CN1266172C - Monodispersity nano/micron polymer microsphere resin and method for preparing same - Google Patents
Monodispersity nano/micron polymer microsphere resin and method for preparing same Download PDFInfo
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- CN1266172C CN1266172C CN 200410072867 CN200410072867A CN1266172C CN 1266172 C CN1266172 C CN 1266172C CN 200410072867 CN200410072867 CN 200410072867 CN 200410072867 A CN200410072867 A CN 200410072867A CN 1266172 C CN1266172 C CN 1266172C
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Abstract
The present invention relates to a monodisperse nanometer/micrometre polymer microsphere resin and a preparation method thereof. The polymer microsphere is a gel polyene monomer copolymer of crosslinking of 20 to 100% or a copolymer microsphere of a polyene monomer and other functional monoene monomers. The particle diameter of the polymer microsphere is from 100 nm to 10mm; the dispersion degree of the particle diameter is from 1.017 to 1.037; the range of the functional group content is from 0.1 to 3.0 mmol/g. A series of monodisperse or narrowly dispersed polymer microspheres with different particle sizes are prepared by a multi-step semi-separated continuous charging method. The present invention which is friendly to the environment has the characteristics of simple condition, easy operation, low price of raw materials, relative low toxicity and high conversion rate. The nanometer/micrometre polymer microsphere resin of the present invention can used as a stuffing material of chromatographic columns, a carrier of medicine slow release agents and catalysts, a carrier of the synthesis of stencil plates, an optic array material, and a solid phase carrier of immobilized biomolecules, such as biologic enzymes, antibodies, etc.
Description
Technical field
The present invention relates to the preparation of nano/micron polymer microsphere, particularly a kind of mono-dispersed nano/micron polymer microballoon resin and preparation method thereof.
Background technology
Polymer microsphere and microcapsule application in a lot of fields with internal structure are full of magnetism, as carrier of the support stationary phase in the separation science, biological device, injection moulding additive and controlled drug release etc.The method of the synthetic polymer microballoon of having reported mainly contains: letex polymerization [Verruer-Charleux, B., Graillat, C., Chevalier, Y., Pichot, C., Revillon, A., Colloid Polym.Sci.1991,269:398.], suspension polymerization [Balakrishnan, T., Lee, J., Ford, W.T., Macromol.Synth.1990,10,19.], seed swelling polymerization [Liang, Y.C., Svec, F., Frechet, J.M.J., J.Polym.Sci., Part A:Polym.Chem.1997,35:2631.], dispersion polymerization [Margel, S., Nov, E., Fisher, I., J.Polym.Sci., Part A:Polym.Chem., 1991,29:347.], precipitation polymerization [Li, W.H., Li, K., St ver, H.D.H., J.Polym.Sci., Part A:Polym.Chem.1999,37:2295.].Letex polymerization can synthesizing submicron monodisperse polymer particles, but negatively charged ion or nonionogenic tenside constantly are deposited on the polymkeric substance and in the polymer beads that is embedded in, and have limited the validity of this method.Dispersion polymerization and suspension polymerization can the single of synthesizing micron-grade disperse and wide dispersive polymer beads, but stablizer and dispersion agent have limited the application of microballoon attached to the surface of microballoon.Precipitation polymerization method is a kind of method for preparing the polymer beads with single-size and shape, can begin reaction from only containing initiator and monomeric homogeneous system system, obtain narrow dispersive polymer microballoon and do not contain any tensio-active agent and stablizer [Sosnowski, S.; Gadzionwski, M.; Slomkowski, S.Macromolecules 1996,29,4556-4564].
Summary of the invention
The present invention provides a kind of mono-dispersed nano/micron polymer microballoon resin and preparation method thereof, can overcome the deficiency of prior art.The present invention is that the distillation precipitation polymerization method prepares the mono-dispersed nano/micron polymer microballoon resin.The particle diameter of Nano/micron functional polymer microballoon resin of the present invention can be controlled in the scope between 100 nanometers to 10 micron, and functional groups wherein can be controlled by the comonomer that adds, perhaps obtain by the conversion between the functional group behind the copolymerization, the content of functional group also can be controlled.It is simple to have condition, easy handling, and cost of material is cheap, and relative low toxicity and environmental friendliness and the higher characteristics of transformation efficiency.
