WO2000064572A2 - Epoxy-functional polymeric microbeads - Google Patents
Epoxy-functional polymeric microbeads Download PDFInfo
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- WO2000064572A2 WO2000064572A2 PCT/US1999/007337 US9907337W WO0064572A2 WO 2000064572 A2 WO2000064572 A2 WO 2000064572A2 US 9907337 W US9907337 W US 9907337W WO 0064572 A2 WO0064572 A2 WO 0064572A2
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- WO
- WIPO (PCT)
- Prior art keywords
- polymeric microbeads
- epoxy
- polymeric
- ethers
- dispersion
- Prior art date
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- UQOXIKVRXYCUMT-UHFFFAOYSA-N C[Si](C)(CCC1CC2OC2CC1)O[Si](C)(C)CCC1CC2OC2CC1 Chemical compound C[Si](C)(CCC1CC2OC2CC1)O[Si](C)(C)CCC1CC2OC2CC1 UQOXIKVRXYCUMT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
- B01D15/361—Ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
- B01D15/3833—Chiral chromatography
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
Definitions
- the present invention relates to epoxy-functional polymeric microbeads that may be prepared by suspension polymerization.
- the present invention relates to a population of polymeric microbeads bearing epoxy functionality on surfaces thereof and having a narrow particle size distribution, such that the particle size of greater than 90% of the polymeric microbeads in said population is equal to ⁇ 20 % of the mean particle size.
- the epoxy functionality arises from one or more multifunctional epoxy monomers chosen from the group consisting of: 3,4- epoxycyclohexyl methyl-3',4'-epoxycyclohexane carboxylate, bis-(3,4- epoxycyclohexyl) adipate, 4-vinylcyclohexene dioxide, epoxy silicone resins, limonene dioxide, dicyclopentadiene dioxide, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, 1 ,4-butanediol diglycidyl ether, diglycidyl ethers of tetrabromo-bisphenol-A, epoxy cresol novolacs, epoxy phenol novolacs, and diglycidyl phthalate.
- multifunctional epoxy monomers chosen from the group consisting of: 3,4- epoxycyclohexyl methyl-3',4'-epoxycyclohexane carboxylate, bis-(3,4- epoxycyclohex
- the epoxy functionality arises from one or more multifunctional epoxy monomers chosen from the group consisting of: 3,4- epoxycyclohexyl methyl-3',4'-epoxycyclohexane carboxylate, 4-vinylcyclohexene dioxide and the compounds of formula I and II:
- the polymeric microbeads may derived from the copolymerization of one or more multifunctional epoxy monomers and one or more cationically polymerizible comonomers.
- the cationically polymerizible comonomers are chosen from the group consisting of: 1 ,2-epoxytetradecane, 1 ,2-epoxydecane, 1 ,2- epoxydodecane, epoxidized soybean oil, epoxidized linseed oil, vinyl ethers, 1-propenyl ethers, 1-butenyl ethers, styrene, indene.
- the present invention relates to polymeric microbeads prepared by suspension photopolymerization of one or more multifunctional epoxy monomers.
- the dispersion comprises a non-aqueous suspending medium. Polymerization is initiated by a cationic photoinitator.
- the present invention relates to a process for the preparation of polymeric microbeads comprising:
- the present invention relates to a method for attaching functional groups to the surface of a polymeric microbead comprising:
- FIG. 1 is a photograph of polymeric microbeads of the present invention showing particle size distribution.
- FIG. 2 is a graph of particle size of the particles shown in the photograph in FIG. 1.
- FIG. 3 shows an exemplary reactor having a high speed stirrer for agitation and a lamp well for transmitting light into the reaction medium;
- FIG. 4 shows an exemplary reactor having a high speed stirrer for agitation and a fiber optic cable for transmitting light into the reaction medium;
- FIG. 5 shows an exemplary reactor having a high speed stirrer for agitation and a transparent window for transmitting light from a lamp fitted with a reflector into the reaction medium;
- FIG. 6 shows an exemplary reactor having an ultrasonic bath for agitation and direct transmission from a lamp fitted with a reflector into the reaction medium.
