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WO2004054709A1 - Sorbants a taille de pores standard - Google Patents

Sorbants a taille de pores standard Download PDF

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Publication number
WO2004054709A1
WO2004054709A1 PCT/EP2003/012951 EP0312951W WO2004054709A1 WO 2004054709 A1 WO2004054709 A1 WO 2004054709A1 EP 0312951 W EP0312951 W EP 0312951W WO 2004054709 A1 WO2004054709 A1 WO 2004054709A1
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WO
WIPO (PCT)
Prior art keywords
polymerization
particles
template
sorbents
solution
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.)
Ceased
Application number
PCT/EP2003/012951
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German (de)
English (en)
Inventor
Egbert Müller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Priority to AU2003303024A priority Critical patent/AU2003303024A1/en
Publication of WO2004054709A1 publication Critical patent/WO2004054709A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • 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
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28088—Pore-size distribution
    • B01J20/2809—Monomodal or narrow distribution, uniform pores
    • 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
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
    • B01J20/285—Porous sorbents based on polymers
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
    • B01J20/3064—Addition of pore forming agents, e.g. pore inducing or porogenic agents
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078

Definitions

  • the invention relates to monolithic or particulate sorbents made from organic polymers and their use in chromatography.
  • Monolithic shaped bodies or particulate materials made from organic or inorganic polymers are typically used as sorbents for chromatography.
  • sorbents for chromatography.
  • materials with a large specific surface For this reason, mostly porous materials are used for chromatography.
  • the pores can be created by chemical processes (e.g. phase separation, salt expansion) or physical processes (e.g. temperature treatment).
  • chemical processes e.g. phase separation, salt expansion
  • physical processes e.g. temperature treatment
  • Pores are formed by adding a porogen to the polymer solution.
  • the statistical distribution of the size of these pores in the Sorbents is mostly of the Gauss type.
  • the production of membranes from organic polymers is disclosed in EP 0 320 023. These polymer membranes are preferably used for the separation of macromolecular substances such as biopolymers, since macroporous materials can be used for such applications.
  • macromolecular substances such as biopolymers
  • mesoporous organic polymers with a narrow pore size distribution for the separation of smaller molecules cannot be produced in the necessary quality.
  • colloidal particles are arranged in a regular package as a template, this template package is impregnated with a polymerization solution,
  • the materials according to the invention are produced from monodisperse silica gel particles which are centrifuged into a polymerization mold with a polymerization solution. The mixture is then polymerized and the silica gel particles are extracted.
  • the separating material obtained in this way can be used as a monolithic sorbent or comminuted as a particulate sorbent.
  • the separating materials according to the invention with a uniform pore size show significantly better separating properties than corresponding conventional materials with a pore size distribution of the Gauss type.
  • the present invention therefore relates to a process for the production of sorbents from organic polymers having a uniform pore size, with the following process steps: a) providing a polymerization form; b) filling the polymerization mold with a polymerization solution and with monodisperse template particles with a diameter between 100 nm and 300 ⁇ m; c) centrifugation of the filled polymerization mold; d) optionally pouring off the excess polymerization solution; e) polymerization; f) Removing the template particles with a washing solution which dissolves the template particles.
  • step c) 1 to 2 hours
  • the treatment with hydrofluoric acid in step f) takes place at temperatures between 50 and 85 ° C.
  • the polymer block formed is removed from the polymerization mold after step e) and comminuted into particles.
  • a mixture of styrene and trimethyl methacrylate ester is used as the polymerization solution.
  • the sorbent obtained after step f) is dried at a temperature between 200 and 350 ° C.
  • the template particles used in step b) carry template molecules on their surface.
  • the present invention also relates to sorbents made from organic polymers having a uniform pore size and produced by the process according to the invention.
