EP1397205A2 - Inorganic absorbent composites, method for the production thereof and use of the same - Google Patents

Inorganic absorbent composites, method for the production thereof and use of the same

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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
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EP
European Patent Office
Prior art keywords
composites
inorganic
matrix
cucurbiturils
alkyl
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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.)
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EP02747180A
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German (de)
French (fr)
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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Publication of EP1397205A2 publication Critical patent/EP1397205A2/en
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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.

Abstract

The invention relates to novel inorganic absorbent composites consisting of an open-pore, solid, inorganic matrix, comprising cucurbiturils of general formula (I) which are chemically linked in the matrix. Said cucurbiturils form a macrocycle having a cage structure, consisting of n repeating units, wherein n is a whole number 5, 6, 7 or 8, R represents hydrogen or C1-C5 alkyl, and X represents O, S or N. X and R can be the same or different. Said composites are produced by reacting cucurbituril with an inorganic matrix-forming agent, such as silica gel, at 15 to 90°C in a liquid medium. The inventive composites can be used as absorption materials and catalyst supports.

Description

Anorganische absorbierende Komposite, Verfahren zur Herstellung und VerwendungInorganic absorbent composites, method of manufacture and use
Die Erfindung betrifft neue anorganische absorbierende Kom- posite auf der Grundlage von Cucurbiturilen sowie die Herstellung und Anwendung der Komposite.The invention relates to new inorganic absorbent composites based on cucurbiturils and to the production and use of the composites.
Cucurbiturile sind Makrocyclen der allgemeinen Formel (l). Sie sind durch eine cyclische Käfigstruktur gekennzeichnet und besitzen die Eigenschaft, Moleküle an oder in den Makrozyklus zu absorbieren.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.
Cucurbit[6]uril (Formel 1, n = 6, R = H, X = 0) stellt dabei den am besten untersuchten Vertreter dar, wobei n=5, R=Methyl, X=0 sowie n=5,6,7,8, R=H, X=0 ebenfalls bekannt sind. Beim Cucurbit[6]uril (Formel 1, n = 6, R = H, X = 0) hat der hydrophobe Hohlraum einen Durchmesser von 550 ppm und die beiden Molekülöffnungen, welche von jeweils 6 Carbonylgruppen gebildet werden, einen Durchmesser von 400 ppm (Freeman, W. A. et al. J.Am.Chem.Soc. 1983, 103, 7367-7368). Cucurbit[6 ]uril fällt bei der Herstellung als ein feinteiliger, amorpher Feststoff an, welcher in organischen und anorganischen Lösungs- mitteln sehr schlecht löslich ist. In wässrigen Salzlösungen und Säuren ist die Löslichkeit höher.Cucurbit [6] uril (formula 1, n = 6, R = H, X = 0) represents the best investigated representative, where n = 5, R = methyl, X = 0 and n = 5,6,7 , 8, R = H, X = 0 are also known. In the case of cucurbit [6] uril (formula 1, n = 6, R = H, X = 0), 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 besitzt die Eigenschaft, mit einer Vielzahl von organischen Verbindungen und anorganischen Kationen Komplexe zu bilden. Dabei werden die Verbindungen entweder am Molekül oder im Molekül ganz oder teilweise komplexiert (zu Gast-Wirt-Komplexen siehe Neugebauer, R. et al. J. Che .Soc. , Perkin Trans. 2. 1998, 529-534).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).
Die Komplexierung wird von der chemischen Struktur der an- und eingelagerten Verbindungen beeinflußt. Deshalb sind Cucurbitu- rile für selektive Absorption von Stoffen aus Lösungen von großem Interesse.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.
Buschmann, H.-J. et al. beschreiben in Textilveredlung, 1991, 26, 153- 157 erfolgreiche Versuche zur Abtrennung von Farbstoffen aus Abwässern mit Cucurbit[6]uril. Die Autoren zeigen jedoch auch, daß Cucurbit[6]uril aufgrund der geringen Teil- chengröße nur eine geringe Durchströmungsgeschwindigkeit für Farbstofflösungen besitzt. Für eine technische Anwendung ist das von Nachteil. Jedoch kann durch Auffällen von Cucurbit[6]uril auf Trägermaterialien (z. B. Kieselgel), die Absorption von Farbstoffen erhöht und eine akzeptable Durch- Strömungsgeschwindigkeit ermöglicht werden (Buschmann, H.J. et al. a.a.O. S. 160- 162).Buschmann, H.-J. et al. describe in Textilveredlung, 1991, 26, 153-157 successful attempts to separate dyes from waste water with cucurbit [6] uril. However, the authors also show that cucurbit [6] uril has only a low flow rate for dye solutions due to the small particle size. This is disadvantageous for a technical application. However, by striking cucurbit [6] uril on support materials (e.g. silica gel), the absorption of dyes can be increased and an acceptable flow rate can be made possible (Buschmann, H.J. et al. Op. Cit. Pp. 160-162).
Die Fällung von Cucurbit[6]uril auf Kieselgel wird z.B. dadurch erreicht, daß man eine Lösung von Cucurbit[6]uril in Salzsäure (Verhältnis 1:6) auf Kieselgel M60 aufziehen läßt und durch Zugabe von Wasser das Cucurbit[6]uril ausfällt.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.
