EP1562700A1 - Corps fa onnes monolithiques inorganiques recouverts d'un revetement de polymeres organiques - Google Patents
Corps fa onnes monolithiques inorganiques recouverts d'un revetement de polymeres organiquesInfo
- Publication number
- EP1562700A1 EP1562700A1 EP03809725A EP03809725A EP1562700A1 EP 1562700 A1 EP1562700 A1 EP 1562700A1 EP 03809725 A EP03809725 A EP 03809725A EP 03809725 A EP03809725 A EP 03809725A EP 1562700 A1 EP1562700 A1 EP 1562700A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- shaped body
- coating
- coated
- polymer
- inorganic
- 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.)
- Withdrawn
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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- B01J20/28014—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 form
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- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
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- B01J20/28092—Bimodal, polymodal, different types of pores or different pore size distributions in different parts of the sorbent
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- B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
- B01J20/3219—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond involving a particular spacer or linking group, e.g. for attaching an active group
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- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
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- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
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- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3268—Macromolecular compounds
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- B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2220/82—Shaped bodies, e.g. monoliths, plugs, tubes, continuous beds
- B01J2220/825—Shaped bodies, e.g. monoliths, plugs, tubes, continuous beds comprising a cladding or external coating
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G01N30/50—Conditioning of the sorbent material or stationary liquid
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Definitions
- the present invention relates to inorganic monolithic moldings, the surface of which is coated with physisorbed or chemisorbed organic polymers, and to processes for producing such materials.
- the materials according to the invention are outstandingly suitable as sorbents for chromatography, in particular for high-pressure liquid chromatography of biological materials.
- Chromatographic carrier materials or sorbents which are used for the separation or purification of biological materials, such as proteins, nucleic acids etc., must have good alkali stability in addition to good separation properties. The reason for this are in particular special cleaning and sterilization processes to which the sorbents are subjected.
- the sorbent is treated with 1 M sodium hydroxide solution over a period of 10 minutes to three hours depending on the column dimension.
- the carrier materials are stored for long-term storage in 0.1 M sodium hydroxide solution. Not all substrates are stable under such conditions. For example, inorganic carrier materials based on silicon dioxide are often not sufficiently stable under the conditions mentioned.
- organic polymers such as dextran, agarose, cellulose, polystyrene or methacrylate ester, or inorganic particulate materials coated with such organic polymers, are frequently used as carrier materials in biochromatography.
- examples of polymer-coated inorganic particles can be found, for example, in US Pat. No. 4,308,254 or US Pat. No. 5,271,833.
- US 4,308,254 discloses inorganic porous particles, for example made of silica, aluminum, magnesium or titanium oxide, which are coated with polysaccharide polymer.
- US 5,271,833 discloses inorganic oxide particles surrounded by an organic polymer.
- Monoliths of course, have the same properties as polymer balls, which are packed directly into a column, and thus also the same disadvantages. To the others there is a great danger that smaller ducts in particular will become completely blocked and uneven pressure conditions in the monolith arise, which in turn lead to a deterioration in the separation properties.
- the inorganic porous monolithic shaped bodies are evenly coated with a coating of organic polymer.
- the predetermined rigid structure of the monolithic material causes a deformation or destruction of the
- sorbents can be produced which show only a moderate column back pressure even at high flow rates.
- the present invention therefore relates to porous inorganic monolithic moldings which are coated with at least one organic polymer.
- the porous inorganic monolithic shaped bodies are materials based on SiO 2 .
- the porous inorganic monolithic shaped bodies have a bimodal pore structure with mesopores with a diameter between 2 and 100 nm and macropores with an average diameter of over 0.1 ⁇ m.
- the organic polymers are polystyrenes or poly (meth) acrylates, and also other poly (meth) acrylic acid derivatives, such as, for example, poly (meth) acrylamide derivatives.
- the organic polymer is physisorbed on the inorganic shaped body.
