MX2008007504A - Acid-functionalized organometallic framework materials - Google Patents

Abstract

The invention relates to porous organometallic framework materials containing at least one at least ambident organic compound L which is coordinatively bound to at least one metal ion M and is provided with at least one functional group G that bindsnon-coordinatively to M and is selected among the group comprising -SO3H, -PO3H2, and the analogues thereof. The invention further relates to method for the production thereof and the use thereof.

Description

ORGANOMETALLIC STRUCTURAL MATERIALS FUNCTIONALIZATION WITH ACID FIELD OF THE INVENTION The invention refers to organic structural materials, metal, processes to prepare them and their use. BACKGROUND OF THE INVENTION Solids having acidic properties are advantageous for numerous applications, one of these applications is ion exchange chromatography. Here, the solid materials, which are usually referred to as ion exchangers, comprise a component that can reversibly replace bound ions in the active exchange groups for other ions. Ion exchangers are divided into cation exchangers and anion exchangers, depending on the charge in the exchangeable ion. The cation exchangers known in the prior art are usually made of a high molecular weight polyvalent anion with mobile cations, for example a hydroxy group, a sulfonic acid group, a carboxy group or a phosphonic acid group as an active exchange group . To make exchange particularly efficient, macroporous reams that sometimes have pore widths of up to 10 nm are of particular interest as solids. For When preparing ion exchangers, functional groups are typically introduced into polycondensation resins and polymerization resins. Conventional strong acid ion exchangers can, for example, be obtained based on the styrene-divinylbenzene copolymers by suspension polymerization and subsequent sulfonation. Commercial ion exchangers are usually spherical particles that have a size from about 0.3 to 1.2 mm. Examples of the ion exchangers can be obtained under the tradenames Dowex® (Dow), Amberlite®, Amberjet® and Amberlyst® (each from Rohm &Haas) and Lewatit K® (Lanxess). For catalytic applications in particular, it is important that the sulfonated polymer matrices have a pore structure as described above that allows diffusion of the reactants to and from the active exchange groups. Macroporous ion exchangers are described, for example, in US-A 5,231,115 and US-B 6,329,435. Here, the swelling of the actual styrene-divinylbenzene polymer matrix is achieved during the polymerization by the addition of additives such as saturated hydrocarbons, saturated alcohols and / or water-soluble polymers to make it possible to obtain a porous structure. To ensure satisfactory mechanical stability of the macroporous polymer matrix, the proportion of crosslinked monomer (eg, divinyl benzene) has to be increased. The subsequent sulfonation makes it possible to derive the skeleton of the copolymer by the sulfonic acid groups. Here, the phenyl groups present are provided with sulfonic acid groups by electrophilic substitution in the aromatic. Ion-exchangers based on the styrene-divmylbenzene matrices comprising only the sulfonic acid groups but also the phosphonic acid groups are described, for example, in US-B 6,488, 859. Recently, structures have been described metallic organic which are conspicuous by their porosity as the aforementioned polymers The organic metal structures typically comprise at least one bidentate organic compound, usually a dicarboxylic, tetracarboxylic or tetracarboxylic acid, coordinated to at least one metal ion.

Such metal organic structures (OFs) are described, for example, in US-A 5,648,508, EP-A 0 790 253, M.O. Keeffe, J. Sol. State Chem. 152 (2000), 2-20; H. P. Li et al., Nature 402 (1999), 276; M. Eddaoudí, Topics m catalysis 9 (1999), 105-111; B. Chen et al., Science 91 (2001), 1021-1023 and DE-A 101 11 230. Although the organic structures of porous metal they comprise carboxylic acids, typically do not have acidic properties. This is because carboxylic acids participate in the form of their carboxylates in the formation of the structure, with the carboxylates being coordinated to the respective metal, and thus are not available as an active acid exchange group. Porous metal organic structures have also been disclosed, which comprise the functional groups that are of particular interest for the cation exchangers, namely sulfonates and phosphates. Thus, ES-A 2 200 681 describes rare earth disulfonates and R. Fu et al., Describe, in Euro. J. Inorg. Chem. 2005, 3211-3213, structures comprising phosphonate groups. However, in both publications, the acid functional group is, as indicated above, used to form the structure. Active, free exchange groups are therefore not available, so that these porous metal organic structures are also not suitable, for example, for ion exchangers. Therefore, there is a need to provide metal organic structures, functionalized with acid which, for example, can be used as ion exchangers and thus have the advantageous properties of the organic structures of metals in the applications that they require porous acid polymers or in which such polymers appear advantageous. DESCRIPTION OF THE INVENTION This objective is achieved by an organic, porous metal structure, comprising at least one bidentate organic compound L coordinated to at least one metal ion M, wherein L has at least one functional group G that is linked not coordinated to M and is selected from the group consisting of -S03H and -P03H2 and their deprotonated analogues. It has surprisingly been found that modifications of porous metal organic structures known per se by the functional group G gives new porous metal organic structures that exhibit acidic properties and can be used, for example, as heat exchangers. ions. The deprotonated analogs of the group G are -S03", P03H" and P032. "However, it is preferred that at least 50% of the group G be present in the protonated form, more preferably at least 75% and the group G is more preferably present in the fully protonated form If G is at least partially present in the deprotonated form, the alkali metal ions and the ammonium ions are suitable counterions.To form the structure, a metal ion M must be coordinated by at least two molecules of compound L.