Auf diese Weise werden Absorbenzien erhalten, die sich in Absorptionssäulen einsetzen lassen. Die auf diese Weise herge- stellten Absorbenzien besitzen jedoch Nachteile:In this way, absorbents are obtained which can be used in absorption columns. However, the absorbents produced in this way have disadvantages:
Bei wiederholter Beladung und Regenerierung kommt es zu einer Ausspülung der aktiven Komponente Cucurbituril, d.h. die Standfestigkeit ist stark begrenzt. Weiterhin ist die Kapazität dieser Absorbenzien zu gering.Repeated loading and regeneration will result in a Rinsing out the active component cucurbituril, ie the stability is severely limited. Furthermore, the capacity of these absorbents is too low.
Der Erfindung liegt die Aufgabe zugrunde, neue Absorptionsmaterialien unter Einbeziehung von Cucurbiturilen bereitzustellen, die eine hohe Absorptionskapazität und Standfestigkeit besitzen.The invention has for its object to provide new absorption materials including cucurbiturils, which have a high absorption capacity and stability.
Eine weitere Aufgabe der Erfindung besteht darin, Trägermaterialien mit Komplexierungseigenschaften und guter Regenier- brakeit zu entwickeln.Another object of the invention is to develop carrier materials with complexing properties and good regenerability.
Eine weitere Aufgabe der Erfindung besteht in der Bereitstellung eines Verfahrens zur Herstellung der neuen Materialien.Another object of the invention is to provide a method for manufacturing the new materials.
Erfindungsgemäß wird die Aufgabe dadurch gelöst, daß Komposite von Cucurbiturilen und deren Gemischen in anorganischen Matrizen hergestellt und eingesetzt werden. Diese Komposite sind dadurch gekennzeichnet, daß die Cucurbiturile in sehr feiner Form in die anorganische Matrix fest eingebaut sind. Durch Wahl geeigneter Matrizen und deren Herstellung wird eine hohe Porosizität erzeugt, die zu einer hohen Absorptionskapaziät dieser Komposite führt.According to the invention 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.
Erfindungsgemäß bereitgestellt werden daher anorganische absorbierende Komposite, wobei die Komposite aus einer offenporigen, festen, anorganischen Matrix bestehen mit in der Matrix chemisch gebundenen Cucurbiturilen der allgemeinen Formel (1)According to the invention, 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
wobei die Cucurbiturile einen Makrocyclus mit Käfigstruktur bilden, bestehend aus n sich wiederholenden Einheiten, worin n eine ganze Zahl 5, 6, 7 oder 8 ist, und worin R die Bedeutung Wasserstoff oder C,-C5-Alkyl hat, und X ist 0, S oder N, und worin X und R jeweils gleich oder verschieden sein können. wherein 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.
Unter "chemisch gebunden" werden sowohl Hauptvalenzbindungen als auch Nebenvalenzbindungen (van der Waals-Bindungen) verstanden .“Chemically bonded” is understood to mean both main valence bonds and secondary valence bonds (van der Waals bonds).
In den neuen Kompositen ist die anorganische Matrix ausgewählt aus der Gruppe, bestehend aus oxididischen Körpern von Sili- cium, Bor, Aluminium, Phosphor, Titanium, Zink, Zinn und Gemischen davon. Bevorzugt sind Oxide von Silicium, Oxide von Alu- minium, Silicate, Alumosilicate und Zeolithe. Unter "Oxide" oder "oxidische Körper" werden auch solche Verbindungen verstanden, die teilweise Hydroxide enthalten, wie im Falle von Silicium (Kieselgele) oder Aluminium (saure Tonerden). Besonders bevorzugt sind Kieselgele, Alumosilicate, Zeolithe und Oxidgemische.In the new composites, 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.
Bevorzugt ist weiterhin ein Komposit, enthaltend ein Gemisch von Cucurbiturilen der Formel l mit n = 5 bis 8, wobei der Anteil von n = 6 im Bereich von 80-85 Gew-% liegt, bezogen auf das Gesamtgemisch.Also preferred is a composite containing a mixture of cucurbiturils of formula I with n = 5 to 8, the proportion of n = 6 being in the range of 80-85% by weight, based on the total mixture.
Eine bevorzugte Bedeutung für R ist Methyl , Ethyl , Propyl , Isopropyl, wenn R die Bedeutung C.,-C5-Alkyl hat.A preferred meaning for R is methyl, ethyl, propyl, isopropyl if R is C.-, C 5 -alkyl.
Eine bevorzugte Bedeutung für X ist Sauerstoff.A preferred meaning for X is oxygen.
