EP2010547A1 - Procédé pour préparer des matériaux structurants organo-métalliques contenant des métaux du sous-groupe iv - Google Patents

Procédé pour préparer des matériaux structurants organo-métalliques contenant des métaux du sous-groupe iv

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Publication number
EP2010547A1
EP2010547A1 EP07728243A EP07728243A EP2010547A1 EP 2010547 A1 EP2010547 A1 EP 2010547A1 EP 07728243 A EP07728243 A EP 07728243A EP 07728243 A EP07728243 A EP 07728243A EP 2010547 A1 EP2010547 A1 EP 2010547A1
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EP
European Patent Office
Prior art keywords
acid
metal
compound
dicarboxylic acid
organic compound
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.)
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Application number
EP07728243A
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German (de)
English (en)
Inventor
Markus Schubert
Ulrich Müller
Stefan Marx
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BASF SE
Original Assignee
BASF SE
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Priority to EP07728243A priority Critical patent/EP2010547A1/fr
Publication of EP2010547A1 publication Critical patent/EP2010547A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages

Definitions

  • the present invention relates to processes for the preparation of porous organometallic Geüstmaterialien.
  • Porous organometallic frameworks are known in the art and form an interesting class of compounds that may be an alternative to organic zeolites for various applications.
  • Organometallic frameworks usually contain an at least bidentate organic compound coordinated to a metal ion.
  • the framework material is in the form of an endless framework.
  • a special group of these organometallic frameworks has recently been described as so-called “limited” scaffold materials, in which the framework, by special choice of the organic compound, does not extend infinitely but rather to form polyhedra (AC Sudik et al., J. Chem. Soc. 127 (2005), 71 10-7118). However, this last-mentioned special group ultimately represents a porous organometallic framework material.
  • organometallic frameworks have been used are, for example, in the field of storage, separation or controlled release of chemicals, such as gases, or in the field of catalysis.
  • chemicals such as gases
  • the choice of the corresponding metal ion plays an important role.
  • the object is achieved by a process for producing a porous organometallic framework material comprising at least one at least one metal ion coordinate bound, at least bidentate organic compound, containing the step
  • At least one metal compound Reacting at least one metal compound with at least one at least bidentate organic compound capable of coordinating with the metal, wherein the metal ion of the at least one metal compound is selected from the group of metals consisting of titanium, zirconium and hafnium, and the at least one at least bidentate organic compound derived from a di-, tri- or tetracarboxylic acid,
  • metal compound is an inorganic salt.
  • the porous organometallic framework material prepared by the process according to the invention contains at least one metal ion.
  • This metal ion is an ion of the metals selected from the group consisting of titanium, zirconium and hafnium.
  • the metal is zirconium.
  • more than one metal ion is present in the porous organometallic framework.
  • This metal ion may be located in the pores of the organometallic framework or be involved in the construction of the framework lattice. In the latter case, such a metal ion would also bind the at least one at least bidentate organic compound or a further at least bidentate organic compound.
  • any metal ion which is suitably suitable for being part of the porous organometallic framework material may be considered.
  • the preparation of such doped organometallic frameworks in general is described in the German patent application with the application no. 10 2005 053430.9 described. In the context of the present invention, a production according to the invention can be carried out by means of these production methods, provided that the metal compounds used represent an inorganic salt.
  • porous organometallic framework may be impregnated with another metal in the form of a metal salt.
  • a method for impregnation is described for example in EP-A 1070538.
  • the further metal ion may be involved in the framework construction or not.
  • the framework is constructed only of metal ions selected from the group consisting of titanium, zirconium and hafnium, and the at least one at least bidentate organic compound. Further preferably, the structure takes place exclusively by one of the metals titanium, zirconium or hafnium.
  • the framework material may be polymeric or polyhedra.
  • more than one metal ion is present in the framework material
  • more than one metal compound is correspondingly used in the process according to the invention, wherein the metal compounds each represent an inorganic salt.
  • the metals titanium, zirconium and hafnium are preferably present in the oxidation state +4.
  • the porous organometallic framework contains at least one at least bidentate organic compound, which is derived from a di-, tri- or tetracarboxylic acid.