In the porous metal organic structure, the molar ratio of G: M is preferably at least 1:75. The ratio is more preferably at least 1:50, still more preferably at least 1:10. The molar ratio of G: M is preferably not more than 4: 1, more preferably not more than 2: 1 and particularly preferably not more than 1: 1. The appropriate ratio of G: M or L: M can be adjusted in the desired form by the appropriate reaction conditions in the preparation of the porous metal organic structure of the invention. This can be achieved by methods known to those skilled in the art and depends on the preparative process employed. Then, for example, organic compound L can have functional group G or an analogous group that can be converted to G in the preparation. To adjust the desired molar ratio of G: M, an organic compound L 'having a structure similar to L but not having G or a derivative of G can also be used in the reaction of compound L with M. Based on the mixing ratio of L to L ', the aforementioned molar ratio of G: M can be appropriately fixed in the reaction with M. A further possible way of adjusting or setting a particular mole ratio is to introduce the group G subsequently, i.e. after a organic structure of metal. This can be achieved, for example, by the sulfonation of an aromatic. In this case, the molar ratio of G: can be controlled by means of the temperature, the concentration of the sulfonation reagent and the time for which it is allowed to act on the organic structure of metal. There are numerous methods known to those skilled in the art to determine the molar ratio. The ratio can be determined by the usual methods such as nuclear magnetic resonance spectroscopy, infrared spectroscopy, thermal desorption of, for example, amines, elemental analysis and / or titration. The content of group G in the porous metal organic structure also determines the acid properties of the structure of the invention. Preference is given to the structure having an acid density of at least 0.1 mmol / g. The acid density is preferably at least 1 mmol / g, more preferably at least 2 mmol / g. The metal component in the structure of the present invention is preferably selected from the groups la, lia, Illa, IVa a Villa and Ib a VIb. Particular preference is given to Mg, Ca, Sr, Ba, Se, Y, Ti, Zr, HF, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Go , Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Ti, Si, Ge, Sn, Pb, As, Sb and Bi. It is given greater preference to Zn, Cu, Ni, Pd, Pt, Ru, Rh, and Co. Particular preference is given to Zn, Al, Ni and Cu. With respect to the ions of these elements, particular mention should be made of Mg -2 + Ca 2 + Sr 2 + Ba 2+ Sc3 +, Y3 +, Ti 4+ Zr 4+ Hf 4 + V 4+ V 3+ V 2 + Nb 3 + Ta3 +, Cr3 +, Mo3 +, 3+, Mn3 +, Mn +, Re3 +, Re2 +, Fe3 +, Fe2 +, Ru3 + Ru 2 + 0s3 +, 0s2 +, Co3 +, Co2 +, Rh2 +, Rh +, Ir2 +, Ni2 +, Ni +, Pd2 +, Pd + P 'Pt +, Cu2 +, Cu +, Ag +, Au +, Zn2 +, Cd2 +, Hg2 +, Al3 +, Ga3 +, In3 + Ti 3 + Si4 +, Si2 +, Ge4 +, Sn4 +, Sn2 +, Pb4 +, Pb2 +, As5 +, As3 +, As +, Sb5 + Sb 3 + Sb +, Bi5 +, Bi3 +, and Bi +. Greater preference is given to the metals Sr, Ba, Mo, W, V, Ni, Co, Se, and Platinum and the rare earth metals and also Mg, Ca, Al, Ga, In, Zn, Cu, Fe and Mn . M is particularly selected from the group consisting of Mg, Ca, Al, Ga, In, Zn, Cu, Fe and Mn. Very particular preference is given to Mg, Al. The term "at least the bidentate organic compound" refers to an organic compound comprising at least one functional group that is capable of forming at least two, preferably two, coordinated bonds to an ion of given metal and / or forms a coordinated bond to each of two or more, preferably two, metal atoms. As functional groups via which the aforementioned coordinate bonds can be formed, mention can be made, by way of exa, of, in particular, OH, SH, NH2, NH (-RH), N (RH) 2, CH2OH, CH2SH, CH2NH2, CH2NH (-RH), CH2N (-RH) 2, -C02H, COSH, -CS2H, -N02, -B (OH) 2, - S02H, -S? (OH) 3, -Ge (OH) 3l -Sn (OH) 3, -S? (SH) 4, Ge (OH) 3, Sn (OH) 3, -S? (SH) 4 , -Ge (SH) 4, -Sn (SH) 3, -P03H2, -As04H, -P (SH) 3 -As (SH) 3, -CH (RSH) 2, -C (RSH) 3, -CH (RNH2) 2, -C (RNH2) 3, -CH (ROH) 2, -C (ROH) 3, -CH (RCN) 2, -C (RCN) 3, where R is preferably, for exa, a group alkylene having 1, 2, 3, 4 or 5 carbon atoms, for exa a methylene, ethylene, n-propylene, ε-propylene, n-butylene, γ-butylene, tert-butylene or n-pentylene group, or a an alpha group comprising 1 or 