In einer weiteren Ausführungsform der Erfindung sind die Komposite auf einem Trägermaterial abgeschieden. Ein solches Trägermaterial ist beispielsweise ein poröses Glas, eine Glas- faser, ein Glasgewebe, eine Glaswolle, ein textiler Träger, eine Aktivkohle, ein Silicagel, ein Tonscherben oder ein Trä- ger, wie er üblicherweise als Katalysatorträger eingesetzt wird. Solche Katalysatorträger sind z.B. Aluminiumoxid, Sili- cate, Zeolithe, Kaolin, Kieselgel, Kieselgur, Hydrotalcite, Zirkoniumoxid, Titaniumoxid, Gemische davon und makroporöse anorganische Oxidgemische.In a further embodiment of the invention, the composites are deposited on a carrier material. Such 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. Such 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.
Die Herstellung der als Ausgangsverbindungen eingesetzten Cucurbiturile kann beispielsweise gemäß DE 100 40 242 AI erfolgen. Dabei wird unter Kühlung Acetylendiharnstoff in kon- zentrierte Schwefelsäure eingetragen und anschließend Formal- dehydlösung hinzugegeben. Bei diesem Verfahren wird weder Wasser hinzugegeben noch Wasser abdestilliert. Das gebildete Cucurbituril, das aus einem Gemisch von Cucurbiturilen der Formel 1 mit n = 5 bis 8 besteht, wird durch Ausfällen in Eiswasser, Abtrennen des Niederschlages, Waschen und Trocknen erhalten und kann in dieser Form für die vorliegende Erfindung eingesetzt werden.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 cucurbituril formed, which consists of a mixture of cucurbiturils of formula 1 with n = 5 to 8, is obtained by precipitation in ice water, removal of the precipitate, washing and drying and can be used in this form for the present invention.
Die neuen Komposite sind, abhängig von der Herstellung, grobe Feststoffe oder feinteilige Pulver. Für den praktischen Einsatz müssen die neuen Komposite, angepaßt an den jeweiligen Verwendungszweck, konfektioniert werden. Dies kann in an sich bekannter Weise durch Mahlen, Sieben, Formpressen und Tablettieren oder durch Aufziehen auf Trägermaterialien, wie Gläser oder Glaswolle oder Glasfasern oder andere textile Träger, erreicht werden.Depending on the manufacturing process, the new composites are coarse solids or fine-particle powders. For practical use, 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.
Die Konfektionierung kann dabei bereits parallel zur Bildung der anorganischen Matrix erfolgen, z. B. indem geeignete Trä- germaterialien mit mindestens einer der Komponenten die zur Bildung der Matrix notwendig sind, behandelt werden. In einem folgenden Schritt findet die eigentliche Matrixbildung durch Sol/Gel-Bildung und chemische Bindung statt.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. In a subsequent step, the actual matrix formation takes place through sol / gel formation and chemical bonding.
Die Konfektionierung wird auch erreicht, indem nach dem Vereinigen aller Komponenten, die für die Bildung des Komposits notwendig sind, ein Trägermaterial mit dieser Mischung behandelt wird und die endgültige Bildung des Komposites auf dem Trägermaterial stattfindet.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.
Die neuen Komposite zeichnen sich durch eine hohe Absorptionskapazität gegenüber vielen Verbindungen aus, wobei die Absorption sowohl in der Gasphase, als auch in der Flüssigphase stattfinden kann. Das macht die neuen Komposite in besonderer Weise für den Einsatz als Absorbenzien für organische und anorganische Verunreinigungen aus Abwässern geeignet.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.
Die neuen Komposite besitzen für verschiedene Stoffe ein unterschiedliches Absorptionsverhalten. Diese Eigenschaft macht sie zu aktiven und selektiven Absorbenzien für chromatographi- sehe Verfahren wie Gaschromatographie und Flüssigchromatographie. Als Besonderheit bei der Absorption ist anzusehen, daß die in der porösen Matrix verankerten Cucurbiturile in dem durch die cyclische Struktur gebildeten inneren Hohlraum hydrophob sind, während die durch =0, =S oder =N gebildeten Por- talgruppen hydrophil sind.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. A special feature of the absorption is that the cucurbiturils anchored in the porous matrix are hydrophobic in the inner cavity formed by the cyclic structure, while the portal groups formed by = 0, = S or = N are hydrophilic.
Das Absorptionsverhalten der neuen Komposite kann durch teilweise oder vollständige Komplexierung der eingelagerten Cucurbiturile in breiten Grenzen modifiziert werden, dies kann insbesondere für den Einsatz als Absorbentien in chromatographischen Systemen von Interesse sein. So können z. B. durch Absorption von aliphatischen und aromatischen Aminen basische Zentren im Komposit geschaffen werden. Durch Absorption von aliphatischen und aromatischen Phosphinen in das Komposit, insbesondere in die oben erwähnte Hohlraumstruktur der Cucurbiturile, können die Liganden für daran zu immobilisierende Katalysatoren gebildet werden und damit Katalysator-Komplexe bereitgestellt werden. Auf diese Weise sind die neuen Komposite als solche oder aufgetragen auf Katalysatorträgermateria- lien auch für die chemische Katalyse einsetzbar. In den neuen Kompositen sind die absorptionsaktiven Curcur- biturile in der porösen Matrix fest durch chemische Bindung eingebaut. Dadurch wird ein Ausschwemmen der Cucurbiturile aus der Matrix verhindert und die Zahl der Beladungs- und Regenerierungszyklen kann auf diese Art erheblich erhöht werden, so daß eine wirtschaftliche Verwertung möglich ist.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. By absorbing aliphatic and aromatic phosphines in the composite, in particular in the cavity structure of the cucurbiturils mentioned above, 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. In the new composites, 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.