  • At least bidentate organic compounds may be involved in the construction of the framework material. However, it is also possible that, moreover, not at least bidentate organic compounds are contained in the framework material. These can be derived, for example, from a monocarboxylic acid.
  • the term "derive" in the context of the present invention means that the di-, tri-or tetracarboxylic acid can be present in the framework material in partially deprotonated or completely deprotonated form.
  • the di-, tri- or tetracarboxylic acid may contain a substituent or independently of one another several substituents.
  • substituents are -OH, -NH 2, -OCH 3, -CH 3, -NH (CH 3), -N (CH 3) 2, -CN and halides.
  • the term "derive" in the context of the present invention means that the di-, tri- or tetracarboxylic acid can also be present in the form of the corresponding sulfur analogs.
  • the term "derive" in the context of the present invention means that one or more carboxylic acid functions can be replaced by a sulfonic acid group (-SO 3 H).
  • a sulfonic acid group may also occur in addition to the 2, 3 or 4 carboxylic acid functions.
  • the di-, tri- or tetracarboxylic acid has, in addition to the abovementioned functional groups, an organic main body or an organic compound to which these are bonded.
  • the abovementioned functional groups may in principle be bound to any suitable organic compound, as long as it is ensured that the organic compound having these functional groups is capable of forming the coordinative bond for the preparation of the framework.
  • the organic compounds are derived from a saturated or unsaturated aliphatic compound or an aromatic compound or a both aliphatic and aromatic compound.
  • the aliphatic compound or the aliphatic portion of the both aliphatic and aromatic compound may be linear and / or branched and / or cyclic, wherein also several cycles per compound are possible. More preferably, the aliphatic compound or the aliphatic portion of the both aliphatic and aromatic see compound 1 to 18, more preferably 1 to 14, more preferably 1 to 13, more preferably 1 to 12, more preferably 1 to 1 1 and particularly preferably 1 to 10 C atoms such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 C atoms. Methane, adamantane, acetylene, ethylene or butadiene are particularly preferred in this case.
  • the aromatic compound or the aromatic part of both aromatic and aliphatic compound may have one or more cores, such as two, three, four or five cores, wherein the cores separately and / or min. at least two nuclei can exist in condensed form.
  • the aromatic compound or the aromatic moiety of the both aliphatic and aromatic compounds has one, two or three nuclei, with one or two nuclei being particularly preferred.
  • each nucleus of the compound mentioned may contain at least one heteroatom, such as, for example, N, O, S, B, P, Si, preferably N, O and / or S.
  • the aromatic compound or the aromatic moiety of the both aromatic and aliphatic compounds contains one or two C 6 cores, the two being either separately or in condensed form.
  • benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl may be mentioned as aromatic compounds.
  • the at least bidentate organic compound an aliphatic or aromatic, acyclic or cyclic hydrocarbon having 1 to 18, preferably 1 to 10 and especially 6 carbon atoms, which also has only 2, 3 or 4 carboxyl groups as functional groups.
  • the at least bidentate organic compound is derived from a dicarboxylic acid such as oxalic acid, succinic acid, tartaric acid, 1,4-butanedicarboxylic acid, 1,4-butenedicarboxylic acid, 4-oxo-pyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid , Decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecane dicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene -1, 4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic
  • the at least bidentate organic compound is one of the above-exemplified dicarboxylic acid as such.
  • the at least bidentate organic compound may be derived from a tricarboxylic acid, such as
  • the at least bidentate organic compound is one of the above-exemplified tricarboxylic acids as such.
  • an at least bidentate organic compound derived from a tetracarboxylic acid such as
  • the at least bidentate organic compound is one of the above exemplified tetracarboxylic acids as such.
  • each of the cores can contain at least one heteroatom, where two or more nuclei have identical or different heteroatoms may contain.
  • monocarboxylic dicarboxylic acids preference is given to monocarboxylic dicarboxylic acids, monocarboxylic tricarboxylic acids, monocarboxylic tetracarboxylic acids, dicercaric dicarboxylic acids, dicercaric tricarboxylic acids, dicercaric tetracarboxylic acids, tricyclic dicarboxylic acids, tricarboxylic tricarboxylic acids, tricarboxylic tetracarboxylic acids, tetracyclic dicarboxylic acids, tetracyclic tricarboxylic acids and / or tetracyclic tetracarboxylic acids.