- the present invention also relates to a process for the production of porous inorganic monolithic shaped bodies which are coated with at least one organic polymer, which has the following process steps: a) providing a porous inorganic monolithic shaped body b) impregnating the porous inorganic monolithic material from step a) with a coating solution containing at least organic prepolymers or mono- and / or oligomers. c) coating the shaped body, the shaped body being tightly coated with an inert material at least on the long sides during the coating or being stored in an inert solvent d) washing and drying the shaped body from step c) to remove reaction residues and solvents
- step c) the prepolymers or monomers and / or oligomers from the coating solution are struck on the inorganic shaped body.
- the precipitation takes place by lowering the temperature.
- the present invention also relates to the use of the moldings according to the invention for the chromatographic separation of at least two substances, in particular for the separation and / or purification of biological materials.
- Shaped bodies in the sense of the present invention are in particular shaped bodies which can be used as a single piece for chromatographic separations and not like a large number of particles in one Sows are filled.
- these are flat or columnar shaped bodies.
- Flat shaped bodies have their greatest extent transverse to the flow direction of the eluent.
- Column-shaped bodies are particularly preferred which have an extension of the same length or length along the axis through which the elution agents flow.
- the size and dimension of the shaped bodies correspond to the dimensions customary for use in chromatography.
- Flat shaped bodies typically have a thickness between 0.2 and 20 ⁇ m
- columnar shaped bodies typically have a diameter between 0.1 cm and 5 cm and a length (longest dimension) between 1 and 30 cm.
- the specified dimensions can be exceeded in accordance with the dimensions of known column dimensions.
- the dimensions specified can fall below the range of capillaries.
- porous inorganic monolithic shaped bodies typically consist of inorganic oxides, such as aluminum oxide, titanium dioxide or preferably silicon dioxide.
- the pore structure of the inorganic shaped bodies is of great importance for the suitability of the coated shaped bodies according to the invention as chromatographic sorbents. On the one hand, it influences how homogeneously the polymer coating can be applied to the molded body. On the other hand, it influences the separation performance and the column back pressure of the coated molded body. Moldings which are suitable according to the invention have at least pores which also allow the molding to flow through after the coating. Materials which have at least macropores are therefore preferred.
- Such materials can be produced, for example, according to a sol-gel process according to WO 95/03256 and particularly preferably according to WO 98/29350.
- Organic polymers suitable for coating the shaped bodies are organic materials which can be applied to the shaped body as an oligomer and / or polymer or organic oligomers and / or monomers which are based on the polymerisation or polycondensation
- the organic polymers can be chemisorbed or physisorbed on the shaped body.
- Suitable organic polymers are, for example, polystyrenes, polymethacrylates, melamines, polysaccharides, polysiloxanes and their derivatives or copolymers of two or more suitable compounds, such as a coating of tetraalkoxysilane and methyltrialkoxysilane. Also suitable are copolymers of the aforementioned substances with monomers which already carry separation effectors suitable for chromatography, such as, for example, copolymers of polystyrenes with compounds which carry ion-exchange groups.
- chemisorbed or physisorbed polystyrenes or polystyrene derivatives particularly preferred are physisorbed poly (meth) acrylates or poly (meth) acrylate derivatives, as well as other poly (meth) acrylic acid derivatives such as poly (meth) acrylamide derivatives.
- physisorbed poly (meth) acrylates or poly (meth) acrylate derivatives as well as other poly (meth) acrylic acid derivatives such as poly (meth) acrylamide derivatives.
- poly (methacrylate) poly (2-hydroxyethyl methacrylate)
- the polymer coating can be carried out in various ways: 1) by polymerization or polycondensation of physisorbed ones
- a solution which is used for the coating of the shaped bodies according to the invention accordingly contains either organic prepolymers or monomers and / or oligomers. In addition, it typically contains a suitable solvent and optional additional components, e.g. Radical initiator. According to the invention, it is referred to as a coating solution.
