CN1132213A - Prepn. of Liquid-phase chromatography-use graininess single dispersion, large hole cross-linked polystyrene microballs - Google Patents
Prepn. of Liquid-phase chromatography-use graininess single dispersion, large hole cross-linked polystyrene microballs Download PDFInfo
- Publication number
- CN1132213A CN1132213A CN95103038A CN95103038A CN1132213A CN 1132213 A CN1132213 A CN 1132213A CN 95103038 A CN95103038 A CN 95103038A CN 95103038 A CN95103038 A CN 95103038A CN 1132213 A CN1132213 A CN 1132213A
- Authority
- CN
- China
- Prior art keywords
- monomer
- polystyrene microsphere
- volume
- linking agent
- crosslinked polystyrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
A process for synthesizing crosslinked polystyrene microspheres that is alone dispersed and has granularity of 5-20 micrometers and apeture of tens to hundreds NM is characterized by that the combination of polymerization technique for heterogeneous solution of organic medium with swelling suspension polymerization tchnigue for aqueous phase medium and during said polymerization, high-molecular solution pore-forming technique is used. Said microspheres may be used as matrix resin of various high performance liquid chromatographic separation filler.
Description
The preparation method of the monodisperse macroporous structure crosslinked polystyrene microsphere of granularity.
The present invention relates to the method for making that a kind of preparation method who is used for the matrix resin of efficient liquid phase chromatographic stuffing specially refers to crosslinked polystyrene microsphere.
Use the monodisperse macroporous structure crosslinked polystyrene microsphere of granularity,, have very excellent performance as the matrix resin of various high performance liquid chromatography (HPLC) filler.
Eur.Pat.0003905 (1979); U.S Pat, 4530956 (1985); J.Chromatogr535 (1990) 147, reported two steps or the active swelling of multistep and the polymerization technique of people such as Ugelstad development.This method be granularity monodisperse polystyrene latex (<1 μ m) with agalactosis polymerization as " seed ", at first allow the water-fast low-molecular weight compound of its " seed " absorption carry out swelling, adsorb monomer, linking agent then again once more by swelling and polymerization.Though this method is successful for the prepared sizes mono-disperse polymer microspheres, the equipment complex steps is many, and technical sophistication is wayward, and this method uses low-molecular-weight pore-creating agent not reach enough big aperture in addition.People such as Frechet had adopted the method for polymer pore [to see AnalClem afterwards, 64 (1992) 1232], but still be to adopt with 1 μ m latex absorption low-molecular weight compound to carry out complicated and difficult operation stepss such as swelling though this method can be made the granularity mono-dispersion microballoon of macroporous structure.
The present invention has overcome in the aforesaid method and to make " seed " with latex and need, operative technique various through series of steps such as swellings in advance and equipment complexity, shortcoming such as wayward, and cause the existing problem of macropore, propose a kind of synthetic method that combines with heterogeneous solution polymerization and swollen-state polymerization and adopt macromolecular solution pore method, synthesize the crosslinked polystyrene microsphere of the monodisperse macroporous structure of granularity.This method is at first to carry out the heterogeneous solution polymerization in the reaction system of organic phase medium, synthesize the monodispersed linear polymeric microballoon of granularity, then the linear polymeric microballoon is carried out swelling and polymerization in the reaction system of aqueous media, in synthetic, utilize simultaneously the linear polymeric solution that is generated to carry out pore, obtain that 5-20 μ m granularity is monodispersed, the aperture reaches tens of crosslinked polystyrene microspheres that arrive nanometers up to a hundred.