  • the present invention also relates to the use of the materials according to the invention for the chromatographic separation of at least two substances.
  • sorbents made from organic polymers are sorbents which are produced by polymerizing one or more organic monomers and / or oligomers.
  • the process according to the invention has the advantage that sorbents with a homogeneous pore distribution are produced which can be used both as monolithic and as particulate sorbent.
  • the preferred thermal aftertreatment can greatly reduce the often undesirable swelling behavior of the sorbents in organic solvents.
  • any form which is stable with respect to the polymerization solution and from which the polymerization block can be removed after the template particles have been washed out or preferably directly after the polymerization has taken place can be used as the polymerization form.
  • the form of polymerization should match the shape of the monolith to be made.
  • Tubular polymerization forms are therefore preferably used, the inside diameter of which typically does not exceed 1 to 2 cm, since otherwise the template particles can only be removed very slowly.
  • Centrifuge tubes are particularly preferably used, which at both ends by means of a
  • Screw lid can be opened and closed. In this way, the polymer block can be pushed out of the polymerization mold after the polymerization.
  • Polytetrafluoroethylene is particularly preferably used as the material of the polymerization form.
  • monodisperse porous or preferably non-porous silica particles ie silica gel particles
  • template particles These materials can be produced in different particle sizes with good monodispersity. It is also possible to use other monodisperse particles made from inorganic oxides, such as Al 2 O 3 , provided that they can be produced in a suitable quality. According to the invention, these materials also fall under the term template particles.
  • the diameter of the template particles is between 100 nm and 300 ⁇ m. Particles between 200 nm and 5 ⁇ m in diameter are preferably used. With these particle sizes, depending on the selected particle size and also depending on the polymerization solution used, sorbents with pore sizes between approx. 30 and 300 nm in diameter are obtained, which are very suitable for chromatographic separations (see Example 1).
  • the process according to the invention enables a wide variety of organic polymeric moldings to be produced.
  • the moldings can be produced, for example, by radical, ionic or thermal polymerization. It can be, for example, poly (meth) acrylic acid derivatives, polystyrene derivatives, polyesters, polyamides or polyethylenes.
  • the monomers to be used accordingly are known to the person skilled in the art in the field of organic polymers.
  • monoethylenically or polyethylenically unsaturated monomers such as vinyl monomers, vinyl aromatic and vinyl aliphatic monomers, for example styrene and substituted styrenes, vinyl acetates or vinyl propionates, acrylic monomers, such as methacrylates and other alkyl acrylates, ethoxymethyl acrylate and higher analogues and the corresponding methacyl acid esters or their corresponding amide, such as acrylamide or acrylonitrile.
  • monoethylenically and polyethylenically unsaturated monomers can be found, for example, in EP 0 366 252 or US 5,858,296. The person skilled in the art is able to combine the various monomers / oligomers accordingly, optionally to choose a suitable free-radical initiator or initiator and thus to put together a polymerization solution with which the polymerization form is filled up.
  • the mold filled with the template particles and the polymerization solution is first centrifuged so that the particles settle and form the densest spherical packing possible. It has been found that materials with a particularly uniform pore distribution can be produced by the centrifugation step according to the invention, i.e. centrifugation leads to a much better packing of the particles than e.g. a sedimentation. Furthermore, the centrifugation step offers process engineering advantages over e.g. a pack under pressure, since the aggressive and mostly unmanageable polymerization solutions only have to be filled in and do not have to be pumped through a suitable vessel to seal the particles under pressure.
  • Centrifugation is preferably carried out at 2000 to 4000 revolutions for 1 to 2 hours.
  • any excess polymerization solution is poured off or pipetted off, and the part of the polymerization solution remaining in the polymerization form is polymerized.
  • the duration and temperature of the polymerization are matched to the respective monomer solution according to customary rules. It was found that it takes a little longer to complete the reaction than a corresponding polymerization in solution would require. A person skilled in the art of polymerization is able to optimize the polymerization conditions and the polymerization time accordingly.