Die Regenerierung der Absorptionsmaterialien ist auf verschiedenen Wegen möglich, z. B. durch Extraktion mit organischen oder anorganischen Lösungsmitteln oder durch Ozonisierung .The regeneration of the absorption materials is possible in various ways, e.g. B. by extraction with organic or inorganic solvents or by ozonization.
Gegenstand der Erfindung ist weiterhin ein Verfahren zur Herstellung von anorganischen absorbierenden Kompositen, das dadurch gekennzeichnet ist, daß man einen anorganischen Matrixbildner bei einer Temperatur im Bereich von 15 bis 90 °C, vorzugsweise bei Raumtemperatur, mit einem Cucurbituril der allgemeinen Formel (1)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)
wobei die Cucurbiturile einen Makrocyclus mit Käfigstruktur bilden, bestehend aus n sich wiederholenden Einheiten, worin n eine ganze Zahl 5, 6, 7 oder 8 ist, und worin R die Bedeutung Wasserstoff oder C,-C5-Alkyl hat, und X ist 0, S oder N, und worin X und R jeweils gleich oder verschieden sein können, in einem flüssigen Medium umsetzt. wherein 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.
Die Herstellung dieser Komposite beruht auf der Bildung der Matrix aus der flüssigen Phase, die auf verschiedenen Wegen erfolgen kann. In jedem Fall ist es jedoch wichtig, daß mindestens eine der Komponenten (Cucurbiturile oder Matrizenbildner) in einer flüssigen Phase vorliegt, wobei es sich dabei um Lösungen, Emulsionen oder Dispersionen handeln kann. Als anorganische Matrizenbildner können z. B. Silicate, Sili- ciumverbindungen, Aluminate oder Aluminiumsalze, Phosphate, Borate, Titanate bzw. deren Mischungen in Form von Lösungen oder Emulsionen in organischen oder anorganischen Lösungsmitteln, wie z. B. Wasser, verwendet werden. Diese Matrizenbildner bilden durch geeignete und an sich bekannter Behandlung mit Wasser, gegebenenfalls in Gegenwart von organischen Lösungsmitteln und/oder Säuren oder Basen, Gele aus. Diese Gel- bildung läuft oft über das Stadium von Solen. Die Gele können durch geeignete Behandlung, z.B. durch Trocknung bei erhöhter Temperatur, z.B. bei einer Temperatur im Bereich von 70 bis 150 °C in feste, hochporöse Matrizen für die Cucurbiturile umgewandelt werden.The production of these composites is based on the formation of the matrix from the liquid phase, which can be done in different ways. In any case, it is important that at least one of the components (cucurbiturils or matrix formers) is in a liquid phase, which may be solutions, emulsions or dispersions. As 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.
Eine bevorzugte Herstellung läuft daher als Sol-Gel-Prozeß ab, bei dem aus gelösten Vorstufen der Matrixbildner durch Hydrolyse und Kondensation zunächst ein Sol aus den diskreten, gelösten Kolloidpartikeln gebildet wird. Diese verschmelzen im weiteren Verlauf unter Ausbildung kovalenter Bindungen zu einem Gel. Durch Entfernung des Lösungsmittels z.B. durch Trocknung des feuchten Gels bilden sich formstabile poröse Körper. Durch Wahl von pH-Werten und Temperaturen können die Porengrößen in weiten Grenzen beeinflußt werden. So erhält man z.B. Kieselgele je nach pH-Wert bei sauerer Reaktion engporige, bei basischer Reaktion mittelporige und weitporige Gele.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.
Die Herstellung der Komposite soll am Beispiel von Cucurbit- [6]uril und Kieselgel erläutert werden.The production of the composites will be explained using the example of cucurbit [6] uril and silica gel.
Cucurbituril löst sich in wäßrigen Lösungen von Alkali- und Erdalkalisalzen. Aus diesem Grund löst es sich in wässrigen Lösungen von Alkalisilikaten. Bei diesen Lösungen handelt es sich um klare, farblose Flüssigkeiten, die bei Zugabe von anorganischen oder anorganischen Säuren zu einem Gel erstarren. Nach einer angemessenen Zeit, wird dieses Gel abgepreßt und mit Wasser ionenfrei gewaschen. Nach dem Trocknen bildet es eine weiße, körnige Masse, die durch Mahlen und Sieben konfektioniert werden kann.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.