2 aromatic rings, for exa 2 C6 rings, which can, if appropriate, be fused and can, independently of each other, be appropriately substituted by in each case at least one substituent and / or can, independently it comprises in each case at least one heteroatom, for exa N, 0 and / or S. In similar preferred embodiments, mention must be made of functional groups in which the radical The aforementioned R is not present. In relation to this, mention should be made inter alia, -CH (SH) 2, -C (SH) 3, -CH (NH2) 2, CH (NH (RH)) 2, CH (N (RH) 2) 2, C (NH (RH)) 3, C (N (RH) 2) 3, -C (NH 2) 3, -CH (0H) 2, -C (0H) 3, -CH (CN) 2, - C (CN) 3. The coordinated link is preferably not formed via -S03H and / or P03H2. The at least two functional groups can, in principle, be bound to any suitable organic compound so long as it is ensured that the organic compound comprises these functional groups, is capable of forming the coordinated bond and of producing the structure. The organic compounds comprising at least two functional groups are preferably derived from a saturated or saturated aliphatic compound or an aromatic compound or both an aliphatic or aromatic compound. The aliphatic compound or the aliphatic part of both aliphatic and aromatic compounds may be linear and / or branched and / or cyclic, with a plurality of rings per compound being also possible. The aliphatic compound or the aliphatic part of both aliphatic and aromatic compounds more preferably comprises from 1 to 16, more preferably from 1 to 14, more preferably from 1 to 13, more preferably from 1 to 12, more preferably from 1 to 11 and more particularly preferably from 1 to 10, carbon atoms, for exa 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Particular preference is given here to inter alia, methane, adamantane, acetylene, ethylene or butadiene. The aromatic compound or the aromatic part of both the aromatic and aliphatic compound may have one or more rings, for exa two, three, four or five rings, with the rings being able to be present separately from each other and / or at least two rings may be present in a fused form. The aromatic compound or the aromatic part of both the aromatic and the preferably preferable aliphatic compounds has one, two or three rings, with particular preference being given to one or two rings. In addition, the rings of said compounds may each comprise, independently of each other, at least one heteroatom such as N, 0, S, B, P, Si, Al, preferably N, O and / or S. More preferably, the compound aromatic or the aromatic part of both the aromatic and the aliphatic compound, comprises one or two C6 rings; in the case of two rings, they may be present either separately from each other or in a fused form. The aromatic compounds of which particular mention may be made are benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl. L is particularly preferably derived from a dicarboxylic, tricarboxylic, tetracarboxylic acid or an analogous sulfur or a diamine. Sulfur analogs are the functional groups -C (= 0) SH and its tautomer and C (= S) SH. The carboxylic acid or the diamine can be, in addition to the functional groups that together with the metal M form the structure, additional substituents that after the transformation give the group G. In addition, the substituents can be present. Such substituents are, for example, -OH, NH2, -SH, -N02, halogens such as fluorine, chlorine, bromine or iodine and pseudohalides such as -CH, -CON, -CNS or the alkyl or alkoxy groups having from 1 to 4 carbon atoms, for example methoxy or ethoxy. The group G can also be linked to L via such substituents. Therefore, it is necessary that G binds to the skeleton of L. As mentioned before, it is not necessary for each of the bidentate organic compounds that participate in the structure of the structure to have a G group. However, as such case it is preferred that at least the bidentate organic compound that is different from L differs from L only in the presence of group G. Preferred diammas are 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 1, 2-cyclohexanediamine, 1,3-c-clohexanodomamine, 1,4-c-clohexanodamma, 3,6-d-azaoctane-1,8-d-amma, diethylenediamma, ethylenediamma, proipilendiamma, trimethylenediamma, 1, 1 '-bifen? L-4, 4' diamma, 1, 7-heptanedi amma, isophoronadiamma, 2-methylpentamethylenediamma, 4-met? Ll, 2-phenyldiamma, 4-met? L-1,3-phenylenediamine , naphthalene-1, 5-d? amma, naphthalene-1, 8 -iamma, neopentanodiamma, 2-n? tro-1, 4-phenylenedimma, 4-n? tro-1, 2-phenylenediamine, 4-nitro- 1 , 3"Femlendiamine, nonamethylendiamma, 1,3-propanediamma, tpethyl endiamma (DABCO), 3, 5-d? Ammobenzoic acid, 3,4-diammabenzoic acid, 4, 4 '-diammo-benzophenone, 1,4-d-ammobutane, 2,4-d? Ammo-6- chloropinmid, 2,2 '-diammo-diethylamine, 1,8 -d? ammo-3,6-dioxaoctane, bis (4-ammophenyl) ether, bis (3-ammophenyl) sulfone, bis (4-ammophene?) sulfone , 1, 6-d? Ammohexane, 4, 5-d? Am? No-6-h? Drox? -2 -mercaptopyridma, 2, 4-d? Ammo-6-h? Drox? P? R? M? dna, diamylmaléne dinitrile, 4,6-d? ammo-2-mercaptopyrimidine, 1,5-d? ammo-2-methylpentane, 1,9-d? ammononan, 1,8-diammooctane, 2,4-d Ammophenol, 2, 6-d? ammo-4-phenyl? -1,3,5-tpazma, 2,3-diamopyridine, 2,6-d? ammop? r? dma, 2,3-diammopropyramic acid, 3, 4-d? Ammop? Pdma, 4,6-d? Ammo-2-pyrimidmothiol, 3,5-d? Ammo-l, 2,4-tr? Azol, 1, 13-d? Ammo-4, 7, 10-tr? Oxatr? Decane and 2,5-d? Ammovalépco acid. For the purposes of the present invention, mention should be made, by way of example, of dicarboxylic acids such as oxalic acid, succinic acid, tartaric acid, 1,4-butanedicarboxylic acid, 1,4-butenecarboxylic acid, acid 4-oxopran-2, 6-d-carboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanecarboxylic acid, 1,9-heptadecanecarboxylic acid? co, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,3-pyrididicarboxylic acid, p? r? dm-2,3-dicarboxylic acid, 1,3-butadiene? -1, 4-d? Carboxyl? Co, 1,4-benzenecarboxylic acid, p-benzenedicarboxylic acid, acid α-dazol-2,4-d-carboxylic acid, 2-methyl-3-methyl-3,4-dicarboxylic acid, quinolin-2, 4-d-carboxylic acid, acid qu? noxalma-2, 3-d? carboxyl? co, 6-chloroqu? noxalma-2, 3-dicarboxylic acid, 4,4 '-diaminophen-l-3-methane-3-dicarboxylic acid, qu? nolma-3 acid, 4-d? Carboxy? Co, 7-chloro-4-hydroxy-quinoline-2, 8-d? Carboxylic acid, dumidicarboxylic acid, p? R? Dm-2, 6-d? Carboxylic acid, 2-acid methylene-4,4-d-carboxylic acid, t-ofen-3,4-dicarboxylic acid, 2-β-sopropyl-l-diazole-4,5-d-carboxylic acid , tetrah? drop? 4-d, 4-d? carboxylic acid, ace? lene-3, 9-dicarboxylic acid, perylenedicarboxylic acid, Pluriol E 200-d? carboxy? acid, 3,6-d acid ? oxa-octanod? carboxy? co, 3,5-c-clohexanod? ene-l, 2-dicarboxylic acid, octadicarboxylic acid, pentane-3, 3-d? carboxylic acid, 4,4 '-d? ammo-1, 1 'bifen? -3, 3' dicarboxylic acid, benzidm-3,3 'dicarboxylic acid, 1,4-bis (phenylammo) benzene-2,5-di acid carboxylic acid, 1,1 '-bubltyldicarboxylic acid, 7-chloro-8-methyl-3-d-carboxylic acid, 1-aminoanthraquinone-2,4'-dicarboxylic acid, poly-tetrahydrofuran- 250-d? Carboxyl? Co, 1,4-bis (carboxymethyl) p? Perazm-2, 3-d? Carboxylic acid, 7-chloroqu? Nolma-3,8-d? Carboxy? Acid, 1- ( -carboxy) phenyl-3 (4-chloro) phen? lp? razolma-4, 5-d? carboxyl? acid 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid Femdomodicarboxylic acid, 1,3-d? benzyl-2-oxo? m? dazol? dm-4, 5-d? carboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-l, 8-d? carboxylic acid Co, 2-benzoylbenzene-1, 3-d? carboxylic acid, 1,3-d? benc? l-2 -oxo? m? dazol? dma-4, 5-c? sd? carboxylic acid Co, 2,2'-b? qumolm-4,4'-dicarboxylic acid, p-ndm-3,4-dicarboxylic acid, 3,6,9-tr? oxadecanecarboxylic acid, hydroxybenzophenone dicarboxylic acid, acid Plupol E 300-dicarboxylic acid, Pluriol E 400-d? Carboxylic acid, Pluriol E 600 -dicarboxylic acid, poly-3-carboxylic acid, 2,3-dicarboxylic acid, 2,3-pyrazidicarboxylic acid, 5,6 acid -d? methyl-2, 3-pyrazidicarboxylic acid, (bis (4-ammophenyl) ether) dicarboxylic acid, 4,4'-diaminodiphenylmethanediimidodicarboxylic acid, (bis (4-ammophenyl) sulfone) dumidodicarboxylic acid, 1,4- Naphthalenedicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalene dicarboxylic acid, Acid or 2, 3-naphthalenedicarboxylic acid, 8-methoxy-2, 3-naphthalenedicarboxylic acid, 8-n-tro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2, 3-acid dicarboxylic acid, 2 ', 3' -diphenyl-p-terfenyl-4,4'-dicarboxylic acid, acid (diphenyl ether) -4,4'-dicarboxylic acid, m? dazol-4, 5-dicarboxylic acid, 4 (1H) -oxot? ocromen-2, 8-d? carboxylic acid, -tert-butyl, 3-benzenedicarboxylic acid, 7,8-qumolmicarboxylic acid, 4, 5? m? dazold? carboxylic acid, 4-c? clohexane-1,2-dicarboxylic acid , hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1, 7-heptad? carboxylic acid, 5-hydroxyl-1, 3-benzenedicarboxylic acid, 2,5-d? hydrox? -l, 4-benzenedicarboxylic acid, p? razm-2, 3 -dicarboxylic acid, furan-2, 5-d? carboxylic acid, l-noneo-6,9-d? carboxylic