  • the solid polymerization block formed which consists of the inorganic template particles and the organic polymer formed around them, is removed and the material of the template particles is washed out and dissolved out. To do this, the polymer block is washed in a washing solution that
  • Particles dissolve, optionally with heating, stored or preferably pivoted.
  • Ammonia solution solutions of amines, alkali metal solutions, such as sodium hydroxide solution, or preferably aqueous hydrofluoric acid can be used as the washing solution which dissolves the template particles.
  • a treatment with aqueous hydrofluoric acid to remove silica gel typically takes 2 to 10 days, depending on the size of the polymer block. This step is preferably carried out at a temperature between 50 and 85.degree.
  • the porous organic polymer molded body is obtained as an impression or counterpart to the polymerization mold used, which is filled with the template particles.
  • the polymerization block obtained after the polymerization can first be comminuted, for example in a mortar, before the template particles are washed out. This procedure is possible if a particulate sorbent is to be produced. By shredding the polymer block, the washing out of the template particles is accelerated. Then the fragments can e.g. be ground in a ball mill and divided by sieving.
  • the shaped bodies or particles are preferably dried for 1 to 7 days after treatment with hydrofluoric acid and corresponding washing at temperatures between 200 and 350 ° C., preferably at about 250 ° C. If necessary, this drying should take place under protective gas, e.g. argon, respectively. It has been found that this undesired swelling behavior of the polymeric moldings can be greatly reduced by this drying at high temperatures. For example, thermal aftertreatment (24 h at 250 ° C.) can increase the length of a 2 cm long polymer rod (diameter 1 cm) made of styrene and trimethyl methacrylate ester when treated with water / acetonitrile (50/50, v / v) by 15% 5% can be reduced.
  • thermal aftertreatment 24 h at 250 ° C.
  • thermal aftertreatment can increase the length of a 2 cm long polymer rod (diameter 1 cm) made of styrene and trimethyl methacrylate ester when treated with water / acetonit
  • the resulting shaped bodies or particles can be used directly for chromatographic separations.
  • a polymer made of polystyrene or derivatives thereof can be used directly for reversed phase separations.
  • the particles are packed in appropriate chromatography columns and the shaped bodies are provided with appropriate connectors, surrounded with a jacket and integrated in a chromatographic separation column.
  • Suitable holders and jackets are already known for inorganic monolithic sorbents (e.g. WO 98/59238 and WO 01/03797) and can be transferred to the moldings according to the invention.
  • plastics e.g. PEEK or fiber reinforced
  • the organic moldings according to the invention can usually be coated more effectively and more densely than the corresponding inorganic moldings, since they can form a stronger bond with the plastic coating.
  • Monomers which, in addition to a polymerizable double bond, also have other functionalities, such as Oxirane rings, are known to the person skilled in the art. Examples can be found in WO 96/22316 or WO 95/10354.
  • suitable functionalities of the sorbents according to the invention can be used to bind or immobilize biomolecules, such as enzymes. Macroporous moldings or particles are particularly suitable for this. Therefore, biomolecules such as Enzymes according to the invention also under the term separation effectors.
  • template molecules can be bound to the surface of the, in this case porous or non-porous, template particles.
  • the method according to the invention has the advantage that the template molecules assume a defined aligned position due to the binding to the template particles. In this way, more defined cavities are created, which can enter into clearer and stronger interactions during the chromatographic separation.
  • Another great advantage of the process according to the invention is that after the polymerization, all template molecules can be washed out. In conventional processes, part of the template molecules are completely surrounded by the polymer after the polymerization and cannot be removed from the polymer at all or only very slowly. Since template molecules can still be released from the polymer even when the polymers are later used for chromatographic separation and falsify the analysis, the use of such materials is mostly limited to purification or qualitative analysis. A trace analysis is hardly possible.
  • Polymers produced according to the invention do not show this bleeding.