- prepolymers means that oligomerized and / or polymerized compounds are already used which, after being introduced into the molded body, are no longer subjected to any further polymerization reaction, i.e. can no longer be networked with each other. Depending on the type of application, they are adsorbed onto the molded body (physisorption) or covalently bound (chemisorption).
- Monomers and / or oligomers are compounds which are suitable for polymerization or polycondensation and, after introduction into the shaped body, are further crosslinked or polymerized by polymerization or polycondensation.
- Oligomers are compounds which have already been generated beforehand by crosslinking or polymerizing monomers.
- Particle coating processes often involve the application of a polymer solution or a solution of monomer and radical initiator. The solvent is then removed. This method cannot be used when coating molded articles.
- the evaporation process of the solvent takes place over a relatively small surface (the outer surface of the monolith).
- polymer solution is repeatedly drawn from the inside of the molded body (blotting paper effect; capillary effect), which makes the production of homogeneous coatings almost impossible.
- Coated moldings are obtained according to the invention which have improved properties, in particular improved stability, for example against alkaline solutions.
- Coating processes in which the coating solution is incorporated into the shaped body are suitable for producing such improved coated shaped bodies. is brought and the chemical or physical sorption of the polymer coating takes place without first removing the solvent of the coating solution. The solvent is only removed after chemical or physical sorption.
- processes are suitable in which a polymerization or polycondensation of monomers and / or oligomers can take place in the presence of the solvent, or preferably processes in which prepolymers or monomers and / or oligomers can be precipitated onto the shaped body from the solvent.
- the coating of the shaped bodies according to the invention is preferably already carried out in a casing which tightly encloses at least the long side of the shaped body.
- the jacket should be inert to the reagents and solvents involved in the coating.
- the coating solution can then preferably, similarly to a chromatography column, be pumped into the coated shaped body via suitable connections.
- Coating can also be carried out by introducing an unclad molded body for the coating into an inert solvent becomes.
- the molding is first soaked with the coating solution. Then, to carry out the coating, it is immersed as completely as possible in an inert solvent.
- inert means that the solvent is not involved in the polymerization or polycondensation.
- the shaped body In order to carry out the method according to the invention, it may be necessary to chemically modify the shaped body before filling it with the coating solution in order to provide the surface of the inorganic material with functional groups which are necessary for the physical or chemisorption of the organic polymer coating.
- Suitable methods are known to the person skilled in the field of sorbents.
- the reactions which are also used to introduce separation effectors into chromatographic support materials are suitable for introducing the functional groups.
- the reaction with suitably functionalized silanes can, for example, carry groups which are capable of polymerization and which, when monomers and / or oligomers are polymerized, enable covalent attachment to the shaped body. Methods for introducing such functionalities are disclosed, for example, in WO 94/19687.
- the shaped body is first impregnated with a coating solution. This can be done, for example, by immersing the molded body in a speaking solution or, in the case of a coated article by pumping through or pumping the coating solution.
- the molding is then coated depending on the type of coating solution. If the coating solution contains prepolymers, these are struck onto the molded body under suitable conditions. If chemisorption of the prepolymers is desired, this can take place, for example, by increasing the temperature, lowering the temperature, irradiation or adding reagents which start the chemical reaction between the molded article and the prepolymer.
- a process variant in which the prepolymers are precipitated from the coating solution by falling below the solubility product, preferably by lowering the temperature, has proven to be particularly advantageous for producing a homogeneous coating.
- the strong temperature reduction results in a supersaturated solution from which the prepolymers are deposited evenly on the molded body.
- the rate of precipitation can e.g. controlled by the rate of temperature change.
- an increase in the temperature can, if appropriate, bring about a uniform coating of the molding, in particular if the polymers melt as a result of the temperature increase and are therefore deposited on the surface of the molding ,
- the binding can be started after the precipitation by suitable initiation, such as irradiation, addition of reaction starters, etc. - 13 -
- the shaped body is rinsed thoroughly with suitable solvents in order to remove reaction residues, such as unreacted monomers or non-adsorbed polymer.
- the coated shaped body is then dried, preferably in vacuo.