acid, eicosenodicarboxylic acid, 4,4'-dihydroxydiphenic acid? l-3-methane-3'-dicarboxylic acid, l-ammo-4-met l-9,10-dioxo-9,10-d? h? -tranthracene-2,3-dicarboxylic acid, 2, 5-p? r acid ? dmd? carboxy? co, c-clohexene-2,3-dicarboxylic acid, 2,9-d? chlorofluorubm-4, 11-d? carboxylic acid, 7-chloro-3-methyqumolm-6 acid, 8-d? Carboxyl? Co, 2,4-dichlorobenzophenone-2,5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-p? R? Dmd? Carboxy? Acid, 1-met? Lp acid Rhod-3, 4 -dicarboxyl, l-benzyl-lH-pyrrol-3, 4-dicarboxylic acid, anthraquone-1, 5-d? carboxylic acid, 3,5-pyrazodicarboxylic acid, 2-n? trobenzene-l, 4- d? carboxyl? co, heptane-1, 7-d? carboxyl? c acid, c? clobutane-1, 1-dicarboxylic acid, 1, 14-tetradecane? carboxyl? acid, 5,6-dehydroorbornanoic acid- 2,3-dicarboxylic acid, 5-et? -1- 2,3-pyriddicarboxylic acid or camphor dicarboxylic acid. Tpcarboxylic acids such as: 2-Hydroxy-1,23-propanedicarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,3-, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, acid 2-phosphono-1,2,4-butanedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-lH-pyrrolo acid [2, 3-F] quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene acid 1, 2,4-trichlocarboxylic acid, 1,2,3-propanetricarboxylic acid or aurinotricarboxylic acid, or tetracarboxylic acids such as: 1,1-dioxideoperylla [1,12-BCD] thiophene-3, 4,9, 10-tetracarboxylic acid , perylene tetracarboxylic acids such as perylene-3, 4, 9, 10-tetracarboxylic acid or (perylene 1, 12-sulfone) -3,4,9,9-tetracarboxylic acid, butanetetracarboxylic acids such as acid 1, 2, 3, 4 -butane tetracarboxylic acid or meso-1, 2 , 3,4-butane tetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13, 16-hexaoxacyclooctadecane-2, 3, 11, 12, tetracarboxylic acid, acid 1,2, 4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanotetracarboxylic acid, 1,2,5,6-hexane tetracarboxylic acid, 1, 2, 7, 8, -octanotetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanotetracarboxylic acid, benzophenonatetracarboxylic acid, 3, 3 ', 4, 4' -benzophenone-tetracarboxylic acid, tetrahydrofurantracarboxylic acid or cyclopentanetetracarboxylic acids such as cyclopentane-1,2,3,4-tetracarboxylic acid. Particular preference is given to optionally using at least monocarboxylic aromatic dicarboxylic, tricarboxylic or tetracarboxylic acids having one, two, three four or more rings and in which each of the rings can comprise at least one heteroatom, with two or more rings that they are capable of understanding identical or different heteroatoms. For example, preference is given to one-ring carboxylic acids, one-ring tricarboxylic acids, one-ring tetracarboxylic acids, two-ring dicarboxylic acids, two-ring tricarboxylic acids, two-ring tetracarboxylic acids, three-ring dicarboxylic acids, acids three-ring tricarboxylic acids, three-ring tetracarboxylic acids, four-ring dicarboxylic acids, four-ring tricarboxylic acids, four-ring tetracarboxylic acids. Suitable heteroatoms are, for example, N, 0, S, B, P, Si and the preferred heteroatoms are N, S and / or 0. Suitable substituents that may be mentioned in this regard are, inter alia, -OH, a nitro group, an amino group or an alkyl or alkoxy group.

Particular preference is given to using acetylenedicarboxylic acid (ADC), camphor dicarboxylic acid, fumaric acid, succinic acid, benzenedicarboxylic acid, naphthalene dicarboxylic acids, biphenyldicarboxylic acids such as 4,4'-biphenyldicarboxylic acid (BPDC), pyrazindicarboxylic acids such as acid 2.5 -pirazindicarboxylic acid, bipyridinedicarboxylic acids such as 2,2'-bipyridinedicarboxylic acids such as 2,2'-bipyridin-5,5'-dicarboxylic acid, benzenetricarboxylic acids such as 1,2,3-, 1,2,4-benzenetricarboxylic acid or 1,3,5-benzenetricarboxylic acid (BTC), benzenetetracarboxylic acid, adamantanetetracarboxylic acid (ATC), adamantanedibenzoate (ADB), benzenetribenzoate (BTB), methane tetrabenzoate (MTB), adamantanotetrabenzoate or dihydroxyteraphthalic acids such as 2, 5-dihydroxyethyl alcohol (DHBDC) as at least bidentate organic compounds. Particular preference is given to using, inter alia, isophthalic acid, terephthalic acid, 2,5-dihydroxyterephthalic acid, 1,2-benzenetricarboxylic acid, 1,3-benzenetricarboxylic acid, 2,6-naphthalene dicarboxylic acid, acid 1,4-naphthalenedicarboxylic acid, 1,2,3,4- and 1,2,4,5-benzenetetracarboxylic acid, camphor dicarboxylic acid or 2,2'-bipyridine-5,5'-dicarboxylic acid.