  • Suitable heteroatoms are, for example, N, O, S, B, P.
  • Preferred heteroatoms here are N, S and / or O.
  • a suitable substituent in this regard is, inter alia, -OH, a nitro group, an amino group or an alkyl or alkoxy group to call.
  • Especially preferred as the at least bidentate organic compounds are acetylenedicarboxylic acid (ADC), campherdicarboxylic acid, fumaric acid, succinic acid, benzenedicarboxylic acids, naphthalenedicarboxylic acids, biphenyldicarboxylic acids such as 4,4'-biphenyldicarboxylic acid (BPDC), pyrazinedicarboxylic acids such as 2,5-pyrazinedicarboxylic acid, bipyridinedicarboxylic acids such as 2,2'-bipyridine dicarboxylic acids, such as, for example, 2,2'-bipyridine-5,5'-dicarboxylic acid, benzene tricarboxylic acids, such as 1,2,
  • phthalic acid isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,2,3-benzenetricarboxylic acid, 1, 2,4-benzenetricarboxylic acid, 1, 3,5-benzenetricarboxylic acid or 1, 2,4,5-benzenetetracarboxylic acid.
  • the organometallic framework material may also comprise one or more monodentate ligands and / or one or more bidentate ligands which are not derived from a di-, tri- or tetracarboxylic acid.
  • the at least one at least bidentate organic compound preferably contains no hydroxyl or phosphonic acid groups.
  • one or more carboxylic acid functions can be replaced by a sulfonic acid function.
  • a sulfonic acid group may additionally be present.
  • all carboxylic acid functions are replaced by a sulfonic acid function.
  • Such sulfonic acids or their salts are, for example, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 1-amino-8-naphthol-3,6-disulfonic acid, 2-hydroxynaphthalene-3,6- disulfonic acid, benzene-1,3-disulfonic acid, 1,8-dihydroxynaphthalene-3,6-disulfonic acid, 1,2-dihydroxybenzene-3,5-disulfonic acid, 4,5-dihydroxynaphthalene-2,7-disulfonic acid, 2.9- Dimethyl-4,7-diphenyl-1,10-phenanthrolinedisulfonic acid, 4,7-diphenyl-1,10-phenanthrolinedisulfonic acid, ethane-1,2-disulfonic acid, naphthalene-1, 5-disulfonic acid, 2- (4-nitrophenylazo) -1
  • the organometallic frameworks according to the invention contain pores, in particular microro- and / or mesopores.
  • Micropores are defined as those having a diameter of 2 nm or smaller and mesopores are defined by a diameter in the range of 2 to 50 nm, each according to the definition as described by Pure Applied Chem. 57 (1985), pages 603-619, in particular on page 606.
  • the presence of micro- and / or mesopores can be checked by means of sorption measurements, these measurements determining the uptake capacity of the organometallic frameworks for nitrogen at 77 Kelvin according to DIN 66131 and / or DIN 66134.
  • the specific surface area - calculated according to the Langmuir model (DIN 66131, 66134) - for a MOF in powder form is more than 5 m 2 / g, more preferably more than 10 m 2 / g, more preferably more than 50 m 2 / g, more preferably more than 500 m 2 / g, even more preferably more than 1000 m 2 / g.
  • Moldings of organometallic frameworks may have a lower specific surface area; but preferably more than 10 m 2 / g, more preferably more than 50 m 2 / g, even more preferably more than 500 m 2 / g.
  • the pore size of the porous organometallic framework can be controlled by choice of the appropriate ligand and / or the at least bidentate organic compound. Generally, the larger the organic compound, the larger the pore size.
  • the pore size is preferably from 0.2 nm to 30 nm, more preferably the pore size is in the range from 0.3 nm to 3 nm, based on the crystalline material.
  • pores also occur whose size distribution can vary.
  • more than 50% of the total pore volume, in particular more than 75%, of pores having a pore diameter of up to 1000 nm is formed.
  • a majority of the pore volume is formed by pores of two diameter ranges. It is therefore further preferred if more than 25% of the total pore volume, in particular more than 50% of the total pore volume, is formed by pores which are in a diameter range of 100 nm to 800 nm and if more than 15% of the total pore volume, in particular more than 25% of the total pore volume is formed by pores is in a diameter range of up to 10 nm.