  • the reason for this is the preferred covalent binding of the template molecules to the template particles. In this way, they are never completely surrounded and held in place by the polymerized molded body, but are completely removed by washing out the template particles together with them.
  • the template is first bound to the template particles. Excess template molecules can be washed off and collected. Only in a second step is the monomer solution added and polymerized.
  • the polymer moldings produced by the process according to the invention using a template can, as already explained in the description of the production process, be used both as moldings or can also be comminuted into particles for certain applications.
  • the method according to the invention thus offers the possibility of producing organic polymer moldings with a defined, narrow pore size manufacture.
  • the pores can be defined by the template particles themselves or by a modification of the particles with template molecules.
  • the method according to the invention is simple and reliable.
  • the centrifugation step ensures that a dense and homogeneous packing of the template particles is generated.
  • the materials according to the invention enable more effective chromatographic separations in comparison to conventional sorbents with a Gaussian-like distribution of the pore size.
  • the surface of the template particles and / or the surface of the shaped body according to the invention can be modified, so that there are a multitude of possibilities for ideally adapting the shaped bodies to the particular separation problem.
  • Approximately 1 g of monodisperse silica gel particles are suspended in about 2 ml of a styrene / divinylbenzene polymerization solution (1: 1, v: v) with the addition of 1% (m: m) azoisobutyronitrile.
  • the solution is evacuated and filled into a plastic sleeve made of PTFE (polytetrafluoroethylene). It is polymerized at 70 ° C for 20 hours.
  • the polymerization block is then removed and shaken in aqueous hydrofluoric acid for 144 hours at room temperature. Then it is carefully washed with water.
  • Particles take place over 10 days in HF at 70 ° C. Then it is shaken twice with deionized water and twice with acetone and dried in vacuo at 70 ° C. A silicon analysis showed ⁇ 0.3%.
  • the fragments obtained are ground in a ball mill with porcelain balls with an average diameter of 5 cm (duration approx. 20 hours) and then dried at 250 ° C. for 5 days. Then they are pre-sorted on a 250 ⁇ m sieve and added for particle size distribution and sieving. 5
  • Monospher ® 250 (diameter 0.25 ⁇ m) particles are suspended in a polymerization solution consisting of 5 ml trimethylolpropane trimethacrylate, 5 ml 0 styrene and 0.04 g azoisobutyronitrile and filled into three centrifuge tubes made of PTFE (inner diameter 1 cm) and allowed to settle.
  • the supernatant solution is suctioned off and the centrifuge tubes are centrifuged for 1 hour at 3000 rpm. They are then stored in the oven for 18 hours at 70 ° C for polymerization. Allow to cool 5 and push the polymer blocks out of the centrifuge tubes.
  • the template particles are extracted in HF at 70 ° C for 10 days. The mixture is then shaken twice with deionized water and twice with acetone, dried in vacuo at 70 ° C. and then dried at 250 ° C. for 5 days. ° A silicon analysis showed ⁇ 0.3%. 4. Comparison with conventional sorbents
  • the theoretical floor height for human insulin was determined by measuring the peak widths: a) LiChrospher ® WP 300 3500 theoretical floors per mb) Chromolith ® RP 18 8040 theoretical floors per mc) particles according to the invention 8100 theoretical floors per m
  • the theoretical plate number of the LiChrospher ® WP 300 material should be 10 ⁇ m (twice the particle size), which corresponds to a plate number of 100,000 for toluene. With the 25 ⁇ m material produced according to the invention, the number of trays would have to be 5 times worse. Instead, it is almost three times as good.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne des matériaux de séparation organiques à taille de pores standard pour la chromatographie. Pour la production desdits matériaux, un moule de polymérisation est rempli de particules matricielles monodispersées et d'une solution de polymérisation appropriée, centrifugé et polymérisé puis les particules matricielles sont éliminées de préférence à l'acide fluorhydrique.
PCT/EP2003/012951 2002-12-14 2003-11-19 Sorbants a taille de pores standard Ceased WO2004054709A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003303024A AU2003303024A1 (en) 2002-12-14 2003-11-19 Sorbents with standard pore sizes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10258491A DE10258491A1 (de) 2002-12-14 2002-12-14 Sorbenzien mit einheitlicher Porengröße
DE10258491.5 2002-12-14