- the present invention relates to polymeric microbeads that are derived from one or more multifunctional epoxy monomers, and that bear residual epoxy functionality on the surfaces thereof.
- the polymeric microbeads also have a narrow particle size distribution.
- the epoxy groups on the surface of the microbeads are residual or unpolymerized epoxy groups that are bound to the microbead through a reacted or polymerized epoxy group.
- Multifunctional epoxy monomers that may be polymerized to form the polymeric microbeads of the present invention include: cycloaliphatic diepoxides such as 3,4- epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, bis-(3,4- epoxycyclohexyl)adipate, and 4-vinylcyclohexene dioxide, epoxy silicone resins, including I and II below, limonene dioxide, dicyclopentadiene dioxide, bisphenol- A diglycidyl ether, bisphenol-F diglycidyl ether, 1 ,4-butanediol diglycidyl ether, diglycidyl ethers of tetrabromo-bisphenol-A, epoxy cresol novolacs, epoxy phenol novolacs, and diglycidyl phthalate.
- cycloaliphatic diepoxides such as 3,4- epoxycyclohexylmethyl-3',4'-ep
- Preferred epoxy monomers are 3,4- epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 4-vinylcyclohexene dioxide, limonene dioxide and I and II. Limonene dioxide and 3,4-epoxy cyclohexylmethyl-3,4-epoxycyclohexane carboxylate, are available from the SEM Corporation, and Ciba Geigy Corporation, respectively. I and II are available as PC 1000 and T8, respectively, from Polyset Chemical, Mechanicville. New York.
- the one or more epoxy monomers may be copolymerized with one or more cationically photopolymerizible monomers, including monofunctional epoxy monomers such as 1,2-epoxytetradecane, 1 ,2-epoxydecane, 1 ,2-epoxydodecane, epoxidized soybean oil, epoxidized linseed oil.
- monofunctional epoxy monomers such as 1,2-epoxytetradecane, 1 ,2-epoxydecane, 1 ,2-epoxydodecane, epoxidized soybean oil, epoxidized linseed oil.
- Other cationically polymerizible monomers that may be used are cycloaliphatic epoxy alcohols, vinyl ethers.
- the present invention relates to a dispersion of polymeric microbeads prepared by suspension photopolymerization of one or more epoxy mononomers.
- the polymeric microbeads are composed of an epoxy resin derived from one or more multifunctional epoxy monomers.
- One or more cationically polymerizible comonomers may be copolymerized as described above
- the polymeric microbeads are dispersed in a suspending medium.
- the suspending medium is non-aqueous.
- Exemplary materials which may be used as a suspending medium are mineral oil, straight chain and branched high and low molecular weight hydrocarbons, dialkyl ethers such as dioctyl and dibutyl ether, dialkyl ethers of polyethylene glycol, dibutylketone, dihexylketone, diphenyl ether. anisole, phenetole, phenyl butyl ether, a mixture of diphenyl ether and biphenyl and commercially available poly(dimethylsiloxane) (silicone) oils. Mixtures of diphenyl ether and biphenyl are available from Dow as the Dowtherm series.
- the present invention relates to a process for the preparation of polymeric microbeads that bear residual epoxy functionality on the surfaces thereof.
- the process comprises the steps of forming a dispersion comprising one or more multifunctional epoxy monomers in a non-aqueous suspending medium in the presence of a photoinitiator; and exposing the dispersion to a source of light to induce polymerization.
- the monomer(s) are dispersed in an appropriate suspending medium, such as those described above.
- a suspending medium with minimum solubility for the monomers is preferred.
- the viscosity of the suspending medium is typically a major factor in determining the particle size of the resulting polymeric microbeads, along with process parameters such as stirring rate and temperature. Therefore, particle size may be manipulated by choice of suspending medium, surfactant level and type, temperature, and stirring rate.
- the particle size of the resulting polymeric microbeads ranges from 1 ⁇ m to 500 ⁇ m, preferably from 10 ⁇ m to 300 ⁇ m.
- the polymeric microbeads also have a narrow particle size distribution, as shown in FIGS. 1 and 2.
- a narrow particle size distribution is defined as where the particle size of greater than 90% of the polymeric microbeads in said population is equal to ⁇ 20 % of the mean particle size.