Weiterhin löst sich Cucurbituril in anorganischen und organischen Säuren, wie z. B. Salzsäure oder Ameisensäure. Diese Lösungen sind klare, farblose Flüssigkeiten. Die Herstellung der neuen Komposite kann in der Weise geschehen, daß eine Lösung von Cucurbituril in einer Säure mit einer Siliziumver- bindung der Formel (2)Furthermore, 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)
in Kontakt gebracht wird, wobei in Formel (2) R1 bis R4 gleiche oder unterschiedliche Reste darstellen, die durch Hydrolyse abgespalten werden können, wie z. B. Alkoxy, Phenoxy, Halogen, Dialkylamino, Diarylamino. Die Bildung des Komposites geschieht beispielsweise über einen Sol-Gel-Prozeß aus der Sili- ciumverbindung und schließt das bei diesem Prozeß ausfallende Cucurbituril in feinst verteilter und gebundener Form in die Matrix ein.is brought into contact, wherein in 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.,, R2, R3 und R4 sind gleiche oder unterschiedliche Reste, die durch Hydrolyse abgespalten werden können, ausgewählt unter geradkettigem oder verzeigtem C,-C5-Alkoxy, Phenoxy, Halogen, Di-C,,-C4-alkylamino und Diarylamino, wobei die Alkyl- oder Arylreste gegebenenfalls substituiert sein können, und X ist eine Gruppe, die gleich oder verschieden sein kann, und die durch Hydrolyse nicht abgespalten werden kann, ausgewählt unter C,-C4-Alkyl und Aryl.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.
Als Arylrest ist Phenyl bevorzugt.Phenyl is preferred as the aryl radical.
Als Halogensubstituent kann Fluor, Chlor, Brom oder Iod eingesetzt werden . Substituenten für die Di-C,,-C4-Alkylaιτιinoreste am Alkylteil oder die Diarylaminoreste am Arylteil können Fluor, Chlor, Brom oder Iod sein.Fluorine, chlorine, bromine or iodine can be used as the halogen substituent. Substituents for the Di-C ,, - C 4 -Alkylaιτιinoreste on the alkyl part or the diarylamino radicals on the aryl part can be fluorine, chlorine, bromine or iodine.
In einer weiteren Ausführungsform kann die Matrix in weiten Grenzen dadurch variiert werden, indem die Siliziumverbindungen der Formel (2) ganz oder teilweise durch Siliziumverbindungen der Formeln (3) bis (5)In a further embodiment, 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)
(3) (4) (5) ersetzt werden, wobei R1 bis R3 ein Rest wie oben angegeben und X eine Gruppe ist, die unter den angewandten Bedingungen am Si gebunden bleibt, wie z. B. C,-C4-Alkyl oder Aryl .(3) (4) (5) can be replaced, where 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.
Der Alkylrest bzw. der Alkylteil im Alkoxyrest kann Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, i-Butyl, t-Butyl, Pentyl sein, wobei Methyl, Ethyl, Propyl und i-Propyl bevorzugt sind.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.
Der Rest X kann gegebenenfalls auch substiuiert sein, beispielsweise durch Fluor, Chlor, Brom oder Iod.The radical X can optionally also be substituted, for example by fluorine, chlorine, bromine or iodine.
Die Herstellung der neuen Komposite kann auch in der Weise erfolgen, daß dispergiertes Cucurbituril in eine der oben erwähnten Matrizenbildner eingebracht und dann in geeigneter Weise durch Zusatz von Säuren oder Basen die Bildung der anorganischen Matrix ausgelöst wird.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.
In einer weiteren Ausführungsform der Erfindung kann die Bildung der neuen Komposite auch durch Matrixbildung aus hydroly- sierbaren Verbindungen, wie Silikaten, Siliziumverbindungen der Formel (2) und (3), Alkalialuminaten, Phosphaten, Boraten oder Titanaten und deren Mischungen, oder aus zeolithischen Synthesegelen in Gegenwart von Kieselgel oder anderen Trägermaterialien, wie z.B. Zeolithen, Tonkugeln, Aktivkohle und ähnlichen durchgeführt werden. Auf diese Weise können die neuen Komposite auf einer Vielzahl unterschiedlicher Träger aufgebracht werden, beispielsweise auch auf übliche Katalysatorträger .In a further embodiment of the invention, 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. In this way, the new composites can be applied to a large number of different supports, for example also to conventional catalyst supports.
Zeolithische Synthesegele bestehen z.B. aus Si02, A1203, Na20 und Wasser. Für eine templatfreie Synthese von Zeolith MFI wird z.B. die Zusammensetzung 100 Si02 : A1203 : 28 Na20 : 4000 H20 verwendet.Zeolitic synthesis gels consist, for example, of Si0 2 , A1 2 0 3 , Na 2 0 and water. For a template-free synthesis of zeolite MFI, for example, the composition 100 Si0 2 : A1 2 0 3 : 28 Na 2 0: 4000 H 2 0 is used.