Synthetic used raw material: monomer is vinylbenzene (St); Linking agent is divinylbenzene (DVB); Initiator is Diisopropyl azodicarboxylate (AIBN) or benzoyl peroxide (BPO); Reaction medium is divided into organic medium and aqueous media, and organic medium is alcohol compound such as ethanol, propyl alcohol etc.; Stablizer is a macromolecular compound, as polyvinylpyrrolidone (PVP), and polyvinyl alcohol (PVA); Co-stabilizer is ionic or nonionic compound, as palmityl trimethyl ammonium chloride (CTAC), hexadecanol (C
16-OH) etc.; Emulsifying agent is that tensio-active agent such as dodecyl sodium sulfonate are received (SDS); Conditioning agent is organic compound such as alkyl hydro carbons, Nitromethane 99Min., methyl-sulphoxide etc.Thinner is the compound of benzene series class, as dibutyl phthalate (DBP) etc.
1, prepares the linear polystyrene microballoon with the heterogeneous solution polymerization process.
Components such as monomer, initiator, stablizer and a small amount of co-stabilizer that is added as required, conditioning agent, equal solubilized in the alcohols reaction medium, system is rendered as homogeneous state.Polyreaction is to carry out on a device that can heat and rotate.When the molecular weight of oligomer that polyreaction produces reaches certain limit, with regard to gathering become a kind of no longer be dissolved in the polymer in the medium and produced with medium be separated, reaction system just becomes the heterogeneous state of a kind of polymer particle suspension in medium.The polymer particulate continues absorption and is dissolved in the monomer in the medium and continues polymerization, and its particulate volume is constantly increased, and has been consumed up to monomer.Polyreaction is removed medium and other components with methods such as precipitation, washing, filtrations after finishing, and has so just obtained the monodispersed linear polystyrene microballoon of granularity.
The proportioning raw materials of polyreaction: the concentration of initiator in monomer is 0.005-0.04g/ml; Monomer is 1 with the ratio (volume) of alcoholic medium: 9-7: 3; The concentration of stablizer in alcoholic medium is 0.01-0.04g/ml.
Polyreaction is to carry out under 50-75 ℃ 10-20 hour.
Institute's synthetic linear polystyrene (PS) microballoon, granularity presents single dispersion in the 2-10 mu m range.
2, with the monodisperse macroporous structure crosslinked polystyrene microsphere of swelling suspension polymerization prepared sizes, perhaps the prepared sizes list disperses linear polystyrene microsphere.
The mixture that dissolves each other of monomer, linking agent, initiator and thinner can be emulsified in the aqueous solution that contains emulsifying agent and stablizer, form a kind of emulsification the aqueous media reaction system.After the prepared linear polystyrene microballoon in front joins in this aqueous media reaction system, with regard to the monomer in the absorbing medium, linking agent, initiator and thinner and by swelling.This by swelling " liquid pearl " be suspended in the medium, the heating and agitation condition under carry out polymerization.Reaction product just obtains the granularity single dispersion, large hole cross-linked polystyrene microballs after washing and extracting.The macroporous structure of this crosslinked polystyrene microsphere is to have utilized the thinner that added in the building-up process and linear polystyrene microballoon to dissolve each other and the macromolecular solution that forms, has played pore-creating agent.After polymerization finishes, the extracting of this macromolecular solution pore-creating agent is fallen, just stayed permanent macropore in resin particle inside.
The proportioning raw materials of polyreaction: the concentration of initiator in monomer and linking agent mixed solution is 0.001-0.03g/ml; Monomer is 9 with the ratio (volume) of linking agent: 1-2: 8; The volume that monomer adds linking agent is 8 with the ratio of diluent volume: 2-3: 7; The cumulative volume of monomer, linking agent and thinner is 1-800 a times of linear polystyrene microsphere volume.
Synthesis condition: swelling is at room temperature to carry out 2-6 hour; Heated polymerizable is to carry out under 50-90 ℃ 10-24 hour.
Institute's synthetic crosslinked polystyrene (PS-DVB) microballoon, granularity presents single dispersion in the 5-20 mu m range, and the aperture reaches tens of to nanometers up to a hundred.