The present invention further provides a process for preparing a structure according to the invention, comprising the step of: contacting a metal ion M with an at least partially protonated bidentate organic compound L having at least one functional group G which it binds non-coordinately to M and is selected from the group consisting of -S02H and -P03H2 and also its deprotonated analogs to form the structure of the invention. In the process described above, the group G is already present in the organic compound L, so that additional conversion steps are not necessary. However, it must be ensured that a sufficient number of group G are present in free form and do not participate in the formation of the structure. The present invention further provides a process for preparing a structure according to the invention, comprising the steps: contacting an M metal ion with an at least optional deprotonated organic compound L 'bidentate having at least one group G' comprising S- and / or P-, which is preferably linked in an uncoordinated manner with M, and - conversion of the group G 'into a group G in L. In this process, use is made of a precursor group G 'which is introduced into the formation of a skeleton of the at least organic compound L' bidentate, L 'is related to L in such a way that the formation of the group G results in the conversion of L 'to L. A) Yes, L 'differs from L in at least group G. However, it is also possible that L' undergoes subsequent chemical changes during the conversion of G 'to G, so that L' may differ from L in the structural characteristics chemical The group G 'is preferably selected so that it can not participate in the formation of the structure. After the formation of the metal organic structure, the group G 'can then be converted to the desired group G, the preferred groups G' are any ester derivative of group G, ie the sulfonic esters or phosphonic esters, or halides, anhydrides or acetals thereof which can be converted by simple hydrolysis to the desired group G. Preference is given to sulfonic or phosphonic esters. In addition, the group G 'can be a sulfur or phosphorous compound that occurs in the lower oxidation state. Any oxidation state is in principle possible here. The conversion to group G is effected by the oxidation methods known to those skilled in the art. The examples of the G 'groups are thiols, sulfides, disulfides, sulfites or sulfmates. Suitable oxidants are, for example, peroxides, oxygen air, permanganate or chromates. To introduce the phosphoric acid group, it is generally possible to use similar processes, for example phosphonation or the introduction of a phosphory group. A person skilled in the art will know additional methods. The present invention further provides a process for preparing a structure according to the invention, comprising the steps: - reacting an organic porous metal structure comprising at least one at least organic compound L 'bidentate coordinated with at least one ion metal M with a compound comprising S- and / or P- to form a group G in L or a group G 'and if G' is present, convert G 'to G or L. In this process, group G is introduced in an organic, porous metal structure, none of the at least organic L bidentate compounds of the structure having a precursor group. Here, porous metal organic structures can be structures known from prior art. A possible way to carry out the process described above is direct sulfonation. This can, for example, take place in an aromatic that is part of the organic compound L '. Otherwise, apply what was mentioned above to L '. L 'differs from L at least in the absence of group G. The aromatic is preferably a phenyl or naphthyl group. However, sulfonation can also be carried out, for example, in a double bond such as a viral double bond. The sulfonation reagents can be S03f, H2SO4, oil, chlorosulfonic acids or sulfonyl chloride or sulfur chloride. Here, also in group G 'can be converted, if appropriate, into group G by hydrolysis and / or oxidation or otherwise. Examples of the metal organic structures known in the prior art are given below. In addition to the MOF designation, the metal and at least the bidentate ligand, the solvent and the cellular parameters are indicated (angles a, β and y, and dimensions A, B and C in A). The last ones were determined by X-ray diffraction.

ADC acetylenedicarboxylic acid NDC naphthalenedicarboxylic acid BDC benzenedicarboxylic acid ATC adamantanotetracarboxylic acid BTC benzene tricarboxylic acid BTB benzenebenzoic acid MTB methanetetrabenzoic acid ATB adamantanotetrabenzoic acid ADB adamantanedibenzoic acid Additional MOFs are MOF-177, MOF-178, MOF-74, MOF-235, MOF-236 , MOF-69 A 80, MOF-501, MOF 502, which are described in the literature. The metalloorganic structures of the present invention comprise pores, in particular micropores and / or mesopores. Micropores are defined as pores having a diameter of 2 nm or less and mesopores are defined by a diameter in the range of 2 to 50 nm, in each case according to the definition given in Puré & Applied Chem. 57 (1985), 603-619, in particular on page 606. The presence of micropores and / or mesopores can be verified by means of sorption measurements, with these measurements determining the absorption capacity of the MOF for nitrogen at 77 kelvm in accordance with DIN 66131 and / or DIN 66134. The specific surface area, calculated in accordance with the Langmuir model in accordance with DIN 66135 (DIN 66131), of an organic metal structure in powder form is preferably more than 5 m2 / g, even more preferably more than 10 m2 / g, even more preferably more than 50 2 / g, even more preferably more than 500 2 / g, even more preferably more than 1000 m2 / g and particularly preferably more than 1250 m2 / g. The shaped MOF bodies may have a lower specific surface area, but preferably more than 10 m2 / g, more preferably more than 50 m2 / g., even more preferably more than 500 m2 / g. The pore size of the metal organic structure can be controlled by selection of the appropriate ligand and / or at least the bidentate organic compound. It is often the case that the larger the organic compound, the larger the pore size. The pore size is preferably from 0.2 nm to 30 nm, particularly preferably in the range from 0.3 nm to 9 nm, based on the crystalline material. However, larger pores whose size distribution can vary also occur in a shaped MOF body. However, preference is given to more than 50% of the total pore volume, in particular more than 75%, being formed by pores having a pore diameter of up to 1000 nm. However, a large part of the pore volume is preferably made by pores having two ranges different in diameter. Therefore, more preferred for more than 25% of the total pore volume, in particular more than 50% of the total pore volume, to be formed by pores that are in a diameter range from 100 nm to 800 nm and for more than 15% of the total pore volume, in particular more than 25% of the total pore volume, to be formed by pores that are in the diameter range of up to 10 nm. The pore distribution can be determined by means of mercury porosimetry. The organic metal structure can be presented in the powder form or as an agglomerate. The structure can be used as such or it becomes a shaped body. The preferred processes here are extrusion or tabletting. In the production of shaped bodies, the structure can be mixed with additional materials such as binders, lubricants or other additives that are added during production. It is similarly conceivable for the structure to be mixed with additional constituents, for example adsorbents such as activated carbon or the like. The possible geometries of the body formed in principle are not subject to any restriction. For example, the possible forms are, inter alia, pellets such as pellets in the form of disks, pills, spheres, granules, extrudates such as rods, honeycombs, grids or hollow bodies.