Die Erfindung soll nachstehend durch Beispiele näher erläutert werden. Alle Angaben erfolgen in Gewichtsprozent, sofern nichts anderes angegeben ist. Beispiel 1 In einem Becherglas werden 400 ml Wasser auf 80°C erwärmt. Man löst darin 30 g Natriumsilicat und gibt 10 g Cucurbit[6]uril hinzu. Nach Zugabe von 20 ml konzentrierter Salzsäure wird das ausgefallende Produkt abgesaugt, gewaschen und 24 Stunden bei 100*C getrocknet. Man erhält 63 g eines weißen Feststoffes, der einen Komposit aus Kieselgel und Cucurbituril darstellt. Beispiel 2The invention will be explained in more detail below by examples. All information is given in percent by weight, unless stated otherwise. 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
In einem Becherglas wird in 50 ml konzentrierter Salzsäure 0,5 g Cucurbituril gelöst, wobei das Cucurbituril der Formel (1) entspricht mit n=5-8 und einem Anteil von n=6 von 84 Gew-%; X ist Sauerstoff; R ist H. Dann gibt man 51,6 g Tetraethylsila- nol hinzu und rührt 12 Stunden (pH = 7). Man saugt das Produkt ab, wäscht mit Wasser und trocknet 12 Stunden bei 100° C. Man erhält 16,2 g eines weißen Feststoffes.0.5 g of cucurbituril is dissolved in 50 ml of concentrated hydrochloric acid in a beaker, the cucurbituril corresponding to formula (1) with n = 5-8 and a proportion of n = 6 of 84% by weight; X is oxygen; R is H. Then 51.6 g of tetraethylsilanol are added and the mixture is stirred for 12 hours (pH = 7). The product is filtered off, washed with water and dried for 12 hours at 100 ° C. 16.2 g of a white solid are obtained.
Die Herstellung des Cucurbiturils erfolgte durch Umsetzung von 1,03 1 konz. Schwefelsäure mit 1,08 kg Acetylendiharnstoff unter Rühren und Kühlen bei 65-70 °C. Dann wurde 1,7521 For - aldehydlösung (37 %ig) innerhalb 1 Stunde zugegeben, wobei die Viskosität der Reaktionslösung stieg. Nach Erwärmung der Lö- sung auf 100-110 °C für 4 Stunden wurde auf Raumtemperatur abgekühlt. Die klare Lösung wurde unter Rühren auf 10 kg Eis und 15 1 Wasser gegossen und abgesaugt. Nach dem Waschen mit 281 Wasser wurde das Produkt im Trockenschrank bei 100-130 °C bis zur Gewichtskonstanz getrocknet. 633 g ensprachen 50 % der theoretischen Ausbeute. Beispiel 3The 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 3
In einem Becherglas wird in 75 ml konzentrierter Salzsäure 0,7 g Cucurbituril gemäß Beispiel 2 gelöst. Dann gibt man 5 g Methoxy-triethoxysilan und 40 g Tetraethylsilanol hinzu und rührt 18 Stunden (pH = 2-3). Man saugt das Produkt ab, wäscht mit Wasser und trocknet 12 Stunden bei 100 °C. Man erhält 16,2 g eines weißen Feststoffes. Beispiel 40.7 g of cucurbituril according to Example 2 is dissolved in 75 ml of concentrated hydrochloric acid in a beaker. Then 5 g of methoxy-triethoxysilane and 40 g of tetraethylsilanol are added and the mixture is stirred for 18 hours (pH = 2-3). The product is suctioned off, washed with water and dried at 100 ° C. for 12 hours. 16.2 g of a white solid are obtained. Example 4
In einem Becherglas werden 400 ml Wasser auf 80°C erwärmt. Man löst dann 30 g Natriumsilikat und gibt dann 10 g Cucurbituril gemäß Beispiel 2 hinzu. Nach Zugabe einer Lösung von 4 g Na- triumaluminat in 70 ml Wasser werden 10 g Natriumhydroxid zugegeben und bei 70°C- 80°C 3 Stunden gerührt (pH = 8). Man läßt abkühlen, saugt ab und trocknet bei 130° C. Man erhält 14,5 g eines weißen Feststoffes. Beispiel 5400 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 (pH = 8). The mixture is allowed to cool, filtered off with suction and dried at 130 ° C. 14.5 g of a white solid are obtained. Example 5
In einem Becherglas werden 200 ml Wasser auf 80°C erwärmt. Man löst darin 15 g Natriumsilikat und gibt 5 g Cucurbituril gemäß Beispiel 2 hinzu. Dann tropft man innerhalb von 30 Minuten 10 ml Titantetraisopropylat hinzu und rührt 2 Stunden (pH = 3-4). Nach Zugabe von 20 ml konzentrierter Salzsäure wird das Produkt abgesaugt, gewaschen und 24 Stunden bei 130°C getrocknet. Man erhält 43 g eines weißen Feststoffes. Beispiel 6 In einem Becherglas werden 400 ml Wasser auf 80° C erwärmt. Man löst darin 30 g Natriumsilikat, und gibt 10 g Cucurbituril gemäß Beispiel 2 hinzu. Dann fügt man 20 g Kieselgel M60 zu und nach der Zugabe von 20 ml konzentrierter Salzsäure (pH = 2-3) wird das Produkt abgesaugt, gewaschen und 24 Stunden bei 100°C getrocknet. Man erhält 77 g eines weißen Feststoffes.200 ml of water are heated to 80 ° C in a beaker. 15 g of sodium silicate are dissolved therein and 5 g of cucurbituril according to Example 2 are added. Then 10 ml of titanium tetraisopropylate are added dropwise within 30 minutes and the mixture is stirred for 2 hours (pH = 3-4). After adding 20 ml of concentrated hydrochloric acid, the product is filtered off, washed and dried at 130 ° C for 24 hours. 43 g of a white solid are obtained. 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. Then 20 g of silica gel M60 are added and after the addition of 20 ml of concentrated hydrochloric acid (pH = 2-3), the product is filtered off with suction, washed and dried at 100 ° C. for 24 hours. 77 g of a white solid are obtained.