The concrete reaction process of the present invention is:
The particle diameter of the mono-dispersed nano/micron polymer microballoon resin that the present invention provides is in 100 nanometers-10 micron, the dispersity of particle diameter is 1.017-1.037, the microsphere surface shape is smooth and have the different functionalities functional group, and the functional group content scope is 0.1-3.0mmol/g; Described polymer microballoon is the crosslinked gel-type polyenoid class monomer homopolymer of 20-100% or polyenoid class monomer and the monomeric copolymer microsphere of other functional monoene class.
Described functional group (F) is hydroxyl, chlorine methylene radical (CH
2Cl), ester group (COOR), carboxyl, amide group (CONH), itrile group (CN) or epoxypropyl (CH
2CH (O) CH).
(linking agent Crosslinker) is divinylbenzene (DVB), two vinylformic acid glycol ester (EGDMA), N to described polyenoid class monomer, inferior acid amides (DREAM) of N '-two alkyl propylene or three vinylformic acid glyceryl ester (Trims).
Described functional monoene class monomer (comonomer, Comonomer) be vinylbenzene (St), right-chlorine methylene-benzene ethene (CMSt), methyl acrylate (MA), methyl methacrylate (MMA), methyl-2-hydroxyethyl acrylate (HEMA), methyl-vinylformic acid-2,3-epoxypropyl ester (GMA), vinylformic acid (AA) or vinyl cyanide (AN).
The preparation method of mono-dispersed nano/micron polymer microballoon resin of the present invention may further comprise the steps:
Crosslinkable polyenoid class monomer that 1) will measure or crosslinkable polyenoid class monomer heat with other functional monoene class monomer and organic solvent, radical initiator, make reaction system be raised to boiling state at 30-60 minute, and be reflected under the boiling state reaction 30-50 minute by room temperature;
2) in 1.5-3 hour the solvent in the reaction system is distilled half then, reaction system is keeping boiling after 10-50 minute, becomes muddy oyster white by the state of transparent and homogeneous, and polymer microballoon steams in the process of removing at solvent and forms;
3) the filtration under diminished pressure separation obtains polymer particles, washs microballoon 3 times with THF, acetone and ether successively again, is dried to constant weight in vacuum drying oven.
Described solvent is acetonitrile, ethyl acetate, butanone or their mixing.
Described radical initiator is azo-bis-isobutyl cyanide (AIBN) or benzoyl peroxide (BPO).
The amount ratio of described polyenoid class monomer or crosslinkable polyenoid class monomer and other functional monoene class monomer and organic solvent, radical initiator:
1)
Degree of crosslinking: 10-100vol% (volume %: linking agent/(linking agent+with comonomer));
2) radical initiator: 0.5-5wt% (quality % :) with respect to the total mass per-cent of polymerization single polymerization monomer;
3) monomer concentration: 1.0-10vol% (volume %: total monomer volume/(total monomer volume+organic solvent)).
The present invention can prepare a series of single dispersion or narrow dispersive polymer microballoons with varying particle size by multistep half point continuous dosing method.
The present invention is that the distillation precipitation polymerization method prepares the mono-dispersed nano/micron polymer microballoon resin.The present invention can be used for the homopolymerization of ethene of vinylbenzene, polyene hydrocarbon and other replacements of homopolymerization, polyene hydrocarbon and vinylbenzene, polyene hydrocarbon and replacement of DVB, EGDMA, DREAM or Trims polyene hydrocarbon and the copolymerization mono-dispersed nano/micron polymer microballoon of these reaction systems.It is simple that the present invention has condition, easy handling, and cost of material is cheap, and relative low toxicity and environmental friendliness and the higher characteristics of transformation efficiency.Preparation-obtained multiple functional nano/micron polymer microsphere resin can be used for the carrier and the immobilized biomolecules of filler, medicament slow release and the catalyzer of chromatographic column, as the solid phase carrier of biological enzyme, antibody etc.
The particle diameter of the Nano/micron functional polymer microballoon resin that the inventive method makes can be controlled in the scope between 100 nanometers to 10 micron, size distribution is narrow distribution, polymer beads is clean, do not contain any additives or stablizer, and functional groups wherein can be controlled by the common monomer that adds, perhaps obtain by the conversion between the functional group behind the copolymerization, the content of functional group also can be controlled.
Description of drawings
Fig. 1: the scanning electron microscope (SEM) of poly--divinylbenzene microspheres resin.
Fig. 2: the scanning electron microscope (SEM) of poly--divinylbenzene microspheres resin.
Fig. 3: the scanning electron microscope (SEM) of poly--divinylbenzene microspheres resin.
Fig. 4: the scanning electron microscope (SEM) of poly--divinylbenzene microspheres resin.