- the shaped articles coated according to the invention can be used directly for chromatographic separations or can be functionalized beforehand with separation effectors. These are, for example, ionic, hydrophobic, chelating or chiral groups. Methods for introducing such functionalities are known to the person skilled in the field of chromatographic support materials and are described in relevant textbooks, e.g. Manual of the HPLC, ed. K.K. Unger; GIT-Verlag (1989) and Porous Silica, K.K. Unger, Elsevier Scientific Publishing Company (1979).
- the moldings according to the invention are particularly suitable for biochromatography, since they are characterized by good base stability when using base-stable organic polymers and at the same time show good separation performances and a low column back pressure.
- the shaped articles coated according to the invention can be used as a solid phase for the immobilization of catalysts, e.g. Biocatalysts such as enzymes can be used.
- catalysts e.g. Biocatalysts such as enzymes
- Suitably functionalized moldings can also serve as reaction partners for the flow synthesis.
- Example 1 Comparison of the properties of a C18-functional molded article with a polymer-coated molded article according to the invention
- the usual method for shielding a silica gel in the chromatography is 0, the surface modification by reacting with a hydrophobic silane.
- the measurement of the elemental analysis shows a content of 16.2% carbon.
- the silica gel surface of the moldings (the same starting material as in 1.1) is coated by polymerizing a mixture of styrene and divinylbenzene.
- a monomer mixture is first prepared from 12 g of styrene and 6 g of divinylbenzene with 0.5 g of azoisobutyronitrile in 50 ml of toluene.
- the impregnated rods are then placed in a reaction apparatus with fresh toluene which has been preheated to 80.degree.
- the reason for this is that only the coating solution inside the molded body is to be reacted so that an outer polymer layer on the molded body and / or solution polymer does not make cleaning more difficult and falsify the subsequent resistance test.
- the moldings are removed and the unreacted monomer and non-adsorbed polymer are removed by extraction with toluene. After drying at 100 ° C in a vacuum, a weight gain of 6% is found.
- the measurement of the elemental analysis shows a content of 5.5% carbon.
- the silica gel surface is coated by in-situ polymerization of a mixture of styrene and divinylbenzene.
- a mixture of styrene and divinylbenzene Around - 16 -
- the molded body was first reacted with a mixture of toluene and methacryloxypropyltrimethoxysilane.
- Length (production according to WO 98/29350), which has a specific surface area of 300 m 2 / g and a pore volume of 1 ml / g, is heated to 80 ° C. in an HPLC oven. A mixture of 20 g of toluene and 2 g of methacryloxypropyltrimethoxysilane is pumped through the shaped body at a flow of 0.5 ml / minute and then washed with toluene.
- a monomer mixture is then prepared from 6 g of styrene and 3 g of divinylbenzene with 0.5 g of azoisobutyronitrile in 50 ml of toluene.
- the previously degassed reaction mixture is pumped at a flow of 0.5 ml / minute through the shaped body, which was heated to 80 ° C. in an HPLC oven.
- the shaped body is then rinsed with 50 ml of toluene at 80 ° C. After drying at 100 ° C in a vacuum, a weight gain of 10% is found.
- the measurement of the elemental analysis shows a content of 9.3% carbon.
- the moldings are placed in 100 ml of a solution of 4 g NaOH in 1 l water (0.1 N sodium hydroxide solution) and after 1 h, 5 h and 24 h in each case - 17 -
- the samples obtained are dried and examined by elemental analysis.
- the PEEK-coated molded body is pumped through with a solution of 4 g of NaOH in 1 l of water (0.1 N sodium hydroxide solution) for 24 hours at a flow of 0.2 ml / minute and washed by washing with water, methanol and toluene.
- Table 1 shows the remaining carbon content of the moldings and their properties after treatment with sodium hydroxide solution for different lengths:
- FK1 C18 functionalized molded body (see 1.1)
- FK2 molded article coated with styrene / divinylbenzene in toluene (see 1.2)
- FK3 Shaped body coated with styrene / divinylbenzene in the jacket
- the encapsulation of the moldings by the polymer coating can be shown by the stability test in alkaline solution. However, it also makes sense for some applications to use coatings
- the example also does not limit the production of polymers on other inorganic supports.