  • the pore distribution can be determined by means of mercury porosimetry.
  • the organometallic framework material can be present in powder form or as an agglomerate.
  • the framework material may be used as such or it may be converted into a shaped body.
  • a further aspect of the present invention is a shaped body, containing the organometallic framework according to the invention.
  • the framework material may include other materials such as binders, lubricants, or other additives added during manufacture. It is also conceivable that the framework material has further constituents, such as absorbents such as activated carbon or the like.
  • pellets such as disk-shaped pellets, pills, spheres, granules, extrudates such as strands, honeycombs, lattices or hollow bodies may be mentioned.
  • Tabletting together with at least one binder and / or other excipient Applying the framework material to at least one optionally porous support material.
  • the material obtained can then be further processed according to the method described above to give a shaped body.
  • Kneading / mulling and shaping can be carried out according to any suitable method, as described, for example, in Ullmanns Enzyklopadie der Technischen Chemie, 4th edition, volume 2, p. 313 et seq. (1972).
  • the kneading / hulling and / or shaping by means of a piston press, roller press in the presence or absence of at least one binder material, compounding, pelleting, tableting, extrusion, co-extruding, foaming, spinning, coating, granulating, preferably spray granulation, spraying, spraying dry or a combination of two or more of these methods.
  • pellets and / or tablets are produced.
  • Kneading and / or molding may be carried out at elevated temperatures such as, for example, in the range of room temperature to 300 ° C and / or elevated pressure such as in the range of normal pressure up to a few hundred bar and / or in a protective gas atmosphere such as in the presence of at least one Noble gas, nitrogen or a mixture of two or more thereof.
  • elevated temperatures such as, for example, in the range of room temperature to 300 ° C and / or elevated pressure such as in the range of normal pressure up to a few hundred bar and / or in a protective gas atmosphere such as in the presence of at least one Noble gas, nitrogen or a mixture of two or more thereof.
  • binders may be both viscosity-increasing and viscosity-reducing compounds.
  • Preferred binders include, for example, alumina-containing or alumina-containing binders, as described, for example, in WO 94/29408, silica, as described, for example, in EP 0 592 050 A1, mixtures of silica and alumina, such as For example, in WO 94/13584, clay minerals, as described for example in JP 03-037156 A, for example, montmorillonite, kaolin, bentonite, Halloysite, Dickit, Nac- rit and anauxite, alkoxysilanes, as described, for example, in EP 0 102 544 B1, for example tetraalkoxysilanes such as, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or, for example, trialkoxysilanes such as trimethoxysilane, triethoxysi
  • an organic compound and / or a hydrophilic polymer such as cellulose or a cellulose derivative such as methyl cellulose and / or a polyacrylate and / or a polymethacrylate and / or a polyvinyl alcohol and / or a polyvinylpyrrolidone and / or a polyisobutene and / or a polytetrahydrofuran and / or a polyethylene oxide.
  • a pasting agent inter alia, preferably water or at least one alcohol such as a monoalcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-1 - propanol or 2-methyl-2-propanol or a mixture of water and at least one of said alcohols or a polyhydric alcohol such as a glycol, preferably a water-miscible polyhydric alcohol, alone or as a mixture with water and / or at least one of said monohydric alcohols be used.
  • a monoalcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-1 - propanol or 2-methyl-2-propanol or a mixture of water and at least one of said alcohols or a polyhydric alcohol such as a glycol
  • the order of the additives such as template compound, binder, pasting agent, viscosity-increasing substance in the molding and kneading is basically not critical.
  • the molding obtained according to kneading and / or molding is subjected to at least one drying, generally at a temperature in the range of 25 to 500 ° C, preferably in the range of 50 to 500 ° C and more preferably in the range of 100 to 350 ° C is performed. It is also possible to dry in vacuo or under a protective gas atmosphere or by spray drying.
  • At least one of the compounds added as additives is at least partially removed from the shaped body.
  • the at least one metal compound is preferably a halide, sulfide, the salt of an inorganic oxygen-containing acid, optionally in the form of a hydrate or a mixture thereof.
  • a halide is, for example, chloride, bromide or iodide.
  • An inorganic oxygen-containing acid is, for example, sulfuric acid, sulfurous acid, phosphoric acid or nitric acid.