Fig. 5: poly--DVB-is common-HEMA microballoon scanning electron microscope (SEM).
Fig. 6: poly--EGDMA-is common-HEMA microballoon scanning electron microscope (SEM).
Embodiment
The raw material that the present invention is used: all linking agents, comonomer, initiator, solvent and reagent all are analytical pure.
Example 1: in 500 milliliters of two mouthfuls of bottles that have fractional column and a prolong, add divinylbenzene (10 milliliters, 9.2 grams, 70.7 N mmole),, N '-Diisopropyl azodicarboxylate (AIBN) (2wt% is with respect to monomeric quality for 0.184 gram, 1.12 mmoles) and 400 milliliters of acetonitriles.The reacting by heating system makes reaction system be raised to boiling state by room temperature about 30 minutes, and is reflected under the boiling state reaction 30 minutes.After in 1.5 hours the solvent in the reaction system being distilled half then, reaction finishes.Reaction system is become the oyster white of muddiness keeping boiling in the time of 15 minutes by the state of transparent and homogeneous.Polymer microballoon steams in the process of removing at solvent and progressively forms, and is precipitated out from reaction system.After reaction finished, filtration under diminished pressure separated and obtains polymer particles, used tetrahydrofuran (THF) (THF), acetone, ether washing copolymer microballoon more successively 3 times.The resulting polymers microballoon is dried to constant weight in vacuum drying oven.
The scanning electron microscope (SEM) of poly--divinylbenzene microspheres resin is seen Fig. 1, Fig. 1: the scanning electron microscope (SEM) of poly--divinylbenzene microspheres resin.The result is 1.99 microns, and the dispersity of particle diameter is 1.019, and the yield of reaction is 31%.
Example 2: in the system after example 1 reaction stops, continuing to add AIBN (0.184 gram, 1.12 mmoles) initiator and 200 milliliters of acetonitriles.The reacting by heating system makes reaction system be raised to boiling state by room temperature about 30 minutes, and is reflected under the boiling state reaction 30 minutes.After in 1.5 hours the solvent in the reaction system being distilled half then, reaction finishes.Polymer microballoon steams in the process of removing at solvent and progressively further grows up, and does not form littler polymer microballoon and do not produce secondary nucleation, and polymer microsphere still keeps good monodispersity.From reaction system, be precipitated out.After reaction finished, filtration under diminished pressure separated and obtains polymer particles, used THF, acetone, ether washing copolymer microballoon more successively 3 times.The resulting polymers microballoon is dried to constant weight in vacuum drying oven.The scanning electron microscope (SEM) of poly--divinylbenzene microspheres resin is seen Fig. 2, Fig. 2: the scanning electron microscope (SEM) of poly--divinylbenzene microspheres resin.The result is 2.34 microns, and the dispersity of particle diameter is 1.017, and the total recovery of reaction is 48%.Can prepare a series of polymer microballoons with varying particle size by this multistep half point continuous dosing method, particle size range is between 1.99 microns to 3.41 microns, and the dispersity of particle diameter remains single dispersion the between the 1.017-1.037.
Example 3: in 100 milliliters of two mouthfuls of bottles that have fractional column and a prolong, add (1.2 milliliters of divinylbenzenes, 1.1 gram, 8.5 right-chlorine methylene-benzene ethene (CMSt mmole),, 0.8 milliliter, 5.2 mmole), AIBN (2wt% is with respect to monomeric quality for 0.04 gram, 0.24 mmole) and 80 milliliters of acetonitriles.The reacting by heating system makes reaction system be raised to boiling state by room temperature about 30 minutes, and is reflected under the boiling state reaction 20 minutes.After in 1.5 hours the solvent in the reaction system being distilled half then, reaction finishes.Reaction system is become the oyster white of muddiness keeping boiling in the time of 15 minutes by the state of transparent and homogeneous.Polymer microballoon steams in the process of removing at solvent and progressively forms, and is precipitated out from reaction system.After reaction finished, filtration under diminished pressure separated and obtains polymer particles, used THF, acetone, ether washing copolymer microballoon more successively 3 times.The resulting polymers microballoon is dried to constant weight in vacuum drying oven.The scanning electron microscope (SEM) of poly--divinylbenzene microspheres resin is seen Fig. 3, Fig. 3: the scanning electron microscope (SEM) of poly--divinylbenzene microspheres resin.It is 3.19 microns that the result obtains particle diameter, and the dispersity of particle diameter is 1.014, and the yield of reaction is 18%.The functional group content of chlorine methylene radical is 0.88 mmole/gram.