Publications (1)

Publication Number Publication Date
WO2004054709A1 true WO2004054709A1 (fr) 2004-07-01

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PCT/EP2003/012951 Ceased WO2004054709A1 (fr) 2002-12-14 2003-11-19 Sorbants a taille de pores standard

Country Status (3)

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AU (1) AU2003303024A1 (fr)
DE (1) DE10258491A1 (fr)
WO (1) WO2004054709A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100410301C (zh) * 2006-02-21 2008-08-13 武汉化工学院 一种用抽滤/浸渍法制备有序多孔导电聚合物的方法
WO2009043191A3 (fr) * 2007-10-05 2009-05-28 Eldgenoessische Tech Hochschul Procédé de production de matériaux macroporeux
CN102604008A (zh) * 2012-03-15 2012-07-25 江南大学 一种培氟沙星表面分子印迹聚合物的制备方法以及应用
CN102775554A (zh) * 2012-07-06 2012-11-14 江南大学 一种肉桂醛表面分子印迹聚合物的制备方法
EP3173146A1 (fr) * 2015-11-27 2017-05-31 InstrAction GmbH Matériau polymère poreux pour la liaison d'ions métalliques ou pour le nettoyage de molécules organiques
CN112316753A (zh) * 2020-09-22 2021-02-05 宁波方太厨具有限公司 高通量疏松型中空纤维纳滤膜的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018000650A1 (de) 2018-01-27 2019-08-01 Friedrich-Schiller-Universität Jena Verfahren zur Bestimmung von Verunreinigungen in Polyalkylenethern oder Polyalkylenaminen und dessen Verwendung

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0341556A1 (fr) * 1988-05-06 1989-11-15 E.I. Du Pont De Nemours And Company Microsphères poreuses organiques pour la chromatographie à haute performance en phase liquide
EP0366252A1 (fr) * 1988-09-26 1990-05-02 Supelco, Inc. Résines poreuses rigides et procédé de fabrication
WO2001023083A1 (fr) * 1999-09-29 2001-04-05 Merck Patent Gmbh Corps moules polymeres organiques poreux
WO2001087575A2 (fr) * 2000-05-12 2001-11-22 The Regents Of The University Of Michigan Fabrication inversee de materiaux poreux

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0341556A1 (fr) * 1988-05-06 1989-11-15 E.I. Du Pont De Nemours And Company Microsphères poreuses organiques pour la chromatographie à haute performance en phase liquide
EP0366252A1 (fr) * 1988-09-26 1990-05-02 Supelco, Inc. Résines poreuses rigides et procédé de fabrication
WO2001023083A1 (fr) * 1999-09-29 2001-04-05 Merck Patent Gmbh Corps moules polymeres organiques poreux
WO2001087575A2 (fr) * 2000-05-12 2001-11-22 The Regents Of The University Of Michigan Fabrication inversee de materiaux poreux

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
C.G. GÖLTNER: "Poröse Festkörper aus rigiden kolloidtemplaten: Morphogenese", ANGEWANDTE CHEMIE, vol. 111, no. 21, 1999, WEINHEIM, pages 3347 - 3349, XP002270872 *
S. JOHNSON, P. OLLIVIER AND T. MALLOUK: "Ordered mesoporous polymers of tunable pore size from colloidal silica templates", SCIENCE, vol. 283, 1999, pages 963 - 965, XP002270952 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100410301C (zh) * 2006-02-21 2008-08-13 武汉化工学院 一种用抽滤/浸渍法制备有序多孔导电聚合物的方法
WO2009043191A3 (fr) * 2007-10-05 2009-05-28 Eldgenoessische Tech Hochschul Procédé de production de matériaux macroporeux
CN102604008A (zh) * 2012-03-15 2012-07-25 江南大学 一种培氟沙星表面分子印迹聚合物的制备方法以及应用
CN102604008B (zh) * 2012-03-15 2014-07-09 江南大学 一种培氟沙星表面分子印迹聚合物的制备方法以及应用
CN102775554A (zh) * 2012-07-06 2012-11-14 江南大学 一种肉桂醛表面分子印迹聚合物的制备方法
EP3173146A1 (fr) * 2015-11-27 2017-05-31 InstrAction GmbH Matériau polymère poreux pour la liaison d'ions métalliques ou pour le nettoyage de molécules organiques
CN112316753A (zh) * 2020-09-22 2021-02-05 宁波方太厨具有限公司 高通量疏松型中空纤维纳滤膜的制备方法

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Publication number Publication date
DE10258491A1 (de) 2004-07-01
AU2003303024A1 (en) 2004-07-09

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