  • the metal ion of the metal compound preferably occurs as Me 4+ or MeO 2+ cation.
  • zirconium in the case of zirconium, further preferred metal compounds are zirconium chloride, zirconium oxychloride, zirconium sulfate, zirconium phosphate, zirconium oxynitrate, zirconium hydrogensulfate. If these compounds are present as hydrates, these can also be used.
  • titanium is titanium chloride, titanium nitrate, titanium oxosulfate, titanium sulfate and titanium sulfides. If these compounds are present as hydrates, these can also be used.
  • the reaction in the process according to the invention is preferably carried out in the presence of a nonaqueous solvent.
  • the reaction is preferably carried out at a pressure of at most 2 bar (absolute). However, the pressure is preferably at most 1230 mbar (absolute). In particular, The reaction takes place at atmospheric pressure. However, this may lead to slight overpressure or depression due to the apparatus. Therefore, in the context of the present invention, the term "atmospheric pressure" is to be understood as the pressure range which results from the actual atmospheric pressure of ⁇ 150 mbar.
  • the reaction can be carried out at room temperature. Preferably, however, this takes place at temperatures above room temperature. Preferably, the temperature is more than 100 ° C. Further preferably, the temperature is at most 180 ° C, and more preferably at most 150 ° C.
  • the organometallic frameworks described above are carried out in water as a solvent with the addition of another base.
  • a polybasic carboxylic acid as at least bidentate organic compound, this is slightly soluble in water. Due to the preferred use of the non-aqueous organic solvent, it is not necessary to use such a base. Nevertheless, the solvent for the process according to the invention can be chosen such that it reacts basicly as such, but this does not necessarily have to be for carrying out the process according to the invention.
  • a base can be used. However, it is preferred that no additional base is used.
  • reaction can take place with stirring, which is also advantageous in a scale-down.
  • the nonaqueous organic solvent is preferably a d-6-alkanol, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), acetonitrile, toluene, dioxane, benzene, chlorobenzene, methyl ethyl ketone (MEK), pyridine, tetrahydrofuran (THF), acetic sigklasted, optionally halogenated Ci -2 oo-alkane, sulfolane, glycol, N-methylpyrrolidone (NMP), gamma-butyrolactone, alicyclic alcohols such as cyclohexanol, ketones such as acetone or Acetylacetone, cycloketones such as cyclohexanone, sulfolene or mixtures thereof.
  • DMSO dimethyl sulfoxide
  • DMF N-d
  • a C- ⁇ -6-alkanol denotes an alcohol having 1 to 6 C atoms. Examples of these are methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, pentanol, hexanol and mixtures thereof.
  • An optionally halogenated d-oo-alkane denotes an alkane having 1 to 200 carbon atoms, it being possible for one or more up to all hydrogen atoms to be replaced by halogen, preferably chlorine or fluorine, in particular chlorine. Examples of these are chloroform, dichloromethane, carbon tetrachloride, dichloroethane, hexane, heptane, octane and mixtures thereof.
  • Preferred solvents are DMF, DEF and NMP. Particularly preferred is DMF.
  • non-aqueous preferably refers to a solvent having a maximum water content of 10% by weight, more preferably 5% by weight, still more preferably 1% by weight, further preferably 0.1% by weight. , particularly preferably 0.01 wt .-% based on the total weight of the solvent does not exceed.
  • the maximum water content during the reaction is 10% by weight, more preferably 5% by weight, and still more preferably 1% by weight.
  • solvent refers to pure solvents as well as mixtures of different solvents.
  • the process step of reacting the at least one metal compound with the at least one at least bidentate organic compound is followed by a calcination step.
  • the temperature set here is typically more than 250 ° C, preferably 300 to 400 ° C.
  • the at least bidentate organic compound present in the pores can be removed.
  • the removal of the at least bidentate organic compound (ligand) from the pores of the porous organometallic framework material can be carried out by treating the resulting framework material with a nonaqueous solvent.
  • the ligand is removed in a kind of "extraction process” and optionally replaced in the framework by a solvent molecule. This gentle method is particularly suitable when the ligand is a high-boiling compound.