Example 4: in 500 milliliters of two mouthfuls of bottles that have fractional column and a prolong, add divinylbenzene (10 milliliters, 9.2 grams, 70.7 mmoles), benzoyl peroxide (BPO) (0.272 gram, 1.12 mmole, 2wt% is with respect to monomeric quality) and 400 milliliters of acetonitriles.The reacting by heating system makes reaction system be raised to boiling state by room temperature about 30 minutes, and is reflected under the boiling state reaction 60 minutes.After in 3 hours the solvent in the reaction system being distilled half then, reaction finishes.Reaction system is become the oyster white of muddiness keeping boiling in the time of 45 minutes by the state of transparent and homogeneous.Polymer microballoon steams in the process of removing at solvent and progressively forms, and is precipitated out from reaction system.After reaction finished, filtration under diminished pressure separated and obtains polymer particles, used tetrahydrofuran (THF) (THF), acetone, ether washing copolymer microballoon more successively 3 times.The resulting polymers microballoon is dried to constant weight in vacuum drying oven.The scanning electron microscope (SEM) of poly--divinylbenzene microspheres resin is seen Fig. 4.Fig. 4: the scanning electron microscope (SEM) of poly--divinylbenzene microspheres resin.The result is 2.1 microns, and the dispersity of particle diameter is 1.008, and the yield of reaction is 43%.
Example 5: in 500 milliliters of two mouthfuls of bottles that have fractional column and a prolong, add (8 milliliters of divinylbenzenes, 7.4 gram, 56.6 hydroxyethyl methylacrylate (HEMA, 2 milliliters, gram mmole),, mmole), (N, N '-Diisopropyl azodicarboxylate (AIBN) (2wt% is with respect to monomeric quality for 0.184 gram, 1.12 mmoles) and 400 milliliters of acetonitriles.The reacting by heating system makes reaction system be raised to boiling state by room temperature about 30 minutes, and is reflected under the boiling state reaction 30 minutes.After in 1.5 hours the solvent in the reaction system being distilled half then, reaction finishes.Reaction system is become the oyster white of muddiness keeping boiling in the time of 15 minutes by the state of transparent and homogeneous.Polymer microballoon steams in the process of removing at solvent and progressively forms, and is precipitated out from reaction system.After reaction finished, filtration under diminished pressure separated and obtains polymer particles, used tetrahydrofuran (THF) (THF), acetone, ether washing copolymer microballoon more successively 3 times.The resulting polymers microballoon is dried to constant weight in vacuum drying oven.Poly--DVB-is common-and HEMA microballoon scanning electron microscope (SEM) sees Fig. 5.Fig. 5: poly--DVB-is common-HEMA microballoon scanning electron microscope (SEM).The result is 1.6 microns, and the dispersity of particle diameter is 1.009, and the yield of reaction is 35%.
Example 6: in 500 milliliters of two mouthfuls of bottles that have fractional column and a prolong, add (8 milliliters of EGDMA, 8.2 gram, 42 mmoles), hydroxyethyl methylacrylate (HEMA, 2 milliliters, gram, mmole), (N, N '-Diisopropyl azodicarboxylate (AIBN) (2wt% is with respect to monomeric quality for 0.184 gram, 1.12 mmoles) and 400 milliliters of acetonitriles.The reacting by heating system makes reaction system be raised to boiling state by room temperature about 30 minutes, and is reflected under the boiling state reaction 30 minutes.After in 1.5 hours the solvent in the reaction system being distilled half then, reaction finishes.Reaction system is become the oyster white of muddiness keeping boiling in the time of 15 minutes by the state of transparent and homogeneous.Polymer microballoon steams in the process of removing at solvent and progressively forms, and is precipitated out from reaction system.After reaction finished, filtration under diminished pressure separated and obtains polymer particles, used tetrahydrofuran (THF) (THF), acetone, ether washing copolymer microballoon more successively 3 times.The resulting polymers microballoon is dried to constant weight in vacuum drying oven.Poly--EGDMA-is common-and HEMA microballoon scanning electron microscope (SEM) sees Fig. 6.Fig. 6: poly--EGDMA-is common-HEMA microballoon scanning electron microscope (SEM).The result is 1.46 little, and the dispersity of particle diameter is 1.01, and the yield of reaction is 46%.
