EP1397205A2 - Composites absorbants inorganiques, procede permettant de les produire et leur utilisation - Google Patents

Composites absorbants inorganiques, procede permettant de les produire et leur utilisation

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Publication number
EP1397205A2
EP1397205A2 EP02747180A EP02747180A EP1397205A2 EP 1397205 A2 EP1397205 A2 EP 1397205A2 EP 02747180 A EP02747180 A EP 02747180A EP 02747180 A EP02747180 A EP 02747180A EP 1397205 A2 EP1397205 A2 EP 1397205A2
Authority
EP
European Patent Office
Prior art keywords
composites
inorganic
matrix
cucurbiturils
alkyl
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
EP02747180A
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German (de)
English (en)
Inventor
Andreas M. Richter
Michael Felicetti
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Sensient Imaging Technologies GmbH
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Sensient Imaging Technologies GmbH
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Filing date
Publication date
Application filed by Sensient Imaging Technologies GmbH filed Critical Sensient Imaging Technologies GmbH
Publication of EP1397205A2 publication Critical patent/EP1397205A2/fr
Ceased legal-status Critical Current

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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
    • B01J20/30—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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/02—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
    • 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
    • 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
    • B01J20/281—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
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • 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
    • B01J20/3248—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 type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3255—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 type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. heterocyclic or heteroaromatic structures
    • 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3272—Polymers obtained by reactions otherwise than involving only 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/52—Sorbents specially adapted for preparative 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography

Definitions

  • the invention relates to new inorganic absorbent composites based on cucurbiturils and to the production and use of the composites.
  • Cucurbiturils are macrocycles of the general formula (I). They are characterized by a cyclic cage structure and have the property of absorbing molecules on or in the macrocycle.
  • the hydrophobic cavity has a diameter of 550 ppm and the two molecular openings, which are each formed by 6 carbonyl groups, have a diameter of 400 ppm ( Freeman, WA et al. J. Am. Chem. Soc. 1983, 103, 7367-7368).
  • Cucurbit [6] uril is produced in the form of a fine, amorphous solid which is dissolved in organic and inorganic solutions. is very poorly soluble. The solubility is higher in aqueous salt solutions and acids.
  • Cucurbit [6] uril has the property of forming complexes with a large number of organic compounds and inorganic cations.
  • the compounds are wholly or partially complexed either on the molecule or in the molecule (for guest-host complexes, see Neugebauer, R. et al. J. Che. Soc., Perkin Trans. 2. 1998, 529-534).
  • the complexation is influenced by the chemical structure of the attached and embedded compounds. That is why cucurbiturils are of great interest for the selective absorption of substances from solutions.
  • the precipitation of cucurbit [6] uril on silica gel is e.g. achieved by letting a solution of cucurbit [6] uril in hydrochloric acid (ratio 1: 6) on silica gel M60 and precipitating the cucurbit [6] uril by adding water.
  • the invention has for its object to provide new absorption materials including cucurbiturils, which have a high absorption capacity and stability.
  • Another object of the invention is to develop carrier materials with complexing properties and good regenerability.
  • Another object of the invention is to provide a method for manufacturing the new materials.
  • the object is achieved in that composites of cucurbiturils and their mixtures are produced and used in inorganic matrices. These composites are characterized in that the cucurbiturils are built into the inorganic matrix in a very fine form. By selecting suitable matrices and their production, a high porosity is created, which leads to a high absorption capacity of these composites.
  • inorganic absorbent composites are therefore provided, the composites consisting of an open-pore, solid, inorganic matrix with cucurbiturils of the general formula (1) chemically bound in the matrix
  • the cucurbiturils form a macrocycle with a cage structure, consisting of n repeating units, where n is an integer 5, 6, 7 or 8, and where R is hydrogen or C, -C 5 alkyl, and X is 0 , S or N, and wherein X and R may each be the same or different.
  • “Chemically bonded” is understood to mean both main valence bonds and secondary valence bonds (van der Waals bonds).
  • the inorganic matrix is selected from the group consisting of oxidic bodies of silicon, boron, aluminum, phosphorus, titanium, zinc, tin and mixtures thereof.
  • Oxides of silicon, oxides of aluminum, silicates, aluminosilicates and zeolites are preferred.
  • Oxides or “oxidic bodies” are also understood to mean those compounds which partially contain hydroxides, as in the case of silicon (silica gels) or aluminum (acidic clays). Silica gels, aluminosilicates, zeolites and oxide mixtures are particularly preferred.
  • n 5 to 8
  • R is methyl, ethyl, propyl, isopropyl if R is C.-, C 5 -alkyl.
  • a preferred meaning for X is oxygen.
  • the composites are deposited on a carrier material.
  • a carrier material is, for example, a porous glass, a glass fiber, a glass fabric, a glass wool, a textile carrier, an activated carbon, a silica gel, a shard of clay or a carrier.
  • ger as is usually used as a catalyst support.
  • catalyst supports are, for example, aluminum oxide, silicates, zeolites, kaolin, silica gel, diatomaceous earth, hydrotalcites, zirconium oxide, titanium oxide, mixtures thereof and macroporous inorganic oxide mixtures.
  • the cucurbiturils used as starting compounds can be prepared, for example, according to DE 100 40 242 AI. With cooling, acetylene diurea is introduced into concentrated sulfuric acid and then formaldehyde solution is added. In this process, neither water is added nor water is distilled off.
  • the new composites are coarse solids or fine-particle powders.
  • the new composites have to be tailored to the respective intended use. This can be achieved in a manner known per se by grinding, sieving, compression molding and tableting or by mounting on carrier materials, such as glasses or glass wool or glass fibers or other textile carriers.
  • the assembly can take place parallel to the formation of the inorganic matrix, for. B. by treating suitable carrier materials with at least one of the components necessary to form the matrix.
  • the actual matrix formation takes place through sol / gel formation and chemical bonding.
  • the assembly is also achieved by combining all the components necessary for the formation of the composite are necessary, a carrier material is treated with this mixture and the final formation of the composite takes place on the carrier material.
  • the new composites are characterized by a high absorption capacity compared to many compounds, whereby the absorption can take place both in the gas phase and in the liquid phase. This makes the new composites particularly suitable for use as absorbents for organic and inorganic contaminants from waste water.
  • the new composites have a different absorption behavior for different substances. This property makes them active and selective absorbents for chromatographic processes such as gas chromatography and liquid chromatography.
  • the absorption behavior of the new composites can be modified within wide limits by partially or completely complexing the stored cucurbiturils; this can be of particular interest for use as absorbents in chromatographic systems.
  • So z. B. can be created by absorption of aliphatic and aromatic amines basic centers in the composite.
  • the ligands for catalysts to be immobilized thereon can be formed and thus catalyst complexes can be provided. In this way the new composites as such or applied to catalyst support materials can also be used for chemical catalysis.
  • the absorption-active Curcurbiturils are firmly integrated in the porous matrix through chemical bonding. This prevents the cucurbiturils from being washed out of the matrix and the number of loading and regeneration cycles can be increased considerably in this way, so that economic utilization is possible.
  • the regeneration of the absorption materials is possible in various ways, e.g. B. by extraction with organic or inorganic solvents or by ozonization.
  • the invention further relates to a process for the preparation of inorganic absorbent composites, which is characterized in that an inorganic matrix former at a temperature in the range from 15 to 90 ° C., preferably at room temperature, with a cucurbituril of the general formula (1)
  • the cucurbiturils form a macrocycle with a cage structure, consisting of n repeating units, where n is an integer 5, 6, 7 or 8, and where R is hydrogen or C, -C 5 alkyl, and X is 0 , S or N, and wherein X and R can each be the same or different, in a liquid medium.
  • the production of these composites is based on the formation of the matrix from the liquid phase, which can be done in different ways.
  • a liquid phase which may be solutions, emulsions or dispersions.
  • inorganic matrix formers such. B. silicates, silicon compounds, aluminates or aluminum salts, phosphates, borates, titanates or mixtures thereof in the form of solutions or emulsions in organic or inorganic solvents, such as. B. water can be used.
  • These matrix formers form gels by suitable and known treatment with water, optionally in the presence of organic solvents and / or acids or bases. This gel formation often runs through the stage of sols.
  • the gels can be converted into solid, highly porous matrices for the cucurbiturils by suitable treatment, for example by drying at elevated temperature, for example at a temperature in the range from 70 to 150 ° C.
  • a preferred production therefore runs as a sol-gel process, in which a sol is first formed from the discrete, dissolved colloid particles from dissolved precursors of the matrix formers by hydrolysis and condensation. These then merge to form a gel, forming covalent bonds. By removing the solvent e.g. By drying the moist gel, dimensionally stable porous bodies are formed.
  • the pore sizes can be influenced within wide limits by the choice of pH values and temperatures. So you get e.g. Depending on the pH value, silica gels have narrow-pore gels for acidic reactions, medium-pore and wide-pore gels for basic reactions.
  • Cucurbituril dissolves in aqueous solutions of alkali and alkaline earth salts. For this reason, it dissolves in aqueous solutions of alkali silicates. These solutions are clear, colorless liquids that solidify into a gel when inorganic or inorganic acids are added. After a reasonable time, this gel is squeezed out and washed ion-free with water. After drying, it forms a white, granular mass that can be made up by grinding and sieving.
  • cucurbituril dissolves in inorganic and organic acids, such as. B. hydrochloric acid or formic acid. These solutions are clear, colorless liquids.
  • the new composites can be produced in such a way that a solution of cucurbituril in an acid with a silicon compound of the formula (2)
  • R 1 to R 4 represent identical or different radicals which can be eliminated by hydrolysis, such as. B. alkoxy, phenoxy, halogen, dialkylamino, diarylamino.
  • the composite is formed, for example, by means of a sol-gel process from the silicon compound and includes the cucurbituril which precipitates in this process in the matrix in a finely divided and bound form.
  • R. ,, R 2 , R 3 and R 4 are identical or different radicals which can be split off by hydrolysis, selected from straight-chain or branched C, -C 5 alkoxy, phenoxy, halogen, di-C ,, - C 4 -alkylamino and diarylamino, where the alkyl or aryl radicals may be optionally substituted, and X is a group which may be the same or different and which cannot be split off by hydrolysis, selected from C 1 -C 4 -alkyl and aryl.
  • Phenyl is preferred as the aryl radical.
  • Fluorine, chlorine, bromine or iodine can be used as the halogen substituent.
  • Substituents for the Di-C ,, - C 4 -Alkyla ⁇ inoreste on the alkyl part or the diarylamino radicals on the aryl part can be fluorine, chlorine, bromine or iodine.
  • the matrix can be varied within wide limits in that the silicon compounds of the formula (2) are wholly or partly by silicon compounds of the formulas (3) to (5)
  • R 1 to R 3 is a radical as indicated above and X is a group which remains bonded to the Si under the conditions used, such as. B. C, -C 4 alkyl or aryl.
  • the alkyl radical or the alkyl part in the alkoxy radical can be methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, t-butyl, pentyl, methyl, ethyl, propyl and i-propyl being preferred.
  • the radical X can optionally also be substituted, for example by fluorine, chlorine, bromine or iodine.
  • the new composites can also be produced by introducing dispersed cucurbituril into one of the matrix formers mentioned above and then triggering the formation of the inorganic matrix in a suitable manner by adding acids or bases.
  • the formation of the new composites can also be formed by forming a matrix from hydrolyzable compounds, such as silicates, silicon compounds of the formula (2) and (3), alkali aluminates, phosphates, borates or titanates and mixtures thereof, or from zeolitic synthesis gels in the presence of silica gel or other carrier materials, such as zeolites, clay balls, activated carbon and similar.
  • hydrolyzable compounds such as silicates, silicon compounds of the formula (2) and (3), alkali aluminates, phosphates, borates or titanates and mixtures thereof
  • zeolitic synthesis gels in the presence of silica gel or other carrier materials, such as zeolites, clay balls, activated carbon and similar.
  • Zeolitic synthesis gels consist, for example, of Si0 2 , A1 2 0 3 , Na 2 0 and water.
  • the composition 100 Si0 2 : A1 2 0 3 : 28 Na 2 0: 4000 H 2 0 is used.
  • Example 1 400 ml of water are heated to 80 ° C. in a beaker. 30 g of sodium silicate are dissolved in it and 10 g of cucurbit [6] uril are added. After adding 20 ml of concentrated hydrochloric acid, the product which has precipitated is filtered off with suction, washed and dried at 100 ° C. for 24 hours. 63 g of a white solid are obtained, which is a composite of silica gel and cucurbituril.
  • Example 2 400 ml of water are heated to 80 ° C. in a beaker. 30 g of sodium silicate are dissolved in it and 10 g of cucurbit [6] uril are added. After adding 20 ml of concentrated hydrochloric acid, the product which has precipitated is filtered off with suction, washed and dried at 100 ° C. for 24 hours. 63 g of a white solid are obtained, which is a composite of silica gel and cucurbituril.
  • the cucurbituril was prepared by reacting 1.03 1 conc. Sulfuric acid with 1.08 kg acetylenediourea with stirring and cooling at 65-70 ° C. Then 1.7521 formaldehyde solution (37% strength) was added within 1 hour, the viscosity of the reaction solution increasing. After the solution had been heated to 100-110 ° C. for 4 hours, it was cooled to room temperature. The clear solution was stirred on 10 kg of ice and 15 1 water poured and suctioned off. After washing with 281 water, the product was dried in a drying cabinet at 100-130 ° C to constant weight. 633 g corresponded to 50% of the theoretical yield.
  • Example 5 400 ml of water are heated to 80 ° C in a beaker. 30 g of sodium silicate are then dissolved and 10 g of cucurbituril according to Example 2 are then added. After adding a solution of 4 g of sodium aluminate in 70 ml of water, 10 g of sodium hydroxide are added and the mixture is stirred at 70 ° C.- 80 ° C. for 3 hours (
  • Example 6 400 ml of water are heated to 80 ° C. in a beaker. 30 g of sodium silicate are dissolved therein, and 10 g of cucurbituril according to Example 2 are added.
  • Example 7 206.5 g of material 1 obtained according to Example 2 are placed on a vertical vibrator with analytical sieves (1.00-0.40 mm; 0.40-0.25 mm and 0.25-0.16 mm), sieve cover and sieve pan Hour shaken. 41.8 g of product with a grain size between 1.00-0.40 mm, 13.2 g of product with a grain size between 0.40-0.25 mm, and 9.5 g of product with a grain size between 0.25 are obtained - 0.16 mm and 57.1 g of product with a grain size smaller than 0.16 mm.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

L'invention concerne de nouveaux composites absorbants inorganiques à base d'une matrice inorganique solide, à pores ouverts, avec des cucurbituriles liés par voie chimique dans la matrice, de formule générale (I). Les cucurbituriles forment un macrocycle à structure en cage, comprenant n unités répétitives. Dans cette formule, n désigne un nombre entier 5, 6, 7, ou 8 et R désigne hydrogène ou alkyle C1-C5 et X désigne O, S ou N et X et R peuvent être identiques ou différents. Lesdits composés sont obtenus par réaction de cucurbiturile avec un générateur de matrice inorganique, tel que du gel siliceux, à une température comprise entre 15 et 90°, dans un milieu liquide. Ces composites s'utilisent comme matériau d'absorption et support de catalyseur.
EP02747180A 2001-05-28 2002-05-27 Composites absorbants inorganiques, procede permettant de les produire et leur utilisation Ceased EP1397205A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10126394A DE10126394A1 (de) 2001-05-28 2001-05-28 Neue Komposite auf der Grundlage von in anorganischen Matrizen eingelagertem Cucurbiturilen sowie deren Herstellung und Anwendung
DE10126394 2001-05-28
PCT/DE2002/001980 WO2002096553A2 (fr) 2001-05-28 2002-05-27 Composites absorbants inorganiques a base de cucurbiturile, procede permettant de les produire et leur utilisation