- the particle size of agglomerated particles is taken as the width of the mass at its widest point.
- the figures show the particle size distribution of an exemplary group of polymeric microbeads.
- FIG. 1 is a photograph of polymeric microbeads produced by suspension photopolymerization.
- FIG. 2 is a graph showing the distribution of particle size of the particles.
- One or more surfactants may be used to stabilize the dispersion.
- the dispersion may contain up to 10% surfactant based on the weight of monomer.
- Suitable surfactants include both ionic and nonionic surfactants.
- nonionic surfactant include block copolymers such as the Pluronics ® and Tectonics ® commercially available from BASF and esters of polyethylene glycol included in the Tween ® series available from ICI Surfactants. In some cases, these surfactants may also serve as porogens.
- Initiators useful for polymerization are cationic photoinitiators such as onium salts. These are diaryliodonium salts, triarylsulfonium salts, diaryliodosonium salts, triarylsulfoxonium salts, dialkylphenacylsulfonium salts, dialkyl(hydroxy dialkylphenyl)sulfonium salts and ferrocenium salts. Such onium salts may be modified by the attachment of alkyl, alkoxy, siloxy and the like groups without decreasing their utility.
- Suitable cationic photoinitiators include, for example, (4- «-decyloxyphenyl) phenyliodonium hexafluoroantimonate, 4-(2- hydroxytetra decyloxyphenyl) phenyliodonium hexafluoroantimonate, and commercially available triarylsulfonium salt photoinitiators such as UV691 available from the Union Carbide Corporation.
- a preferred initiator is (4-n- decyloxyphenyl) phenyliodonium hexafluoroantimonate.
- the photoinitiator is employed in concentrations ranging from 0.1 to 10% by weight based on the monomer or monomers.
- the photoinitiator is typically soluble in the monomer or mixture of monomers, but exhibits minimal solubility in the suspending medium.
- the dispersion may additionally contain a photosensitizer.
- the function of a photosensitizer is to change the wavelength of sensitivity for the initiator.
- polymerizations can be conveniently carried out employing visible light provided that a photosensitizer is also included in the dispersion.
- a photosensitizer it is possible to accelerate the polymerization and hence, the formation of the microbeads.
- the many useful photosensitizers which may be used are anthracene, phenanthracene, pyrene, perylene, thioxanthone.
- concentration ranging from 10 to 50% by weight, based on the weight of the photoinitiator.
- Accelerators may also be employed for the polymerization.
- suitable accelerators are alcohols, comprising ethanol, ethylene glycol, triethylene glycol, glycerol, pentaerythritol, and hydroxy-functional oligomers and polymers, including hydroxyl-terminated polyesters and hydroxyl-terminated poly ethers.
- An apparatus for preparation of the polymeric microbeads typically includes means of dispersing the monomer(s), a temperature controller, and a source of light.
- FIGS. 3 through 6 illustrate exemplary methods of agitating the dispersion and of exposing the dispersion to a source of light.
- FIGS. 3, 4 and 5 show the use of a high speed stirrer for agitation of the dispersion.
- an arc lamp enclosed in a lamp well serves as a source of light.
- FIG. 4 shows how the light may be conducted into the reaction medium via a fiber optic cable.
- FIG. 5 light is conducted through a light-transparent reaction vessel.
- FIG. 6 illustrates the use of an ultrasonic bath for agitation of the reaction medium, and direct transmission of light from a lamp positioned above the reaction medium.
- the present invention relates to a method for attaching functional groups to the surface of a polymeric microbead comprising preparing a dispersion of polymeric microbeads bearing residual epoxy groups on surfaces.
- the dispersion comprises the one or more multifunctional epoxy monomers and, if desired, the cationically photopolymerizible monomers described above, in a non-aqueous suspending medium in the presence of a photoinitiator.
- the polymeric microbeads may be contacted with a compound which is reactive toward the residual epoxy groups, including acid anhydrides, alcohols, amides, amines, carboxylic acids, isocyanates, Grignard reagents, and thiols.