- the FK2 in the coated molded body was characterized by measuring the specific surface area and the pore volume. there - 19 -
- Shaped body not completely filled with polymer. Accessible pore spaces thus remain in the monolith coated according to the invention.
- Example 2 Production of coated foreign bodies by precipitation of prepolymers 2.1 synthesis
- the following reactions were carried out in an apparatus according to Figure 1.
- the molded body (1) is surrounded by a pressure-stable casing (2).
- the coating solution and other washing solutions etc. are premixed in containers (3) and by means of a pump (4) via a pressure reservoir (5) into a storage container (6) made of pressure-resistant steel and from there through the molded body (1) into a waste container ( 7) pumped.
- DMF dimethylformamide
- HPLC pump “Bischoff brand)
- the pressure reservoir (5) which is partially filled with air, generates pressure and thus presses the coating solution into the molded body. Since air acts as a pressure mediator (air cushion), it is ensured that the 20
- the pressure to be applied here is - 0.4 bar at a flow rate of 1 min "1.
- the molded body is removed, tightly by means of screw connections sealed and then added to the prepared cooling bath (methanol / dry ice), which was heated to -55 ° C. for 40 min, after which the solvent was removed by means of a vacuum line at 40 ° C., 1 Torr for 12 h.
- the coating can be made using poly (methacrylate) instead of
- PEMA poly (2-hydroxyethyl methacrylate)
- P2HEMA poly (2-hydroxyethyl methacrylate
- P2HE.-E poly (2-hydroxyethyl methacrylate
- POMA poly (octadecyl methacrylate)
- a container with compressed gas e.g. a nitrogen bomb.
- the carbon content of the coated moldings is shown in Table 2.
- FIG. 1 shows the comparison of a scanning electron micrograph of an uncoated shaped body (Chromolith ® from Merck KGaA) ( Figure 2 A) and one with a copolymer of 2-hydroxy- - 21 -
- lysozyme cytochrome C
- myoglobin (LCM test mixture) as the test mixture.
- the proteins were dissolved in water without added trifluoroacetic acid (TFA).
- TFA trifluoroacetic acid
- An organic-aqueous eluent with TFA addition in gradient mode was used as the mobile phase:
- the back pressure was approx. 20 bar for poly (methacrylate) -coated moldings and approx. 30 bar for the uncoated moldings (Chromolith ® ).
- the chromatograms obtained show that the elution profiles of the protein mixture change as expected depending on the hydrophobicity of the coating.
- the separation efficiency and the low column back pressure 0 demonstrate the good suitability of the materials according to the invention as sorbent for chromatography, - 22 -
- Example 3 Production of coated foreign bodies by chemisorption
- a mixture of 3.95 g (16.04 mmol) of p- (chloromethyl) phenyltrimethoxysilane and 25 ml of dry tetrahydrofuran (THF; p.a.) is prepared.
- the monolith was conditioned with dry tetrahydrofuran (THF). Then the above mixture was blown with nitrogen (over
- the monolith derivatized with silane.
- the monolith was then removed, tightly closed by means of screw connections, and placed vertically in an oven at 50 ° C. for 11 h, in which the monolith had good thermal contact. After the reaction has ended, the monolith is washed with toluene and then with methanol.
- the monolith derivatized with azo initiator was conditioned with dry toluene. A solution of 1.86 g (15 mmol) was then
- Ethyl methacrylate (EMA), 0.30 g (1.5 mmol) ethylene glycol dimethacrylate (EDMA) and 15 ml dry toluene were treated with nitrogen (dried over H 2 S0) and added to the storage container.
