparing monodisperse polymer microsphere in micro level |
| CN1876688B (en) * | 2006-05-22 | 2012-09-19 | 深圳华明科技有限公司 | Method for preparing mono dispersed micrograde polymer microsphere |
| CN102234343B (en) * | 2010-04-20 | 2015-08-19 | 南开大学 | Monodispersed surface functionalized polymer microballoon resin and preparation method thereof |
| CN101864020A (en) * | 2010-05-19 | 2010-10-20 | 北京化工大学 | Method for preparing highly crosslinked polystyrene microsphere by stable dispersion polymerization of charge |
| CN103275275B (en) * | 2013-06-05 | 2016-01-20 | 南京工业大学 | A kind of preparation method of monodisperse polystyrene hybrid colloid emulsion of functionalization |
| CN103852580B (en) * | 2014-02-18 | 2015-12-09 | 温州市康泰生物科技有限公司 | Staphylococcus aureus identification kit and preparation method thereof |
| CN103922881A (en) * | 2014-04-21 | 2014-07-16 | 江苏赛宝龙石化有限公司 | Styrene polymerization inhibitor removing tower |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132213A (en) * | 1995-03-31 | 1996-10-02 | 中国科学院化学研究所 | Prepn. of Liquid-phase chromatography-use graininess single dispersion, large hole cross-linked polystyrene microballs |
| US5589230A (en) * | 1992-10-09 | 1996-12-31 | Henkel Kommanditgesellschaft Auf Aktien | Polymerizable, curable molding composition and a molding or coating process using this molding composition |
| US5714237A (en) * | 1996-01-16 | 1998-02-03 | Minnesota Mining Manufacturing Company | Partially crosslinked microspheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5589230A (en) * | 1992-10-09 | 1996-12-31 | Henkel Kommanditgesellschaft Auf Aktien | Polymerizable, curable molding composition and a molding or coating process using this molding composition |
| CN1132213A (en) * | 1995-03-31 | 1996-10-02 | 中国科学院化学研究所 | Prepn. of Liquid-phase chromatography-use graininess single dispersion, large hole cross-linked polystyrene microballs |
| US5714237A (en) * | 1996-01-16 | 1998-02-03 | Minnesota Mining Manufacturing Company | Partially crosslinked microspheres |
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