Beispiel 7 In auf einem Vertikalrüttler mit Analysensieben (1,00 - 0,40 mm; 0,40 - 0,25 mm und 0,25 - 0,16 mm), Siebdeckel und Siebpfanne werden 206,5 g von nach Beispiel 2 erhaltenem Material 1 Stunde gerüttelt. Man erhält 41,8 g Produkt mit einer Korngröße zwischen 1,00 - 0,40 mm, 13,2 g Produkt mit einer Korngröße zwischen 0,40 - 0,25 mm, 9,5 g Produkt mit einer Korngröße zwischen 0,25 - 0,16 mm und 57,1 g Produkt mit einer Korngröße kleiner 0,16 mm.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.
40 g des Produktes mit einer Korngröße zwischen 0,40 - 0,25 mm wurde zur Chromatographie eines Gemisches von 30 mg C.I. Acid red 44 und 60 mg Remazol® Brilant Violet 5R in 5 ml Wasser verwendet. Man erhält 75 ml einer Remazol® Brilant violet 5R- Lösung und 100 ml einer C.I. Acid red 44-Lösung.40 g of the product having a particle size between 0.40 to 0.25 mm was used for chromatography of a mixture of 30 mg of CI Acid Red 44 and 60 mg of Remazol Violet 5R ® Brilant used in 5 ml of water. This gives 75 ml of a Remazol ® Brilant violet 5R solution and 100 ml of a CI Acid red 44 solution.
Im Vergleich wurde die Trennung von C.I. Acid red 44 und Remazol® Brilant Violet unter gleichen Bedingungen (eingesetzte Mengen und Laufgeschwindigkeit) mit Kieselgel 100 0,2 - 0,5 mm durchgeführt. Es konnte keine Auftrennung beobachtet werden.In comparison, the separation of CI Acid red 44 and Remazol ® Brilant Violet was carried out under the same conditions (amounts used and running speed) with silica gel 100 0.2-0.5 mm. No separation was observed.
Ein Vergleich mit einem nach dem Stand der Technik auf Kieselgel ausgefälltem Cucurbit[6]uril zeigte zwar im ersten und zweiten Trenngang ein noch nahezu gleiches Trennergebnis, das jedoch nach 3-8 maliger Regenierung des Produktes deutlich herabgesetzt wurde und schließlich bei <20 % lag. A comparison with a cucurbit [6] uril precipitated on silica gel according to the prior art showed an almost identical separation result in the first and second separation, but this was significantly reduced after the product had been regenerated 3-8 times and was ultimately <20% ,

Claims

Patentansprüche claims
1. Anorganische absorbierende Komposite, dadurch gekennzeichnet, daß die Komposite aus einer offenporigen, festen, anorganischen Matrix bestehen mit in der Matrix chemisch gebundenen Cucurbiturilen der allgemeinen Formel (1)1. Inorganic absorbent composites, characterized in that the composites consist of an open-pore, solid, inorganic matrix with chemically bound cucurbiturils of the general formula (1) in the matrix.
wobei die Cucurbiturile einen Makrocyclus mit Käfigstruktur bilden, bestehend aus n sich wiederholenden Einheiten, worin n eine ganze Zahl 5, 6, 7 oder 8 ist, und worin R die Bedeutung Wasserstoff oder C--C5-Alkyl hat, und X ist 0, S oder N, und worin X und R gleich oder verschieden sein können. wherein 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 be the same or different.
2. Komposite nach Anspruch 1, dadurch gekennzeichnet, daß die anorganische Matrix ausgewählt ist aus der Gruppe, bestehend aus bestehend aus oxidischen Körpern von Silicium, Bor, Aluminium, Phosphor, Titanium, Zink, Zinn und Gemischen davon.2. Composites according to claim 1, characterized in that the inorganic matrix is selected from the group consisting of consisting of oxide bodies of silicon, boron, aluminum, phosphorus, titanium, zinc, tin and mixtures thereof.
3. Komposite nach Anspruch 2, dadurch gekennzeichnet, daß die anorganische Matrix ausgewählt ist aus der Gruppe, bestehend aus Kieselgelen, Aluminiumoxiden, Alumosilicaten und Zeolithen.3. Composites according to claim 2, characterized in that the inorganic matrix is selected from the group consisting of silica gels, aluminum oxides, aluminosilicates and zeolites.
4. Komposite nach Anspruch 1, dadurch gekennzeichnet, daß die Komposite auf einem Trägermaterial abgeschieden sind.4. Composites according to claim 1, characterized in that the composites are deposited on a carrier material.
5. Komposite nach Anspruch 4, dadurch gekennzeichnet, daß das Trägermaterial ein poröses Glas, eine Glasfaser, ein Glasgewe- be, eine Glaswolle, ein textiler Träger, eine Aktivkohle, ein Silicagel, ein Tonscherben oder ein üblicher Katalysatorträger ist.5. Composite according to claim 4, characterized in that the carrier material is a porous glass, a glass fiber, a glass fabric. be, a glass wool, a textile carrier, an activated carbon, a silica gel, a shard of clay or a conventional catalyst carrier.