With above-mentioned same synthetic method, when raw materials used need not be with addition of linking agent and thinner the time, also can synthesize the either large or small different linear polystyrene microballoon of the monodispersed molecular weight of granularity once more, and can continue to synthesize the monodisperse macroporous crosslinked copolymer beads of granularity again with it.
Technical characterstic of the present invention is, a kind of synthetic method that combines with the swelling suspension polymerization of aqueous media with the heterogeneous solution polymerization of organic medium has been set up in proposition, and in building-up process, adopted linear polymeric solution pore method, synthesized the crosslinked polystyrene microsphere of the monodisperse macroporous structure of granularity.This method had both comprised the single synthetic technology of disperseing of a whole set of granularity, had comprised that also macromolecular solution causes the technology of macropore.Institute's synthetic product can be used as various high performance liquid chromatography and (comprises anti-phase, ion-exchange, hydrophobic interaction, volume is got rid of, biological affinity isochromatic spectrum) matrix resin of separating column packing, its correlation parameter index (as single fineness of dispersion, aperture, degree of crosslinking etc.) all can reach best service requirements.Compare with the synthetic technology that existing document and patent are reported, the then more single easy row of this synthetic method, its step is few, simple to operate, be easy to control, do not need complex apparatus just can obtain needed product, and productive rate quite high (more than 90%) also is convenient to amplify preparation.
Embodiment 1:St 7.5ml, PVP 0.5g, AIBN 0.15g, ethanol 17.5ml, join in the flask after these raw materials are mixed, and place on the device of 50-75 ℃ of heating and rotation and carry out the heterogeneous solution polymerization, 70 ℃ of reactions 10-20 hour down, the gained throw out is the single PS microballoon that disperses (4 μ m) of granularity, isolates standby.Get St 22.5ml, add ultrasonic emulsification in (1%PVA-0.1%SDS) solution behind the BPO 0.9g mixed dissolution, emulsion is mixed in stirring with prepared PS microballoon, at room temperature swelling is 6 hours, 70 ℃ of following polymerizations 12 hours, make the polystyrene microsphere (single fineness of dispersion 7 μ m) that contains low linear molecule amount.Get St 10ml, DVB 25ml, DBP 30ml, BPO 0.53g joins ultrasonic emulsification in the 200ml 1%PVA-0.1%SOS solution behind the mixed dissolution, emulsion and obtained containing than harmonic component polystyrene microsphere (together with its medium) are mixed stirring, at room temperature swelling is 6 hours, 70 ℃ of following polymerizations 24 hours, polymerization product promptly obtained the monodispersed macroporous cross-linked polystyrene resin of 10 μ m granularities after washing and toluene extracting, and productive rate is 95%.
Embodiment 2: get St 4.5ml, and PVP 0.3g, AIBN 0.09g, ethanol 10.5ml, hexadecyl base trimethyl ammonium chloride 0.15ml presses embodiment 1 method and handles, and synthesizes the single PS of dispersion of 3 μ m granularities microballoon.Get St 18ml, BPO 0.9g presses embodiment 1 method and handles, and synthesizes the polystyrene microsphere (single dispersible granule 5 μ m) that contains lower molecular weight.Get St 37.5ml, DVB 37.5ml, BPO 0.75g, DBP 54ml presses embodiment 1 method and handles, and synthesizes the monodispersed macroporous cross-linked polystyrene resin of 9 μ m granularities, and productive rate is 90%.