  • the treatment is preferably at least 30 minutes and may typically be carried out for up to 2 days. This can be done at room temperature or elevated temperature. happened. This is preferably carried out at elevated temperature, for example at at least 40 ° C., preferably 60 ° C. Further preferably, the extraction takes place at the boiling point of the solvent used instead (under reflux).
  • the treatment can be carried out in a simple boiler by slurrying and stirring the framework material. It is also possible to use extraction apparatuses such as Soxhlet apparatuses, in particular technical extraction apparatuses.
  • Suitable solvents are any of the above, so as beispiels- Ci -6 alkanol, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N 1 N-
  • MEK methylethyl acetate
  • optionally halogenated d- 200- alkane sulfolane
  • glycol N-methylpyrrolidone (NMP)
  • NMP N-methylpyrrolidone
  • gamma-butyrolactone alicyclic alcohols such as cyclohexanol
  • ketones such as Acetone or acetylacetone
  • cycloketones such as cyclohexanone or mixtures thereof.
  • a most preferred extraction solvent is methanol.
  • the solvent used for the extraction may be the same as or different from that for the reaction of the at least one metal compound with the at least one at least bidentate organic compound.
  • the solvent is anhydrous.
  • the porous organometallic framework material prepared according to the invention can be used, for example, to take up at least one substance, store it, separate it, control it by controlled release or chemical reaction and as carrier or precursor material for producing a corresponding metal oxide.
  • porous organometallic framework material is used for storage, this is preferably carried out in a temperature range from -200 ° C to +80 ° C. More preferred is a temperature range of -40 ° C to + 80 ° C.
  • the at least one substance may be a gas or a liquid.
  • the substance is a gas.
  • gas and liquid are used in a simplified manner, but here too gas mixtures and liquid mixtures or liquid solutions are to be understood by the term “gas” or "liquid”.
  • Preferred gases are hydrogen, natural gas, town gas, saturated hydrocarbons, in particular methane, ethane, propane, n-butane and i-butane, unsaturated hydrocarbons, in particular ethene or propene, carbon monoxide, carbon dioxide, nitrogen oxides, oxygen, sulfur oxides, halogens, halide hydrocarbons, NF 3 , SF 6 , ammonia, boranes, phosphines, hydrogen sulfide, amines, formaldehyde, noble gases, in particular helium, neon, argon, krypton and xenon.
  • the at least one substance may also be a liquid.
  • a liquid examples of such a liquid are disinfectants, inorganic or organic see solvents, fuels - especially gasoline or diesel -, hydraulic, radiator, brake fluid or oil, especially machine oil.
  • the liquid may be halogenated aliphatic or aromatic, cyclic or acyclic hydrocarbons or mixtures thereof.
  • the at least one substance may be an odorant.
  • the odorous substance is preferably a volatile organic or inorganic compound which contains at least one of the elements nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine or iodine or an unsaturated or aromatic hydrocarbon or a saturated or unsaturated aldehyde or a ketone is. More preferred elements are nitrogen, oxygen, phosphorus, sulfur, chlorine, bromine; especially preferred are nitrogen, oxygen, phosphorus and sulfur.
  • the odorant is ammonia, hydrogen sulfide, sulfur oxides, nitrogen oxides, ozone, cyclic or acyclic amines, thiols, thioethers and aldehydes, ketones, esters, ethers, acids or alcohols.
  • ammonia hydrogen sulphide
  • organic acids preferably acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, heptanoic acid, lauric acid, pelargonic acid
  • cyclic or acyclic hydrocarbons which contain nitrogen or sulfur and saturated or unsaturated Aldehydes, such as hexanal, heptanal, octanal, nonanal, decanal, octenal or nonenal, and in particular volatile aldehydes such as butyraldehyde, propionaldehyde, acetaldehyde and formaldehyde, and furthermore fuels such as gasoline, diesel (ingredients).
  • the odorous substances may also be fragrances which are used, for example, for the production of perfumes.