In order to produce hollow bodies, it is the principle that it is possible to use all suitable methods. In particular, the following processes are preferred: kneading / milling or amalgamating the structure either alone or together with at least one binder and / or at least one paste-forming agent and / or at least one standard compound to give a mix; forming the resulting mixture by means of at least one suitable method such as extrusion; optionally washing and / or drying and / or calcining the extrudate; optionally finishing treatment. - application of the structure to at least one porous support material optionally. The material obtained can then be further processed by the method described above to give a shaped body. - application of the structure to at least one porous substrate optionally. Kneading and milling and shaping can be carried out by any suitable method, for example as described in Ullmanns Enzyklopadie of the Technischen Chemie, 4 edition, volume 2, P. 313 ff (1972). For example, kneading / milling and / or shaping can be carried out by means of a piston press, roller press in the presence or absence of at least one binder, compounding, pelletization, tabletting, extrusion, coextrusion, foaming, centrifugation, coating, granulation, preferably spray granulation, spraying, spray drying or a combination of two or more of these methods. Particular preference is given to the production of pellets or spheres and / or tablets. The kneading and / or shaping can be carried out at elevated temperatures, for example in the range from room temperature to 300 ° C, and / or under superatmospheric pressure, for example in the range of atmospheric pressure to a few hundred bar, and / or in a protective gas atmosphere, for example in the presence of at least one noble gas, nitrogen or a mixture of two or more thereof. The kneading and / or shaping is, in a further embodiment, carried out with the addition of at least one binder, with the binder basically used which is capable of being any chemical compound that ensures the desired viscosity for kneading and / or forming of the composition to be kneaded and / or shaped. Accordingly, the binders may be, for the purposes of the present invention, either compounds that increase viscosity or reduce viscosity. Preferred binders are, for example, inter alia aluminum oxide or binders comprising aluminum, as described, for example in WO 94/29408, silicon dioxide as described in, for example, EP 0 592 050 A1, mixtures of silicon dioxide and silicon oxide, as described in, for example, WO 94/13584, clay minerals as described in, for example, JP 03-037156 A, for example montmorillonite, kaolin, bentonite, hallosite, dickite, nacrite and anauxite, alkoxysilanes as described in, for example, EP 0 102 544 Bl, for example tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane , tetrabutoxysilane, or, for example, tpalcoxisilanos such as trimetoxisialno, triethoxysilane, tripropoxysilane, tpbutoxisilano, alkoxytitanates by trialkoxysilanes example such as tpmetoxisilano, tpetoxisilano, tppropoxisilano, tpbutoxisilkano, alkoxytitanates by tetraalkoxytitanates example such as tetrametoxititanato, tetraethoxytitanate, tetrapropoxytitanate, tetrabutoxytitanate or, ejmplo, tpalcoxititanatos such as tpmetoxititanato, tptotoxititanato, tripropoxititanato, tp butoxytitanate, alkoxy zirconates, for example tetraalkoxy zirconates tetrabutoxizirconate or, for example, trialkoxy zirconates such as trimethoxy zirconates, triethoxy zirconate, t-propoxy zirconate, tributoxizirconate, silica sols and / or amphiphilic substances.