Embodiment 3: get St 15ml, and PVP 1g, AIBN 0.3g, ethanol 33.5ml, normal heptane 1.5ml, hexadecanol 0.125g presses embodiment 1 method and handles, and synthesizes the single PS of dispersion of 7 μ granularities microballoon.Get St 12ml, DVB 12ml, BPO 0.24g, DBP 16ml presses embodiment 1 final step method and handles, and synthesizes the monodisperse porous cross-linked polystyrene resin of 10 μ granularities, productive rate 93%
The granularity single dispersion, large hole cross-linked polystyrene microballs of the present invention preparation can be used as the matrix resin of various HPLC fillers, excellent property.After for example matrix resin being used the covering of polymine bonding also crosslinked, make high-effect ionic exchange chromatography filler, in the gradient elution system of Tris-HCl+NaCl, have the good separation effect for protein example.And for example matrix resin is covered with the dextran bonding and crosslinked after, get rid of chromatograph packing material as efficient volume, for the exclusion limit of water-soluble polymer (Dextran) 10
6More than the molecular weight, separating ranges is 10
4-10
6Molecular weight.Institute's synthetic granularity single dispersion, large hole cross-linked polystyrene microballs also can be directly as efficient anti-phase and gel permeation chromatography filler.For example, on reverse-phase chromatography, can make benzene series one compounds obtain fine separation with acetonitrile-aqueous solution drip washing; The molecular weight exclusion limit of p-poly-phenyl ethene sample is 10 on gel permeation chromatography
6More than.
Claims (5)
1, a kind of preparation method of granularity single dispersion, large hole cross-linked polystyrene microballs, it is characterized in that preparing crosslinked polystyrene microsphere with a kind of synthetic method that combines with heterogeneous solution polymerization and swelling suspension polymerization technique, the concentration of initiator in monomer is 0.005-0.04g/ml; Monomer is 1 with the ratio (volume) of alcoholic medium: 9-7: 3; The concentration of stablizer in alcoholic medium is 0.01-0.04g/ml, and polymeric reaction temperature is 50-75 ℃, and the reaction times is 10-20 hour; With the monodisperse macroporous structure crosslinked polystyrene microsphere of swelling suspension polymerization prepared sizes, the concentration of initiator in monomer and linking agent mixed solution is 0.001-0.03g/ml; Monomer and linking agent volume ratio are 9: 1-2: 8; The volume that monomer adds linking agent is 8 with the ratio of diluent volume: 2-3: 7; The cumulative volume of monomer, linking agent and thinner is 1-800 a times of linear polystyrene microsphere volume, and swelling temperature is a room temperature, and the time is 2-6 hour, and the heated polymerizable temperature is 50-90 ℃, and the time is 10-24 hour.
2, the preparation method of crosslinked polystyrene microsphere according to claim 1 is characterized in that: initiator is Diisopropyl azodicarboxylate or benzoyl peroxide.
3, the preparation method of crosslinked polystyrene microsphere according to claim 1 is characterized in that: stablizer is a polyvinylpyrrolidone, polyvinyl alcohol.
4, the preparation method of crosslinked polystyrene microsphere according to claim 1 is characterized in that described linking agent is a divinylbenzene.
5, the preparation method of crosslinked polystyrene microsphere according to claim 1 is characterized in that described thinner is a dibutyl phthalate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN95103038A CN1045610C (en) | 1995-03-31 | 1995-03-31 | Prepn. of Liquid-phase chromatography-use graininess single dispersion, large hole cross-linked polystyrene microballs |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN95103038A CN1045610C (en) | 1995-03-31 | 1995-03-31 | Prepn. of Liquid-phase chromatography-use graininess single dispersion, large hole cross-linked polystyrene microballs |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1132213A true CN1132213A (en) | 1996-10-02 |