Claims (8)
1, a kind of monodispersed polymer microsphere resin, the particle diameter that it is characterized in that it is in 100 nanometers-10 micron, the dispersity of particle diameter is 1.017-1.037, and the microsphere surface shape is smooth and have the different functionalities functional group, and the functional group content range is 0.1-3.0mmol/g;
Described polymer microballoon is the crosslinked gel-type polyenoid class monomer homopolymer of 20-100% volume or polyenoid class monomer and the monomeric copolymer microsphere of other functional monoene class.
2,, it is characterized in that described functional group is hydroxyl, chlorine methylene radical, ester group, carboxyl, amide group, itrile group or epoxypropyl according to the described monodispersed polymer microsphere resin of claim 1.
3,, it is characterized in that described polyenoid class monomer is divinylbenzene, two vinylformic acid glycol ester, N, N '-two alkyl acrylimides or three vinylformic acid glyceryl ester according to the described monodispersed polymer microsphere resin of claim 1.
4, according to the described monodispersed polymer microsphere resin of claim 1, it is characterized in that described functional monoene class monomer be vinylbenzene, to chlorine methylene-benzene ethene, methyl acrylate, methyl methacrylate, methacrylic acid-2-hydroxyethyl ester, methacrylic acid-2,3-epoxypropyl ester, vinylformic acid or vinyl cyanide.
5, the preparation method of the described monodispersed polymer microsphere resin of claim 1 is characterized in that may further comprise the steps:
Crosslinkable polyenoid class monomer that 1) will measure or crosslinkable polyenoid class monomer heat with other functional monoene class monomer and organic solvent, radical initiator, make reaction system be raised to boiling state at 30-60 minute, and under boiling state, reacted 30-50 minute by room temperature;
2) in 1.5-3 hour the solvent in the reaction system is distilled half then, reaction system keeps boiling 10-50 minute, and polymer microballoon steams in the process of removing at solvent and forms;
3) the filtration under diminished pressure separation obtains polymer particles, washs microballoon 3 times with tetrahydrofuran (THF), acetone and ether successively again, is dried to constant weight in vacuum drying oven;
4) prepare a series of monodispersed polymer microsphere resins by multistep half point continuous dosing method with varying particle size.
6,, it is characterized in that the amount ratio of described polyenoid class monomer or crosslinkable polyenoid class monomer and other functional monoene class monomers and organic solvent, radical initiator according to the preparation method of the described monodispersed polymer microsphere resin of claim 5:
Degree of crosslinking: 10-100vol%, volume %: linking agent volume/(linking agent volume+comonomer volume) %;
Radical initiator: 0.5-5wt%, quality %: with respect to the total mass per-cent of polymerization single polymerization monomer;
Monomer concentration: 1.0-10vol%, volume %: total monomer volume/(total monomer volume+organic solvent volume).
7,, it is characterized in that described solvent is acetonitrile, ethyl acetate, butanone or their mixture according to the preparation method of the described monodispersed polymer microsphere resin of claim 5.
8,, it is characterized in that described radical initiator is Diisopropyl azodicarboxylate or benzoyl peroxide according to the preparation force method of the described monodispersed polymer microsphere resin of claim 5.
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| CN100478380C (en) * | 2006-08-24 | 2009-04-15 | 中国科学院合肥物质科学研究院 | Chemical preparation method of hollow polymer microsphere with controllable open pores |
| CN101928365A (en) * | 2010-09-27 | 2010-12-29 | 天津市富集科技有限公司 | Method for preparing amphiphilic monodisperse microspherical resin |
| CN102838709B (en) * | 2011-06-21 | 2016-03-30 | 南开大学 | Atom transferred free radical precipitation polymerization method prepares monodispersed polymer microsphere resin |
| CN103554316A (en) * | 2013-11-08 | 2014-02-05 | 上海第二工业大学 | Method for quickly preparing monodisperse polymer microspheres |
| CN103755867A (en) * | 2013-12-12 | 2014-04-30 | 中国科学院深圳先进技术研究院 | Preparation method for monodisperse nanometer/micrometer hydrogel microsphere |
| GB201512725D0 (en) | 2015-07-20 | 2015-08-26 | Life Technologies As | Polymeric particles |
| GB201700983D0 (en) * | 2017-01-20 | 2017-03-08 | Life Tech As | Polymeric particles |
| CN112521541B (en) * | 2020-11-02 | 2022-10-25 | 济南大学 | Preparation method of monodisperse porous polymer microspheres |
| CN115558169A (en) * | 2022-09-27 | 2023-01-03 | 南开大学 | Preparation method of bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity |
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