- a compound which is reactive toward the residual epoxy groups including acid anhydrides, alcohols, amides, amines, carboxylic acids, isocyanates, Grignard reagents, and thiols.
- Other types of compounds that are reactive toward epoxy groups and that are useful for attaching functionality to the surface of the bead include acetals, acetoacetates, acetonitriles. acetylenes, acyl halides, alkyl halides, alkyl hydroperoxides, amines, aminothiols. ammonia, antimony trihalides, arsinic trihalides.
- aryldichloroarsines aryllithiums. azides, carbamyl halides, carbon dioxide, carbon disulfide, cyanates, cyanoacetates. diborane, ethylene imine, halohydrins, hydrogen cyanide, hydrogen sulfide, ketones, malonates, nitrogen dioxide, nitrosyl chloride, phenols, phosgene, phosphines, phosphoric acid, phosphorous acid, phosphorous oxychloride, phthalimide, silicon tetrahalides, sodium sulfite, sulfur dioxide, sulfuryl chloride, thiocyantes, thiocyanic acid, thiolacids, thionyl chloride, thiosulfates. water and many others. Others may be found in the literature, including Handbook of Epoxy Resins. Lee and Neville, 1967, p 2-32.
- the polymeric microbeads may be directly employed for a variety of final applications. Some exemplary applications are supports for the chromatographic separations of simple compounds, ion exchange resins, polymer-bound catalysts, polymer-bound reagents, diagnostic reagents for the binding of enzymes and catalytic antibodies, and reagents for peptide and polynucleic acid synthesis.
- Epoxy functionallized beads are ideal for this purpose since the epoxy groups are highly reactive towards such a wide variety of reagents. Reactions of epoxy groups have been extensively described in the chemical literature, as noted above, and a person of ordinary skill in the art is able to prepare desired derivatives of the epoxy groups on the surface of the polymeric microbeads without undue experimentation.
- polymeric microbeads bearing functional groups allows the beads to interact in various manners with other molecules of interest. For example, reaction with a chiral amine results in the bonding of this species to the surface of the microbead producing a bead with essentially a chiral surface. Such beads are be useful for the chiral separation of enantiomers. This process is of critical interest to the pharmaceutical industry since the separation of stereoisomeric drugs into their respective enantiomers is widely practiced today by laborious and expensive methods.
- the use of chiral microbead chromatography provides a simple, direct and low cost method of separation of these substrates.
- the microbeads may be fitted with a variety of diagnostic agents. These beads can be employed for blood and urine tests for glucose, drug metabolites, and for the presence of bacterial and viral infectious agents.
- Functionallized microbeads can be used directly as prepared in various uses such as catalysts in transition metal, acid and base mediated reactions.
- polymer bound enzymes and catalytic antibodies can be directly added to reaction mixtures to achieve their desired action.
- they may be assembled into columns and the substrate passed through a solid phase bed of the microbeads to produced the desired reaction. They may also be incorporated into column form for use in high pressure liquid chromatography, preparative liquid chromatography and gas chromatography.
- Tables 1 and 2 show the composition of the dispersions prepared and the resulting bead size and epoxy content.
- the photopolymerizations were carried out in a 100 ml reaction vessel equipped with a mechanical paddle stirrer and a General Electric 150 W lamp. The reaction mixtures were stirred for a brief time to suspend the monomer mixture and then the lamp was switched on for 30 minutes.
- the polymeric microbeads were recovered by suction filtration and washed with an appropriate solvent to remove the suspending medium. The beads were characterized by optical microscopy.
- VCHDO is 4-vinylcyclohexene dioxide
- DEN 439 is an epoxy novolac available from Dow
- ELO is an epoxidized linseed oil.
- Tween 80 is a nonionic surfactant obtainable from ICI Surfactants.
- A11 compositions contained 40 mL of the dispersing medium, 0.2 g of (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate (IOC-8) and 0.02 perylene. Photopolymerizations were conducted for 30 minutes using a GE 150 W spotlight. *Suspending agent, determined by titration. "Agglomeration of the beads occurred. "Reaction temperature 60°C. b Reaction temperature 55°C. c Contains 6.2 g nitromethane as a porogen.