CN1045610C CN1045610C (en) | 1999-10-13 |
Family
ID=5074569
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN95103038A Expired - Fee Related CN1045610C (en) | 1995-03-31 | 1995-03-31 | Prepn. of Liquid-phase chromatography-use graininess single dispersion, large hole cross-linked polystyrene microballs |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1045610C (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1120178C (en) * | 1999-07-02 | 2003-09-03 | 申丰化学工业股份有限公司 | Process for preparing dispersed-in-water hard particles containing water in them |
CN1298751C (en) * | 2004-09-14 | 2007-02-07 | 清华大学 | Process for synthesis of monodisperse micron crosslinked polystyrene copolymerization microsphere |
CN1300190C (en) * | 2005-03-02 | 2007-02-14 | 东南大学 | Method for preparing mono dispersed functionalized polymer microsphere |
CN100349923C (en) * | 2003-12-23 | 2007-11-21 | 南开大学 | High molecule nano ball and its preparing method of quasi-critical polymerization |
CN100478388C (en) * | 2006-11-21 | 2009-04-15 | 南京大学 | Method for preparing conductive, high molecular compound particles of polystyrene / polyaniline |
CN101257969B (en) * | 2005-12-02 | 2011-08-24 | 积水化学工业株式会社 | Hydrophilic polymer microparticle, filler for ion exchange liquid chromatography, and method for production of filler for ion exchange liquid chromatography |
CN102500431A (en) * | 2011-10-18 | 2012-06-20 | 浙江大学 | Preparation method of surface-grafted type anion chromatographic filling material |
CN103611509A (en) * | 2013-11-06 | 2014-03-05 | 四川师范大学 | Cross-linked polystyrene liquid chromatography stationary phase, and preparation and application thereof |
CN104276564A (en) * | 2014-10-29 | 2015-01-14 | 苏州纳微科技有限公司 | Application of carbonized microspheres |
CN104769693A (en) * | 2012-10-19 | 2015-07-08 | 阿尔斯通技术有限公司 | Current connection and/or cut-off device comprising permanent contacts with reduced wear |
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 |
CN108164649A (en) * | 2018-01-29 | 2018-06-15 | 北京石油化工学院 | A kind of high-crosslinking-degree polymer microballoon with super macropore and preparation method thereof |
CN108250216A (en) * | 2016-12-29 | 2018-07-06 | 天津领世生物科技开发有限公司 | The method of tacrolimus, double hydrogen tacrolimus, ascosin in one one-step refining crude tacrolimus |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100360239C (en) * | 2005-07-14 | 2008-01-09 | 上海交通大学 | Macroporous cross-linked polystyrene mixed acid ion exchange resin and its prepn process |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6130046A (en) * | 1984-07-23 | 1986-02-12 | Nec Corp | Manufacture of semiconductor integrated circuit device |
JPH0692443B2 (en) * | 1987-06-25 | 1994-11-16 | 日本ゼオン株式会社 | Method for producing polymer particles |
US5412048A (en) * | 1993-07-26 | 1995-05-02 | General Electric Company | Process for producing cross-linked monodispersed polymeric particles |
-
1995
- 1995-03-31 CN CN95103038A patent/CN1045610C/en not_active Expired - Fee Related
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1120178C (en) * | 1999-07-02 | 2003-09-03 | 申丰化学工业股份有限公司 | Process for preparing dispersed-in-water hard particles containing water in them |
CN100349923C (en) * | 2003-12-23 | 2007-11-21 | 南开大学 | High molecule nano ball and its preparing method of quasi-critical polymerization |
CN1298751C (en) * | 2004-09-14 | 2007-02-07 | 清华大学 | Process for synthesis of monodisperse micron crosslinked polystyrene copolymerization microsphere |
CN1300190C (en) * | 2005-03-02 | 2007-02-14 | 东南大学 | Method for preparing mono dispersed functionalized polymer microsphere |
CN101257969B (en) * | 2005-12-02 | 2011-08-24 | 积水化学工业株式会社 | Hydrophilic polymer microparticle, filler for ion exchange liquid chromatography, and method for production of filler for ion exchange liquid chromatography |
CN100478388C (en) * | 2006-11-21 | 2009-04-15 | 南京大学 | Method for preparing conductive, high molecular compound particles of polystyrene / polyaniline |
CN102500431A (en) * | 2011-10-18 | 2012-06-20 | 浙江大学 | Preparation method of surface-grafted type anion chromatographic filling material |