6. Verfahren zur Herstellung von anorganischen absorbierende- Kompositen, dadurch gekennzeichnet, daß man einen anorganischen Matrixbildner bei einer Temperatur im Bereich von 15 bis 90 °C mit einem Cucurbituril der allgemeinen Formel (1)6. A process for the preparation of inorganic absorbent composites, characterized in that an inorganic matrix former at a temperature in the range from 15 to 90 ° C with a cucurbituril of the general formula (1)
wobei die Cucurbiturile einen Makrocyclus mit Käfigstruktur bilden, bestehend aus n sich wiederholenden Einheiten, worin n eine ganze Zahl 5, 6, 7 oder 8 ist, und worin R die Bedeutung Wasserstoff oder C^Cj-Alkyl hat, und X ist 0, S oder N, und worin X und R gleich oder verschieden sein können, in einem flüssigen Medium umsetzt. wherein the Cucurbiturils form a macrocycle with cage structure consisting of n repeating units, wherein n is an integer of 5, 6, 7 or 8, and wherein R is hydrogen or C ^ Cj alkyl has, and X is 0, S or N, and wherein X and R may be the same or different, in a liquid medium.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß man als Matrixbildner eine hydrolysierbare organische Siliciumver- bindung, ein Silicat, Aluminat, Alumosilicat, Borat, Titanat oder ein Gemisch davon oder ein zeolithisches Synthesegel einsetzt.7. The method according to claim 6, characterized in that a hydrolyzable organic silicon compound, a silicate, aluminate, aluminosilicate, borate, titanate or a mixture thereof or a zeolitic synthesis gel is used as the matrix former.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß als organische Siliciumverbindung eine Verbindung der Formel ( 2 ) , (3), (4) oder (5)8. The method according to claim 7, characterized in that a compound of formula (2), (3), (4) or (5) as the organic silicon compound
(2) (3) (4) (5) einsetzt, worin R.,, R2, R3 und R4 gleiche oder unterschiedliche einsetzt, worin R.,, R2, R3 und R4 gleiche oder unterschiedliche Reste sind, die durch Hydrolyse abgespalten werden können, ausgewählt unter geradkettigem oder verzeigtem C,-C5-Alkoxy, Phenoxy, Halogen, Di-C1-C4-alkylamino und Diarylamino, wobei die Alkyl- oder Arylreste gegebenenfalls substituiert sein können, und X eine Gruppe ist, die gleich oder verschieden sein kann, und die durch Hydrolyse nicht abgespalten werden kann, ausgewählt unter C,-C4-Alkyl und Aryl.(2) (3) (4) (5) in which R 1 , R 2 , R 3 and R 4 are the same or different where R 1 , 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 1 - 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, -C 4 alkyl and aryl.
9. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß das flüssige Medium aus der Gruppe ausgewählt ist, bestehend aus einer echten Lösung, einer Dispersion oder Emulsion des Matrixbildners in einem anorganischen oder organischen Lösungsmittel, einer Lösung der Cucurbiturile oder einem Gemisch davon.9. The method according to claim 6, characterized in that the liquid medium is selected from the group consisting of a real solution, a dispersion or emulsion of the matrix former in an inorganic or organic solvent, a solution of the cucurbiturile or a mixture thereof.
10. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß die Umsetzung in Gegenwart von Trägermaterialien durchgeführt wird.10. The method according to claim 6, characterized in that the reaction is carried out in the presence of carrier materials.
11. Verwendung der Komposite nach Anspruch 1 als aktive und selektive Absorbenzien für chromatographische Verfahren wie Gaschromatographie und Flüssigchromatographie.11. Use of the composites according to claim 1 as active and selective absorbents for chromatographic processes such as gas chromatography and liquid chromatography.
12. Verwendung der Komposite nach Anspruch l für als Basis für daran immobilisierte Katalysatorkomplexe. 12. Use of the composites according to claim 1 for as the basis for immobilized catalyst complexes.
EP02747180A 2001-05-28 2002-05-27 Inorganic absorbent composites, method for the production thereof and use of the same Ceased EP1397205A2 (en)

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DE10258830A1 (en) * 2002-12-17 2004-07-08 Henkel Kgaa Process for temporary finishing of textiles
KR100528959B1 (en) * 2003-02-11 2005-11-16 학교법인 포항공과대학교 Silica gel bonded with cucurbiturils
KR100545583B1 (en) * 2003-07-05 2006-01-24 학교법인 포항공과대학교 Solid substrate bonded with cucurbituril derivatives and bio chip using the same
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KR100988321B1 (en) * 2003-07-26 2010-10-18 포항공과대학교 산학협력단 Polymer comprising cucurbiturils, stationary phase and column using the same
KR100638478B1 (en) * 2004-04-20 2006-10-25 학교법인 포항공과대학교 Silica gel bonded with disubstituted cucurbiturils
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