  • fragrances or oils which release such fragrances include: essential oils, basil oil, geranium oil, mint oil, cananga oil, cardamom oil, lavender oil, peppermint oil, nutmeg oil, chamomile oil, eucalyptus oil, rosemary oil, lemon oil, lime oil, orange oil, bergamot oil, clary sage oil, coriander oil , Cypress oil, 1, 1-dimethoxy-2-pherylethane, 2,4-dimethyl-4-phenyltetrahydrofuran, dimethyltetrahydrobenzaldehyde, 2,6-dimethyl-7-octene-2-ol, 1, 2-diethoxy-3,7-dimethyl 2,6-octadiene, phenylacetaldehyde, rose oxide, ethyl 2-methylpentanoate, 1- (2,6,6-trimethyl-1,3-cyclo
  • a volatile odorant preferably has a boiling point or boiling point range of less than 300 ° C. More preferably, the odorant is a volatile compound or mixture. Most preferably, the odorant has a boiling point or boiling range of less than 250 ° C, more preferably less than 230 ° C, most preferably less than 200 ° C.
  • odors which have a high volatility.
  • a volatile odorant preferably has a vapor pressure greater than 0.001 kPa (20 ° C). More preferably, the odorant is a volatile compound or mixture. Most preferably, the odorant has a vapor pressure of greater than 0.01 kPa (20 ° C), more preferably a vapor pressure greater than 0.05 kPa (20 ° C). Most preferably, the odors have a vapor pressure of greater than 0.1 kPa (20 "C).
  • porous organometallic frameworks prepared according to the invention can be used to prepare corresponding metal oxides.
  • metal oxides of titanium, zirconium and hafnium and mixed oxides of these with each other or with other metals are possible.
  • the material has 26.4% by weight of Zr, 32.8% by weight of C, 37.5% by weight of O, 2.7% by weight of H and traces of Cl and N.
  • This composition indicates the formation of a Zr-organic compound.
  • Fig. 1 shows the associated X-ray diffraction (XRD), where I indicates the intensity (Lin (counts)) and 2 ⁇ describes the 2-theta scale.
  • the pore structure is shown in Fig. 2.
  • the pore volume V (ccm / g) is shown as a function of the pore diameter d (nm).
  • the surface area is determined by N 2 sorption to be 836 m 2 / g (Langmuir model).
  • the pore volume is 0.5 ml / g.
  • Both the XRD and the pore structure indicate the actual formation of a porous MOF structure.
  • the material has 26.0% by weight Zr, 34.1% by weight C, 36.7% by weight O, 2.6% by weight H and small amounts of N (traces of solvent) ,
  • the surface area is determined to be 546 m 2 / g by means of N 2 sorption (Langmuir model).
  • the material has 19.8% by weight of Ti, 13.7% by weight of C, 3.4% by weight of H, 13.9% by weight of S and 5.1% by weight of N on. The remainder is oxygen.
  • Example 5 Hydrogen uptake on the framework according to Example 1
  • the measurement is carried out on a commercially available device of the company Quantachrome with the designation Autosorb-1.
  • the measurement temperature was 77.4 K.
  • the samples were each pretreated for 4 h at room temperature before the measurement and then for a further 4 h at 200 ° C in vacuo.
  • the curve obtained is shown in FIG.
  • the H 2 uptake is shown in m 2 / g MOF (V) as a function of the pressure p / po.
  • the zirconium terephthalic acid MOF from Example 1 is calcined at 500 ° C. for 48 h.
  • the product is a zirconia with an N 2 surface area of 61 m 2 / g (Langmuir).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention concerne un procédé pour préparer un matériau structurant organo-métallique poreux contenant au moins un composé organique au moins bidenté lié par liaison dative à au moins un ion métallique, comprenant une opération qui consiste à convertir au moins un composé métallique avec au moins un composé organique au moins bidenté qui peut se lier au métal par liaison dative, l'ion métallique du ou des composés métalliques étant choisi dans le groupe de métaux comprenant le titane, le zirconium et l'hafnium, et le ou les composés organiques au moins bidentés étant dérivés d'un acide di-, tri- ou tétracarboxylique, le composé métallique étant un sel minéral.
EP07728243A 2006-04-18 2007-04-18 Procédé pour préparer des matériaux structurants organo-métalliques contenant des métaux du sous-groupe iv Withdrawn EP2010547A1 (fr)

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EP07728243A EP2010547A1 (fr) 2006-04-18 2007-04-18 Procédé pour préparer des matériaux structurants organo-métalliques contenant des métaux du sous-groupe iv

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CA2648225A1 (fr) 2007-10-25
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