- An HPLC pump (Bischoff brand) was used to generate pressure in the air-filled pressure reservoir and thus the solution in the one coupled with the azo initiator
- Monolith pressed The monolith was then removed, tightly closed by means of screw connections, and placed vertically in an oven at 90 ° C. for 4 h, in which the monolith had good thermal contact. After the reaction has ended, the monolith is washed with toluene and then with methanol.
- the carbon content of the product can be influenced by changing the concentrations of the reactants used.
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicon Compounds (AREA)
Abstract
La présente invention concerne des corps façonnés monolithiques inorganiques dont la surface est recouverte d'un revêtement de polymères organiques physisorbés ou chimisorbés, ainsi qu'un procédé de production de produits de ce type. Les produits obtenus selon l'invention sont particulièrement adaptés en tant que sorbants pour la chromatographie, notamment la chromatographie liquide haute pression de matières biologiques.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03809725A EP1562700A1 (fr) | 2002-10-31 | 2003-10-21 | Corps fa onnes monolithiques inorganiques recouverts d'un revetement de polymeres organiques |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02024251 | 2002-10-31 | ||
EP02024251 | 2002-10-31 | ||
EP02024250 | 2002-10-31 | ||
EP02024250 | 2002-10-31 | ||
PCT/EP2003/011612 WO2004039495A1 (fr) | 2002-10-31 | 2003-10-21 | Corps façonnes monolithiques inorganiques recouverts d'un revetement de polymeres organiques |
EP03809725A EP1562700A1 (fr) | 2002-10-31 | 2003-10-21 | Corps fa onnes monolithiques inorganiques recouverts d'un revetement de polymeres organiques |
Publications (1)
Publication Number | Publication Date |
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EP1562700A1 true EP1562700A1 (fr) | 2005-08-17 |
Family
ID=32232194
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP03809725A Withdrawn EP1562700A1 (fr) | 2002-10-31 | 2003-10-21 | Corps fa onnes monolithiques inorganiques recouverts d'un revetement de polymeres organiques |
Country Status (5)
Country | Link |
---|---|
US (1) | US7648761B2 (fr) |
EP (1) | EP1562700A1 (fr) |
JP (1) | JP4628105B2 (fr) |
AU (1) | AU2003301743A1 (fr) |
WO (1) | WO2004039495A1 (fr) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102007008360A1 (de) * | 2007-02-16 | 2008-08-21 | Merck Patent Gmbh | Ummantelung für monolithische Chromatographiesäulen |
DE102009017943A1 (de) * | 2009-04-17 | 2010-10-21 | Merck Patent Gmbh | Poröse, magnetische Kieselgelformkörper, deren Herstellung und Anwendung |
JP6123466B2 (ja) * | 2013-01-25 | 2017-05-10 | 日立化成株式会社 | コアシェル型粒子及びその製造方法 |
JP7019293B2 (ja) * | 2013-03-15 | 2022-02-15 | リキグライド,インコーポレイテッド | 耐久性を向上させた液体含浸表面 |
DE102014216500A1 (de) | 2014-08-20 | 2016-02-25 | Hochschule Offenburg | Poröse monolithische oder faserförmige Produkte aus anorganischen Polymeren und deren Herstellung |
WO2017002871A1 (fr) * | 2015-06-30 | 2017-01-05 | 株式会社エスエヌジー | Procédé de réaction pour réaction en contact avec un corps poreux granulaire |
FR3143018A1 (fr) | 2022-12-09 | 2024-06-14 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Procédé de fabrication d'un dispositif fluidique comportant un substrat portant au moins un élément solide poreux ou creux |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2403098A1 (fr) | 1977-09-19 | 1979-04-13 | Merieux Inst | Nouveau materiau capable de fixer de facon reversible des macromolecules biologiques, sa preparation et son application |