- compositions contained 100 mL of the dispersing medium, 2.0 g of (4-octyloxyphenyl)phenyliodonium hexafluoroantimonate (IOC-8), 25 g monomers and 0.2 g perylene. Photopolymerizations were conducted for 60 minutes at 25 °C. 'Formulation did not contain a photosensitizer. determined by tiration. "2-isopropylthioxanthone (0.2 wt%) used as a photosensitizer. a Porogens (15g) NM, nitromethane, DG, diglyme.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1999/007337 WO2000064572A2 (en) | 1999-04-26 | 1999-04-26 | Epoxy-functional polymeric microbeads |
EP99943607A EP1377451A2 (en) | 1999-04-26 | 1999-04-26 | Epoxy-functional polymeric microbeads |
US10/019,835 US6602602B1 (en) | 1999-04-26 | 1999-04-26 | Epoxy-functional polymeric microbeads |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1999/007337 WO2000064572A2 (en) | 1999-04-26 | 1999-04-26 | Epoxy-functional polymeric microbeads |
Publications (2)
Publication Number | Publication Date |
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WO2000064572A2 true WO2000064572A2 (en) | 2000-11-02 |
WO2000064572A3 WO2000064572A3 (en) | 2003-10-30 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1999/007337 WO2000064572A2 (en) | 1999-04-26 | 1999-04-26 | Epoxy-functional polymeric microbeads |
Country Status (2)
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EP (1) | EP1377451A2 (en) |
WO (1) | WO2000064572A2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003076491A1 (en) * | 2002-03-08 | 2003-09-18 | Rensselaer Polytechnic Institute | Accelerators for cationic photopolymerization |
US7015462B2 (en) | 2001-05-28 | 2006-03-21 | Michael Karas | Separation of components of an analysis sample in an ion mobility spectrometer using a supply of selectively interactive gaseous particles |
WO2007067141A1 (en) * | 2005-12-07 | 2007-06-14 | Mip Technologies Ab | Agglomerated mip clusters |
WO2014058755A1 (en) * | 2012-10-10 | 2014-04-17 | Rohm And Haas Company | Synthesis support resin |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4774189A (en) * | 1984-12-24 | 1988-09-27 | Flow Cytometry Standards Corp. | Fluorescent calibration microbeads simulating stained cells |
US5084394A (en) * | 1984-12-24 | 1992-01-28 | Vogt Robert F | Method for corrective calibration of a flow cytometry using a mixture of fluorescent microbeads and cells |
-
1999
- 1999-04-26 WO PCT/US1999/007337 patent/WO2000064572A2/en not_active Application Discontinuation
- 1999-04-26 EP EP99943607A patent/EP1377451A2/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4774189A (en) * | 1984-12-24 | 1988-09-27 | Flow Cytometry Standards Corp. | Fluorescent calibration microbeads simulating stained cells |
US5084394A (en) * | 1984-12-24 | 1992-01-28 | Vogt Robert F | Method for corrective calibration of a flow cytometry using a mixture of fluorescent microbeads and cells |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7015462B2 (en) | 2001-05-28 | 2006-03-21 | Michael Karas | Separation of components of an analysis sample in an ion mobility spectrometer using a supply of selectively interactive gaseous particles |
DE10292304B4 (en) * | 2001-05-28 | 2015-09-10 | Excellims Corp. | Separation of components of an analytical sample in an ion mobility spectrometer by supplying selectively interacting gaseous particles |
WO2003076491A1 (en) * | 2002-03-08 | 2003-09-18 | Rensselaer Polytechnic Institute | Accelerators for cationic photopolymerization |
US6863701B2 (en) | 2002-03-08 | 2005-03-08 | Rensselaer Polytechnic Institute | Accelerators for cationic photopolymerizations |
WO2007067141A1 (en) * | 2005-12-07 | 2007-06-14 | Mip Technologies Ab | Agglomerated mip clusters |
WO2014058755A1 (en) * | 2012-10-10 | 2014-04-17 | Rohm And Haas Company | Synthesis support resin |
Also Published As
Publication number | Publication date |
---|---|
WO2000064572A3 (en) | 2003-10-30 |
EP1377451A2 (en) | 2004-01-07 |
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