Publications (1)

Publication Number Publication Date
EP1397205A2 true EP1397205A2 (fr) 2004-03-17

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Application Number Title Priority Date Filing Date
EP02747180A Ceased EP1397205A2 (fr) 2001-05-28 2002-05-27 Composites absorbants inorganiques, procede permettant de les produire et leur utilisation

Country Status (5)

Country Link
US (1) US20040147396A1 (fr)
EP (1) EP1397205A2 (fr)
AU (1) AU2002317682A1 (fr)
DE (2) DE10126394A1 (fr)
WO (1) WO2002096553A2 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6869466B2 (en) * 1999-05-07 2005-03-22 Unisearch Limited Cucurbiturils and method for binding gases and volatiles using cucurbiturils
DE10258830A1 (de) * 2002-12-17 2004-07-08 Henkel Kgaa Verfahren zur temporären Ausrüstung von Textilien
KR100528959B1 (ko) * 2003-02-11 2005-11-16 학교법인 포항공과대학교 쿠커비투릴이 결합된 실리카 겔
KR100545583B1 (ko) * 2003-07-05 2006-01-24 학교법인 포항공과대학교 쿠커비투릴 유도체가 공유결합된 고체 기판 및 이를이용한 바이오칩
KR100554156B1 (ko) * 2003-07-26 2006-02-22 학교법인 포항공과대학교 쿠커비투릴 유도체가 응집되어 형성된 나노 입자, 그 나노입자에 약물이 담지된 약제학적 조성물, 및 이들의 제조방법
KR100988321B1 (ko) 2003-07-26 2010-10-18 포항공과대학교 산학협력단 쿠커비투릴을 포함하는 고분자, 이를 이용한 정지상 및 컬럼
KR100638478B1 (ko) * 2004-04-20 2006-10-25 학교법인 포항공과대학교 이치환 쿠커비투릴이 결합된 실리카겔
CN101935400B (zh) * 2010-08-23 2012-07-25 贵州大学 一类碱金属-瓜环多层次网状有机框架聚合物及其合成方法和应用
CN104722276B (zh) * 2015-04-14 2016-09-28 中国工程物理研究院材料研究所 一种瓜环/氧化石墨烯磁性复合材料及其制备方法
CN111992177B (zh) * 2020-09-07 2022-09-02 贵州大学 一种非热活化赤泥颗粒吸附剂及其制备方法
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DE10292294D2 (de) 2004-04-15
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US20040147396A1 (en) 2004-07-29
WO2002096553A2 (fr) 2002-12-05

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