It is also possible to use a viscosity-increasing compound which is, for example, if appropriate in addition to the aforementioned compounds, an organic compound and / or a hydrophilic polymer such as cellulose or cellulose derivative such as methylcellulose and / or a polyacrylate. and / or polymethacrylate and / or a polyvinyl alcohol and / or a polyvinylpyrrolidone and / or a polusobutene and / or a polytetrahydrofuran and / or a polyethylene oxide. A paste forming agent, it is possible to use, inter alia, preferably water or at least one alcohol such as a monoalcohol having from 1 to 4 carbon atoms, for example methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol or 2-methyl-2-propanol or a mixture of water and at least one of the alcohols mentioned or a polyhydric alcohol such as a glycol, preferably a miscible polyhydric alcohol in water, either alone or as a mixture with water and / or at least one of the monohydric alcohols mentioned. Additional additives that can be used for kneading and / or forming are, inter alia, lubricants such as graphites, amines or amine derivatives such as tetraalkylammonium compounds or soft alcohols and compounds comprising carbonate such as calcium carbonate. Such additional additives are described, for example in EP 0 389 041 Al, EP O 200 260 Al or WO 95/19222. The order of the additives such as the standard compound, binders, paste-forming agent, substance which increases the viscosity during forming and kneading is, in principle, not critical. In a further embodiment, the shaped body obtained by kneading and / or shaping, is subjected to at least one drying step which is generally carried out at a temperature in the range from 25 to 300 ° C, preferably in the range from 50 to 300 ° C and particularly preferable in the range from 100 to 300 ° C. It is similarly possible to carry out drying under reduced pressure or under a protective gas atmosphere or spray drying. The present invention further provides the use of a porous metal organic structure, according to the invention as an ion exchanger, Brónsted acid or support material. The porous structures can be used, for example, in chemical reactions such as esterifications, etherifications, transesterifications, transeterifications, alkylations, acylations, isomerizations, dehydrations and hydrations, alkoxylations, dimerizations, oligomerizations and polymerizations and also aminations. Examples Example 1 - Preparation of an organic structure of aluminum metal ("Al-MOF"). 250.1 g of terephthalic acid (BDC) and 292.9 g of Al2 (S04) 3.18H20 were suspended in 1257 g of N, N-dimethylformamide (DMF) and heated at 130 ° C for 24 hours while stirring. The suspension is subsequently filtered and the filtrate washed with DMF. The filter cake is dried at 120 ° C in a drying oven for 2 hours. It is subsequently calcined at 320 ° C in a muffle furnace for 2 hours. Example 2 - Preparation of a sulfonated Al-MOF according to the invention. 3.0 g of the powdered Al-MOF of Example 1 was introduced into an exchange tube made of glass and provided with a P3 glass frit and heated to 80 ° C under nitrogen (16 1 / h standard). The powder is reacted at 80 ° C with 1.2 g of sulfur trioxide gas for a period of 5 minutes. After the reaction, the powder is dried at 50 ° C and 100 mbar for 16 hours. It was found that the surface area (BET) is 494 m2 / g. The XRD is shown in Fig. 1, where I (Lin (counts)) is shown as a 2T function (2-Theta scale). Elemental analysis indicates a S: C ratio of 1:31. The Al: S ratio is approximately 7: 1. From this it is possible to calculate an acid density of approximately 1.0 mmol / g for the sulphonated Al-MOF powder. Example 3 - The acid catalyzed esterification of butanol with acetic acid using an organic metal structure according to the invention. In a 100 ml three neck flask fitted with a reflux condenser, 50 g of a mixture of butanol: acetic acid (67: 33% by weight) were mixed with 1.0 g of sulfonated Al-MOF from Example 2 and stirred. The mixture is then heated to 75 ° C and a sample is taken after a reaction time of 6 hours. The sample is subsequently analyzed by gas chromatography to determine the composition. It comprises 7% by acetic acid area, 58% by butanol area and 35% by butyl acetate area. Comparative Example 4 - The esterification of butanol with acetic acid on an unsulfonated MOF. The experiment is carried out in a manner analogous to Example 3, but 1.0 g of powdered Al-MOF of Example 1 is used here. The sample after a reaction time of 5.5 hours comprises 11% by acetic acid area, 73% per butanol area and 16% per area of butyl acetate.

Claims (10)

1. CLAIMS 1. An organic, porous metal structure characterized in that it comprises at least one at least organic compound L bidentate coordinated to at least one metal ion M, wherein L has at least one functional group G which is linked in a non-coordinated manner to M and is selected from the group consisting of -S03H and its de-protonated analogue.
2. 2. The structure according to claim 1, characterized in that the molar ratio of G: M is at least 1:75.
3. 3. The structure according to any of claims 1 or 2, characterized in that it has an acid density of at least 0.1 mmol / g of the structure.
4. 4. The structure according to any of claims 1 to 3, characterized in that M is selected from the group consisting of Mg, Ca, Al, Ga, In, Zn, Cu, Fe and Mn.
5. 5. The structure according to any one of claims 1 to 4, characterized in that L is derived from a dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid or a sulfur analogue or a diamine.
6. 6. A process for preparing a structure according to any of claims 1 to 5, characterized in that it comprises the step: - contacting a metal ion M with a compound organic L bidentate optionally at least deprotonated, having at least one functional group G that binds non-coordinatedly to M and is selected from the group consisting of -SO 3 H and its deprotonated analog to form the structure.
7. 7. A process for preparing a structure according to any of claims 1 to 5, characterized in that it comprises the step: - contacting a metal ion M with an optionally at least deprotonated organic compound L at least, which has at least a group G 'comprising S which is preferably linked in an uncoordinated manner to M, and - the conversion of group G' into a group G into L.
8. 8. A process according to claim 7, characterized in that G 'is a sulfonate, sulphite, disulfite, sulfinate group or a corresponding acid, ester or halide, mercapto or phosphine group.
9. 9. A process for preparing a structure according to any of claims 1 to 5, characterized in that it comprises the steps: - the reaction of a porous metal organic structure, comprising at least one bidentate organic L 'compounds, coordinated with at least one metal ion M containing a vinyl or aromatic double bond with a compound comprising S to form a group G in L or a group G 'in L, and - if G 'is present, the conversion of G' to G. The use of an organic metal structure according to any of claims 1 to 5, as an ion exchanger, Brónsted acid or support material. , for example in esterifications, etherifications, transesterifications, transeterifications, alkylations, acylations, isomerizations, dimerizations, oligomerizations and polymerizations, alkoxylations, dehydrations and hydrations and also aminations.