US4483940A (en) * | 1981-11-24 | 1984-11-20 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for manufacture of honeycomb catalyst |
US4851163A (en) * | 1988-11-04 | 1989-07-25 | The Refraction Corporation | Biofouling resistant apparatus for wastewater treatment |
US5271833A (en) | 1990-03-22 | 1993-12-21 | Regents Of The University Of Minnesota | Polymer-coated carbon-clad inorganic oxide particles |
CZ286859B6 (en) | 1993-02-26 | 2000-07-12 | Merck Patent Gmbh | Stationary phase for chromatography |
EP0710219B1 (fr) | 1993-07-19 | 1997-12-10 | MERCK PATENT GmbH | Materiau poreux inorganique et procede de fabrication |
US6054052A (en) * | 1995-12-14 | 2000-04-25 | Mobil Oil Corporation | Selective sorption of organics by metal-containing M41S |
EP0912242A1 (fr) * | 1996-07-19 | 1999-05-06 | MERCK PATENT GmbH | Sorbants non particulaires chirals |
EP0921847B1 (fr) * | 1996-07-19 | 2003-04-02 | MERCK PATENT GmbH | Utilisation de sorbants non particulaires pour des procedes de separation a "lit mobile simule" |
US5897915A (en) | 1996-10-28 | 1999-04-27 | Corning Incorporated | Coated substrates, method for producing same, and use therefor |
ES2183236T3 (es) | 1996-12-26 | 2003-03-16 | Merck Patent Gmbh | Procedimiento para la produccion de materiales inorganicos. |
DE19725639A1 (de) * | 1997-06-18 | 1998-12-24 | Merck Patent Gmbh | Gradientenelutionsverfahren |
EP0991940B1 (fr) * | 1997-06-18 | 2010-08-25 | Merck Patent GmbH | Utilisation de sorbants pour procedes de separation chromatographiques a usage preparatif |
DE19726164A1 (de) * | 1997-06-20 | 1998-12-24 | Merck Patent Gmbh | Halterung für monolithische Sorbentien |
DE19929073C2 (de) | 1999-06-25 | 2002-02-21 | Ulrich Kunz | Monolithische Chromatographietrennsäule und deren Verwendung |
DE10016825A1 (de) * | 2000-04-07 | 2001-10-11 | Merck Patent Gmbh | Monolithische Sorbentien mit faserverstärkter Kunststoffummantelung |
DE10030665A1 (de) * | 2000-06-23 | 2002-01-03 | Merck Patent Gmbh | Gelierform zur Herstellung von Formkörpern |
US20020041041A1 (en) * | 2000-10-05 | 2002-04-11 | Johnson Kerry K. | Hollow monolithic ceramic gas diffuser and method of manufacture |
JP2002301367A (ja) * | 2001-04-05 | 2002-10-15 | Gl Sciences Inc | クロマトグラフィー用多孔質体の製造方法 |
EP1417366A4 (fr) * | 2001-08-09 | 2010-10-27 | Waters Technologies Corp | Materiaux monolithiques hybrides inorganiques/organiques utilises pour les separations chromatographiques, et leur procede de preparation |
US7125488B2 (en) * | 2004-02-12 | 2006-10-24 | Varian, Inc. | Polar-modified bonded phase materials for chromatographic separations |
-
2003
- 2003-10-21 AU AU2003301743A patent/AU2003301743A1/en not_active Abandoned
- 2003-10-21 JP JP2004547532A patent/JP4628105B2/ja not_active Expired - Fee Related
- 2003-10-21 EP EP03809725A patent/EP1562700A1/fr not_active Withdrawn
- 2003-10-21 US US10/532,877 patent/US7648761B2/en not_active Expired - Fee Related
- 2003-10-21 WO PCT/EP2003/011612 patent/WO2004039495A1/fr active Application Filing
Non-Patent Citations (1)
Title |
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See references of WO2004039495A1 * |
Also Published As
Publication number | Publication date |
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JP2006504515A (ja) | 2006-02-09 |
AU2003301743A1 (en) | 2004-05-25 |
US7648761B2 (en) | 2010-01-19 |
JP4628105B2 (ja) | 2011-02-09 |
US20060099402A1 (en) | 2006-05-11 |
WO2004039495A1 (fr) | 2004-05-13 |
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