CN102500431B (en) * | 2011-10-18 | 2013-09-04 | 浙江大学 | Preparation method of surface-grafted type anion chromatographic filling material |
CN104769693A (en) * | 2012-10-19 | 2015-07-08 | 阿尔斯通技术有限公司 | Current connection and/or cut-off device comprising permanent contacts with reduced wear |
CN103611509A (en) * | 2013-11-06 | 2014-03-05 | 四川师范大学 | Cross-linked polystyrene liquid chromatography stationary phase, and preparation and application thereof |
CN104276564A (en) * | 2014-10-29 | 2015-01-14 | 苏州纳微科技有限公司 | Application of carbonized microspheres |
CN104276564B (en) * | 2014-10-29 | 2016-08-24 | 苏州纳微科技有限公司 | A kind of application of carbonization microsphere |
CN108250216A (en) * | 2016-12-29 | 2018-07-06 | 天津领世生物科技开发有限公司 | The method of tacrolimus, double hydrogen tacrolimus, ascosin in one one-step refining crude tacrolimus |
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 |
CN108164649A (en) * | 2018-01-29 | 2018-06-15 | 北京石油化工学院 | A kind of high-crosslinking-degree polymer microballoon with super macropore and preparation method thereof |
CN108164649B (en) * | 2018-01-29 | 2020-06-16 | 北京石油化工学院 | High-crosslinking-degree polymer microsphere with super macropores and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN1045610C (en) | 1999-10-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1045610C (en) | Prepn. of Liquid-phase chromatography-use graininess single dispersion, large hole cross-linked polystyrene microballs | |
EP0575488B1 (en) | Process for producing uniform macroporous polymer beads | |
US5114577A (en) | Composite separating agent | |
EP0763064B1 (en) | A method of manufacturing particles, and particles that can be produced in accordance with the method | |
US3957698A (en) | Thermally reversible, amphoteric ion exchange resins consisting of crosslinked microbeads embedded in crosslinked matrix of opposite exchange group type | |
Yoshida et al. | Metal ion imprinted microsphere prepared by surface molecular imprinting technique using water‐in‐oil‐in‐water emulsions | |
JPH02233147A (en) | Ion-exchange compound using resin bond of dispersion agent | |
JP2011503293A (en) | Porous polymer resin | |
JP2002536478A (en) | Method for producing porous cross-linked polymer monolith | |
CN101229509A (en) | Method of synthetizing closely graded polymer high efficiency liquid chromatography stuffing | |
JP3158186B2 (en) | Alkyl group-containing porous resin, production method thereof and use thereof | |
EP1589045B1 (en) | Polymeric adsorbent, and method of preparation and use | |
Yu et al. | Diazoresin modified monodisperse porous poly (glycidylmethacrylate-co-divinylbenzene) microspheres as the stationary phase for high performance liquid chromatography | |
US7540962B2 (en) | Method of preparing spheroid polymer particles having a narrow size distribution by dispersion polymerization, particles obtainable by the method and use of these particles | |
KR0140099B1 (en) | Composite ion exchange compositions for ion chromatography | |
CN101362068B (en) | Precipitation polymerization preparation method of crosslinked polystyrene microspheres | |
WO2019110318A1 (en) | Porous materials, method for producing same and uses thereof | |
JP3087332B2 (en) | Packing material for liquid chromatography | |
JPH0513168B2 (en) | ||
CN1116319C (en) | Cross-linking polyvinyl pyridine microspheres for liquid-phase chromatography and its preparing process | |
CN115160603A (en) | High-rigidity macroporous polysaccharide microsphere and preparation method thereof | |
CN1233438C (en) | Method for preparing microspheric PGDT separating medium with two kinds of pore forms | |
Stolberg et al. | Microspheres of chitosan/poly (vinylalcohol) incorporating tetrasulphonated copper (II) phthalocyanine: preparation and characterization | |
Horváth et al. | Preparation of terbutylazine imprinted polymer microspheres using viscous polymerization solvents | |
US20060266707A1 (en) | Drying method for macroporous polymers, and method of preparation and use of macroporous polymers made using the method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |