MX2008006060A - Porous organo-metallic skeleton material containing an additional polymer - Google Patents

Abstract

The invention relates to a porous organo-metallic skeleton material for accommodating at least one substance. The skeleton material contains at least one at least bidentate organic compound that is coordinatively bound to at least one metal ion, whereby the skeleton material has, at least in part, pores that contain a polymer, which is suited for adsorbing a substance. The invention also relates to a method for producing the skeleton material, to a method for accommodating at least one substance by the skeleton material, and to the use of the skeleton material, in particular, for storing, separating, controlled release or chemically converting an accommodated substance.

Description

MATERIAL OF ESQU E LETO ORGAN-M ETHELIC POROSO CONTAINING AN ADDITIONAL POLYMER The present invention relates to a structure material comprising a porous metal-organic structure material and also another polymer, methods for the production thereof, use thereof and also methods for absorbing at least one substance by the material of structure. Porous metal-organic structure materials are used for various purposes. An important field of use in this case is the storage of gases. EP-B 727 608 describes, for example, the storage of methane gas using metal-organic structure materials having a one-dimensional channel structure. WO-A 03/064036 also describes the storage of gases using metal-organic structure materials. The gases to be stored in this case are hydrogen, nitrogen, noble gases, carbon monoxide, carbon dioxide and also compounds that generate and / or supply these gases. Another important field of use is the separation of gases from gas mixtures. E P-B 1 070 538 describes the separation of carbon dioxide, water, N2O, ethylene and carbon monoxide and also separating hydrocarbons from air. The separation of xenon from a mixture of krypton / xenon is described in DE-A 1 0 2005 000 938.

Also, the separation of odor substances from gases using metal-organic structure materials becomes possible. Said separation is the subject of German patent application No. 10 2005 022 844.5. However, metal-organic structure materials are also used in chemical synthesis. For example, WO-A 03/035717, for example, describes the alkoxylation of organic compounds in the presence of a metal-organic structure material. The alkoxylation of monooles is described in WO-A 2005/003069. In order to obtain novel metal-organic structure materials having properties that lead to improved results for example in gas storage, separation or chemical synthesis, WO-A 2005/049892 proposes the production of metal-organic structure materials by an electrochemical route. In this case, metal-organic structure materials are obtained which, in comparison with conventional structural materials, comprise the same metal ions and also ligands, but have differences in structure that may result in improved properties. For example, WO-A 2005/049484 describes the use of said metal-organic structure materials produced by an electrochemical route for the storage of gases, in particular saturated and unsaturated hydrocarbons, saturated and unsaturated alcohols, oxygen, nitrogen, noble gases, carbon monoxide, carbon dioxide, synthesis gas, natural gases and also hydrogen, methane, ethane, propane, butanes, ethylene, propylene, acetylene, neon, argon, krypton and also xenon. Although by proper choice of metal ions and ligands can be produced porous metal-organic structure materials "made to order" and despite alternative production methods that can introduce structure materials having improved properties, there is still a requirement for structural materials novel porous metal-organic having improved properties compared to those described in the prior art. Thus, an object of the present invention is to prepare structure materials having improved properties compared to the prior art, in particular in storage and also gas separation and chemical synthesis. The object is achieved by a porous metal-organic structure material for absorbing at least one substance, the structure material comprising an organic compound of at least bidentate bound by coordination to at least one metal ion, and the structure material having at least in part pores comprising a polymer that is suitable for adsorbing the at least one substance. This is because it has been discovered that the pores of the metal-organic structure material can be occupied by a polymer that can be formed in the pores so that the absorption of a substance by the metal-organic structure material, also via the adsorption to the polymer formed in the pores of the structure material, can lead to improved separation. Furthermore, in comparison with the pure porous metal-organic structure material, the improved absorption of a substance in the presence of the polymer can proceed at comparatively low pressures and thus have varied uses. Likewise, the absorption of the substance can proceed with its absorption, storage and release in the structure material at elevated temperatures. Finally, the absorption of at least one substance can be used for a chemical reaction later to proceed in the presence of the structure material. The porous metal-organic structure materials are described in the prior art as such without an additional polymer. The porous metal-organic structure material comprises an organic compound of at least bidentate linked by coordination to at least one metal ion. This metal-organic structure material (MOF) is described, for example, in US-A 5,648,508, EP-A 0 790 253, M. O-Keeffe et al., J. Sol. State Chem., 152. (2000). , pages 3 to 20, H. Li et al., Nature 402 (1999), page 276, M. Eddaoudi and others, Topics in Catalysis 9, (1999), pages 105 to 111, B. Chen et al., Science 291. (2001), pages 1021 to 1023 and DE-A-101 11 230. The metal-organic structure materials according to the present invention comprise pores, in particular micropores and / or mesopores. Micropores are defined as those 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 in accordance with the definition as specified by Pure & Applied Chem. 57 (1985), 603-619, in particular on page 606. The presence of micropores and / or mesopores can be studied using absorption measurements, these measurements determining the absorption capacity of the MOF for nitrogen at 77 Kelvin as is specified in DIN 66131 and / or DIN 66134. Preferably, the specific surface area, calculated in accordance with the Langmuir model as specified in DIN 66135 (DIN 66131, 66134) for a MOF in powder form, is greater than 5 m2 / g, more preferably greater than 50 m2 / g, still more preferable greater than 500 m2 / g, even more preferably greater than 1000 m2 / g, and in particular preferably greater than 1500 m2 / g. The bodies in the form of MOF may have a smaller specific surface area; however, preferably, greater than 10 m2 / g, more preferably greater than 50 m2 / g, still more preferable greater than 500 m2 / g. The metal component in the structure material is preferably selected from the groups la, lia, Illa, IVa a Villa and Ib a Vlb. Particular preference is given to Mg, Ca, Sr, Ba, Sc, 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, B, Al, Ga, In, TI, Si, Ge, Sn, Pb, As, Sb, and Bi. More preference is given to Zn, Al, Mg, Ca, Cu, Ni, Fe, Pd, Pt, Ru, Rh and Co. In particular preference is given to Zn, Al, Ni, Cu, Mg, Ca, Fe. With respect to the ions of these elements, those that can be mentioned in particular are Mg2 +, Ca2 +, Sr2 +, Ba2 +, Sc3 + Y3 +, Ti4 +, Zr4 +, Hf4 +, V4 +, V3 +, V2 +, Nb3 +, Ta3 + , Cr3 +, Mo3 +, W3 +, Mn3 + Mn2 +, Re3 +, Re2 +, Fe3 +, Fe2 +, Ru3 +, Ru2 +, Os3 +, Os2 +, Co3 +, Co2 +, Rh2 + Rh +, lr2 +, lr +, Ni2 +, Ni +, Pd2 +, Pd +, Pt2 +, Pt +, Cu2 +, Cu +, Ag +, Au +, Zn2 + Cd2 +, Hg2 +, Al3 +, Ga3 +, ln3 +, Tl3 +, Si +, Si2 +, Ge4 +, Ge2 +, Sn +, Sn2 + Pb4 +, Pb2 +, As5 +, As3 +, As +, Sb5 +, Sb3 +, Sb +, Bi5 +, Bi3 + and Bi +. The term "organic compound of at least bidentate" refers to an organic compound comprising at least one functional group which is capable of forming, at a given metal ion, at least two, preferably two, coordinated bonds, and / or two or more, preferably two metal atoms, in each case a coordinated bond. As functional groups via which such coordinated links can be formed, in particular, for example, the following functional groups can be mentioned: -CO2H, -CS2H, -NO2, -B (OH) 2, -SO3H, -Si (OH) 3, -Ge (OH) 3, -Sn (OH) 3) -Si (SH) 4, -Ge (SH) 4, -Sn (SH) 3, -PO3H, -AsO3H, -AsO4H, -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, wherein R, for example, is preferably an alkylene group having 1, 2, 3, 4 or 5 carbon atoms, for example, a methylene, ethylene, n-propylene, i-propylene, n-butylene, i-butylene, tert-butylene or n-pentylene group, or a group aryl comprising 1 or 2 aromatic nuclei, for example 2 C6 rings which, if appropriate, can be condensed and, independently of one another, in each case, a substitute can be suitably substituted, and / or independently of one another, in each case, they can comprise at least one heteroatom, for example N, O and / or S. Likewise, according to Preferred, functional groups may be mentioned wherein the aforementioned radical R is not present. In this respect, among other things, it can be mentioned -CH (SH) 2, -C (SH) 3, -CH (NH 2) 2, -C (NH 2) 3, -CH (OH) 2, -C (OH) ) 3, -CH (CN) 2 or -C (CN) 3. The at least two functional groups can in principle be linked by any suitable organic compound, as long as it is ensured that the organic compound having these functional groups is capable of forming the coordinated bond and of producing the structure material. Preferably, the organic compounds comprising the at least two functional groups are derived from a saturated or unsaturated aliphatic compound or an aromatic compound or a compound that is both aliphatic and aromatic. The aliphatic compound or the aliphatic part of both the aliphatic compound and the aromatic compound can be linear and / or branched and / or cyclic, a plurality of cycles also being possible per compound. In addition, preferably, the aliphatic compound or the aliphatic part of both the aiiphatic and aromatic compound comprises 1 to 15, further preferably 1 to 14, further preferably 1 to 13, further preferably 1 to 12, further preferably 1 to 11, and in particularly preferably 1 to carbon atoms, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Particular preference is given here, inter alia, to methane, adamantane, acetylene, ethylene or butadiene. The aromatic compound or the aromatic part of both the aromatic and aliphatic compound may have one or otherwise a plurality of nuclei, for example, two, three, four or five nuclei, the nuclei being able to be present separately from each other and / or by at least two nuclei being able to be present in condensed form. Particularly preferably, the aromatic compound or the aromatic part of both the aliphatic and the aromatic compound has one, two or three cores, one or two cores being particularly preferred. Independently from one another, furthermore, each nucleus of said compound may comprise at least one heteroatom, for example N, O, S, B, P, Si, Al, preferably N, O and / or S. In addition, preferably, the aromatic compound or the aromatic part of both the aromatic and aliphatic compounds comprises one or two C6 nuclei, both being present either separately from one another or in condensed form. In particular, benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl can be mentioned as aromatic compounds. For example, among other things, trans-muconic acid or fumaric acid or phenylenebisacrylic acid may be mentioned. For example, in the context of the present invention, mention may be made of dicarboxylic acids, such as oxalic acid, succinic acid, tartaric acid, 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid , heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2 acid, 3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimidodicarboxylic acid, pyridine acid -2 , 6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylenedicarboxylic acid, Pluriol E 200 dicarboxylic acid, , 6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-di-carboxylic acid, octadicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1 '-diphenyl-3,3-acid '-dicarboxylic acid, 1,4-bi- (phenylamino) benzene-2,5-dicarboxylic acid, 1,1' -bubfethyl-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, acid 1-anilinoanthraquinone-2,4'-dicarboxylic acid polytetrahydrofuran-250-dicarboxylic acid, 1,4-bi- (carboxymethyl) piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1- (4-carboxy) phe nor l-3- acid (4-chloro) nyl-pyridine-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexa-chloro-5-norbornene-2,3-dicarboxylic acid, phenylanedicarboxylic acid, 1,3-dicarboxylic acid -dibenzyl-2-oxoimidazolidine, 4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1, 8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazole acid -dine-4,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedi-carboxylic acid, hydroxybenzophenone-dicarboxylic acid , Pluriol E 300-dicarboxylic acid, Pluriol E 400-dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinadi carboxylic acid, 5,6-dimethyl-2,3-acid pyrazinadicarboxylic acid, 4,4'-diaminodiphenyletheriimido dicarboxylic acid, 4,4'-diaminodiphenylmethanediimidocarboxylic acid, 4,4'-diaminodiphenyl-sulfonadiimidocarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, -methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenecarboxylic acid, 8-sulfo-2,3-naphthalene-dicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2 ', 3'-diphenyl acid -p-terphenyl-4,4'-dicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4 (1 H) -oxothiochromen-2,8-dicarboxylic acid, -tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolineadicarboxylic acid, 4,5-imidazolecarboxylic acid, 4- acid cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzene-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5- acid dicarboxylic acid, 1-noneeno-6,9-dicarboxylic acid, eicosenodicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl 1-9,10-dioxo-9 acid , 10-dih id roa nt racen o-2,3-dicarboxílico, 2,5-piridinadicarboxílico acid, acid cyclohexene-2,3-dicarboxílico, acid 2,9-dichlorofluorubin-4,11-dicarboxílico, acid 7-chloro- 3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2 ', 5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4- acid dicarboxylic acid, 1-benzyl-1 H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1, 5-dicarboxylic acid, 3,5-pyrazodicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane- 1, 7-dicarboxylic, Cyclobutane-1,1-dicarboxylic acid, 1,4-tetradecanedicarboxylic acid, 5,6-de-hydronorbornane-2,3-dicarboxylic acid or 5-ethyl-2,3-pyridinedicarboxylic acid, tricarboxylic acids such as 2-hydroxy-1, 2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1 acid 2, 4-butanethri carboxylic acid, 1, 3,5-benzenetricarboxylic acid, 1-hydroxy-1, 2,3-propanecarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrole [ 2,3-F] quinoline- 2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tri-carboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1, 2,4- tricarboxylic acid, 1,3-propanetricarboxylic acid or aurintricarboxylic acid, or tetracarboxylic acids such as 1, 1-di-oxido per i lo [1, 12-BCD] thiophene-3,4,9,10-tetra-carboxylic acid, perylenetetracarboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid or perylene acid -1, 12-sulfone-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic acids such as 1,2,4,4-butanetetracarboxylic acid or meso-1, 2,3,4-butanetetra-carboxylic acid, decane-2 acid , 4,6,8-tetracarboxylic acid 1,4,7,10,13, 16-hexaoxaciclooctadecano-2,3,11, 12-tetracarboxílico, 1, 2,4,5-bencenotetracarboxílico acid, acid 1, 2,11, 12-dodecano-tetracarboxílico, acid 1 2,5,6-hexane tetracarboxylic acid, 1,2,7,8-octanotetracarboxylic acid, 1, 4,5,8-naphthalenetetracarboxylic acid, 1, 2,9, 10-decacanotetra carboxylic acid, benzophenonetracarboxylic acid, 3,3 ', 4,4'-benzophenonetracarboxylic acid , tetrahydrofuran-tetracarboxylic acid or cyclopentanotetracarboxylic acids such as cyclopentane-1, 2,3,4-tetracarboxylic acid. Very particularly preferably, at least mono-, di-, tri-, tetranuclear or nuclear mono-substituted aromatic di-, tri- or tetracarboxylic acids are optionally used, each of the nuclei being capable of understand at least one heteroatom, two or more cores being able to understand identical or different heteroatoms. For example, preference is given to mononuclear dicarboxylic acids, mononuclear tricarboxylic acids, mononuclear tetracarboxylic acids, dinuclear dicarboxylic acids, dinuclear tricarboxylic acids, dinuclear tetracarboxylic acids, trinuclear dicarboxylic acids, trinuclear tricarboxylic acids, trinuclear tetracarboxylic acids, tetranuclear dicarboxylic acids, tetranuclear tricarboxylic acids and / or tetranuclear tetracarboxylic acids. Suitable heteroatoms are, for example, N, O, S, B, P, Si, Al, the preferred heteroatoms in this case are N, S and / or O. A suitable substitute which can be mentioned in this respect is, other things, -OH, a nitro group, an amino group or an alkyl or alkoxy group. Particularly preferably, as organic compounds of at least bidentate, use is made of acetylenedicarboxylic acid (ADC), benzenedicarboxylic acids, naphthalenedicarboxylic acids, biphenyldicarboxylic acids, for example, 4,4'-biphenyldicarboxylic acid (BPDC), bipyridinedicarboxylic acids, for example 2,2'-bipyridinedicarboxylic acids, for example 2,2'-bipyridine-5,5'-dicarboxylic acid, benzenetricarboxylic acids, for example 1, 2,3-benzenetricarboxylic acid or 1,3,5-benzenetricarboxylic acid (BTC) , adamantanotetracarboxylic acid (ATC), adamantanediibenzoate (ADB), benzenetribenzoate (BTB), methane tetrabenzoate (MTB), adamantanotetrabenzoate, or acids dihydroxyterephthalic, for example, 2,5-dihydroxyterephthalic acid (DHBDC). Very particularly preferably, it is used, inter alia, isophthalic acid, terephthalic acid, 2,5-dihydroxyterephthalic acid, 1,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, or 2,2-acid. '-bipyridine-5,5'-dicarboxylic acid. In addition to these organic compounds of at least bidentate, the MOF may also comprise one or more monodentate ligands. Suitable solvents for producing the MOFs are, inter alia, ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethyl sulfoxide, water, hydrogen peroxide, methylamine, sodium hydroxide solution, N-methylpolydone ether, acetonitrile, benzyl chloride, triethylamine, ethylene glycol and mixtures thereof. Additional metallic ions, organic compounds of at least bidentate and solvents for producing MOFs are described, inter alia, in US-A 5,648,508 or DE-A 101 11 230. The pore size of the MOF can be controlled by the selection of the appropriate ligand and / or the at least bidentate organic compound. In general, it is true that the greater the organic compound, the greater the pore size. Preferably, the pore size is 0.2 nm to 30 nm, particularly preferably the pore size is in the range of 0.3 nm to 3 nm, based on the crystalline material.

However, in a body in the form of MOF, larger pores may also occur, the size distribution of which may vary. However, preferably, more than 50% of the total pore volume, in particular more than 75%, is formed by pores having a pore diameter of up to 1000 nm. Preferably, however, a majority of the pore volume is formed by pores of two diameter ranges. Therefore it is 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 that are in a diameter range of 100 nm to 800 nm, and if more of 15% of the total pore volume, in particular more than 25% of the total pore volume, is formed by pores that are in a diameter range of up to 10 nm. The pore distribution can be determined by means of mercury porosimetry. Examples of metal-organic structure materials are given hereinafter. In addition to the designation of the MOF, the metal and also the ligand of at least bidentate, in addition to the solvent and also the cellular parameters are given (angle a, β and y and also the distances 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 benzenetricarboxylic acid BTB benzenetribenzoic acid MTB methanetetrabenzoic acid ATB adamantanotetrabenzoic acid ADB adamantanedibenzoic acid The additional metal-organic structure materials are MOF-2 to 4, MOF-9, MOF 31 to 36, MOF-39, MOF-69 to 80, MOF-103 to 106, MOF-122, MOF-125, MOF-150, MOF-177, MOF-178, MOF-235, MOF-236, MOF-500, MOF-501, MOF-502, MOF-505, IRMOF-1, IRMOF-61, IRMOP-13, IRMOP-51, MIL-17, MIL-45, MIL-47, MIL-53, MIL-59, MIL-60, MIL-61, MIL-63, MIL-68, MIL- 79, MIL-80, MIL-83, MIL-85, CPL-1 to 2, SZL-1 that are described in the literature. Particular preference is given to a porous metal-organic structure material in which Zn, Mg, Ca, Fe, Al, Ni or Cu is present as a metal ion and the organic compound of at least bidentate is terephthalic acid, isophthalic acid, , 6-naphthalenedicarboxylic acid or 1, 3,5-benzenetricarboxylic acid. In addition to the conventional method for producing metal-organic structure materials, as described, for example, in US 5,648,508, they can also be produced in an electrochemical manner. In this regard, reference is made to WO-A 2005/049892. The MOFs produced in this manner exhibit particularly good properties in connection with the adsorption and desorption of chemical substances, in particular gases. In this way, they differ from those that are conventionally produced, even when they are formed of the same organic and metal ion constituents. In the context of the present invention, MOFs produced electrochemically are particularly preferred. Accordingly, the electrochemical production refers to a crystalline porous metal-organic structure material comprising at least one organic compound, at least bidentate, linked by coordination of at least one metal ion, which at least one metal ion is produced in a reaction medium comprising the organic compound of at least bidentate by oxidation of at least one anode comprising the corresponding metal. The term "electrochemical production" refers to a production method in which the formation of at least one reaction product is associated with the migration of electric charges or the occurrence of electric potentials. The term "at least one metal ion", as used in connection with electrochemical production, designates embodiments according to at least one ion of a metal or at least one ion of a first metal and at least one ion of at least one a second metal different from the first metal is provided by anodic oxidation. Accordingly, electrochemical production comprises embodiments wherein at least one ion of at least one metal is provided by anodic oxidation and at least one ion of at least one metal is provided by a metal salt, the at least one metal in the metal salt and the at least one metal that is provided as a metal ion via anodic oxidation being able to be identical or different from one another. Therefore, the present invention, in relation to electrochemically produced MOFs comprises, for example, an embodiment according to which the reaction medium comprises one or more different salts of a metal and the metal ion present in this salt or in these salts is additionally provided by oxidation Anodic of at least one anode comprising this metal. Also, the reaction medium may comprise one or more different salts of at least one metal and at least one other metal of these metals may be provided via anodic oxidation as a metal ion in the reaction medium. According to a preferred embodiment of the present invention in connection with electrochemical production, the at least one metal ion is provided by anodic oxidation of at least one anode comprising this at least one metal, without providing additional metal via a metal salt. The term "metal", as used in the context of the present invention in connection with the electrochemical production of MOFs, comprises all the elements of the Periodic Table of the Elements that can be supplied via anodic oxidation in the electrochemical method in a medium of reaction and are capable with at least one organic compound of at least bidentate of forming at least one porous metal-organic structure material. The porous metal-organic structure material according to the present invention comprises, in its pores, a polymer that is suitable for adsorbing at least one substance that can also be absorbed by the porous metal-organic structure material.

Of course, the polymer that is at least partly absorbed in at least a portion of the pores of the structure material can be present not only in the pores. Instead, it may additionally be in contact with the structure material outside the pores, for example on its surface. In the context of the present invention, the term "polymer" is also used for polymer blends for reasons of simplicity. For example, at least in part, at least a portion of the pores of the structure material may comprise one or more polymers and / or a plurality of pores may have one or more identical or different polymers. Preferably, the pore volume that is given by the sums of the pore volumes of all the pores of the structure material is not completely occupied by the polymer. It is preferred that at least 5% by weight of at most 95% by weight of the maximum possible amount absorbed in the structure material of the polymer-forming monomer (s) be used in the polymerization. The maximum amount that can be absorbed can be determined by Fisher-Mottiau titration. If a plurality of monomers is used for the polymerization, the amount to be used is guided by the monomer whose maximum absorption capacity for the structure material is lower. More preferably, the amount is 10% by weight to 80% by weight, more preferably 20% by weight to 60% by weight, of the maximum amount that can be absorbed. In addition, there is a possibility, in particular when the monomer or monomers are present in liquid form, to first determine the maximum absorption of the monomer or monomers by the porous metal-organic structure material and subsequently add the desired proportion of this amount to the porous metal-organic structure material. The porous metal-organic structure material according to the present invention must be suitable for absorbing at least one substance, in which case the absorption can be further increased by a further adsorption of the at least one substance to the polymer, so that the porous metal-organic structure material in accordance with the present invention, in comparison with the porous metal-organic structure material as such from the prior art, can absorb a greater amount of the at least one substance. The at least one substance can be a gas or a liquid. Preferably, the substance is a gas. In the context of the present invention, for simplicity, the terms "gas" and "liquid" are used, but in this case, here, the term "gas" or "liquid" is also absorbed to mean gas mixtures and also mixtures of liquid or liquid solutions, respectively. Preferred gases are hydrogen, alkanes, in particular methane, ethane, propane, n-butane and also isobutane, carbon monoxide, carbon dioxide, nitrogen oxides, oxygen, sulfur oxides, halogens, noble gases, in particular helium, neon, argon, krypton and also xenon. Particular preference is given to energy sources such as hydrogen, natural gas, coal gas, methane, propane, butane.

However, the at least one substance can also be a liquid. Examples of said liquid are disinfectants, inorganic or organic solvents, motor fuels, in particular gasoline or diesel, hydraulic fluid, freezing fluid, brake fluid or an oil, in particular machine oil. In addition, the liquid may be halogenated aliphatic or aromatic, cyclic or acyclic hydrocarbons or mixtures thereof. In particular, the liquid may be acetone, acetonitrile, aniline, anisole, benzene, benzonitrile, bromobenzene, butanol, tert-butanol, quinoline, chlorobenzene, chloroform, cyclohexane, diethylene glycol, diethyl ether, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, dioxanes, glacial acetic acid, acetic anhydride, ethyl acetate, ethanol, ethylene carbonate, ethylene dichloride, ethylene glycol, ethylene glycol dimethyl ether, formamide, hexane, isopropanol, methanol, methoxypropanol, 3-methyl-1-butanol, methylene chloride, ethyl methyl ketone, N-methylformamide, N-methylpyrrolidone, nitrobenzene, nitromethane, piperidine, propanol , propylene carbonate, pyridine, carbon disulfide, sulfolane, tetrachloroethane, carbon tetrachloride, tetrahydrofuran, toluene, 1,1,1-trichloroethane, trichlorethylene, triethylamine, triethylene glycol, triglyme, water or mixtures thereof. In addition, the at least one substance can be an odor substance. Preferably, the odor substance is a volatile organic or inorganic compound comprising at least one of the elements nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine or iodine, or is an unsaturated or aromatic hydrocarbon or a saturated or unsaturated aldehyde or ketone. More preferred elements are nitrogen, oxygen, phosphorus, sulfur, chlorine, bromine; in particular preference is given to nitrogen, oxygen, phosphorus and sulfur. In particular, the odor substance is ammonia, hydrogen sulfide, sulfur oxides, nitrogen oxides, ozone, cyclic or acyclic amines, thiols, thioethers and also aldehydes, ketones, esters, ethers, acids or alcohols. Particular preference is given to ammonia, hydrogen sulphide, organic acids (preferably acetic acid, propionic acid, butyric acid, isobutyric acid, valoric acid, isovaleric acid, caproic acid, heptylic acid, lauric acid, perlargonic acid) and also cyclic hydrocarbons or acyclics comprising nitrogen or sulfide and also saturated or unsaturated aldehydes, such as hexanal, heptanal, octanol, nonanal, decanal, octenal or nonenal and, in particular, volatile aldehydes such as butyraldehyde, propionaldehyde, acetaldehyde and formaldehyde and in addition motor fuels such as gasoline, diesel (constituents). The odor substances may be fragrances that are used, for example, to produce perfumes. Fragrances or oils that release such fragrances that can be mentioned by way of example are: essential oils, basil oil, geranium oil, peppermint oil, cananga oil, cardamom acide, lavender oil, peppermint oil, oil of nutmeg, Camila oil, eucalyptus oil, rosemary oil, lime oil, lemon oil, orange oil, bergamot oil, amaro oil, coriander oil, cypress oil, 1, 1-dimethoxy-2-ferylethane , 2,4-dimethyl-4-phenyltetrahydrofuran, dimethyltetrahydro-benzaldehyde, 2,6-dimethyl-7-octen-2-ol, 1,2-diethoxy-3,7-dimethyl-2,6-octadiene, phenylacetaldehyde, oxide of rose, ethyl 2-methylpentanoate, 1- (2,6,6-trimethyl-1,3-cyclohexadien-1-yl) -2-buten-1-one, et i I-vanillin, 2,6-dimethyl -2-octenol, 3,7-dimethyl-2-octenol, cyclohexyl-tert-butyl acetate, anisyl acetates, allyl cyclohexyloxyacetate, ethylinalool, eugenol, coumarin, ethyl acetoacetate, 4-phenyl-2,4,6 -trimethyl-1,3-dioxane, 4-methylene-3,5,6,6-tetramethyl-2-heptanone, ethyl tetrahydrofuran, geranylnitrile, cis-3-hexen-1-ol, cis-3-hexenyl acetate , carbonates of cis-3-hexenyl methyl, 2,6-dimethyl-5-hepten-1-al, 4- (tricyclo [5.2.1.0] decylidene) -8-butanal, 5- (2,2,3-tri) -methyl-3-cyclopentenyl) -3- [5.2.1. 0] tricyclodecanocarboxylate, geraniol, citronellol, citral, linalool, linalyl acetate, ionones, phenylethanol or mixtures thereof. In the context of the present invention, a substance with a volatile odor preferably has a boiling point or boiling range of less than 300 ° C. More preferably, the odor substance is a highly volatile compound or mixture. Particularly preferably, the odor substance has a boiling point or boiling range less than 250 ° C, more preferably less than 230 ° C, particularly preferably less than 200 ° C. Also, preference is given to odor substances that have a high volatility. Vapor pressure can be used as an index of volatility. In the context of the present invention, a volatile odor substance preferably has a vapor pressure of more than 0.001 kPa (20 ° C). More preferably, the odor substance is a highly volatile compound or mixture. Particularly preferably, the odor substance has a vapor pressure of more than 0.01 kPa (20 ° C), more preferably a vapor pressure of more than 0.05 kPa (20 ° C). Particularly preferably, the odor substances have a vapor pressure of more than 0.1 kPa (20 ° C). The porous metal-organic structure material according to the present invention comprises a polymer which is also suitable for adsorbing the at least one substance. Preferably, the polymer comprises double bonds, very particularly preferably conjugated double bonds, and in particular aromatic rings and / or functional groups, such as ether, sulfide, amine, ester, amide, sulfamide, carbonate, urethane groups. The polymer is preferably an aromatic polymer and / or a polyamide and / or a polyester and / or a polyether and / or a polyacetal and / or a polycarbonate and / or a polyacrylate. Particular preference is given to polyesters. Preferred monomers which can form the polymer are vinylogous compounds, in particular vinyl compounds wherein the double vinyl bond is conjugated to additional conjugated double bonds of the monomer compound. Suitable monomers are styrene and also styrene derivatives, acrylates, butadiene, isoprene, acrylamide, acrylonitrile, vinyl acetate, vinyl ethers, esters of acrylic and / or methacrylic acid with alkanes having 1 to 12 carbon atoms, vinyl alcohols, vinyl halides, vinyl pyrrolidone, vinyl carbazole, divinyl formal or esters of vinyl and also unsaturated, if appropriate halogenated, hydrocarbons, such as isobutylene, butadiene, ethylene, propylene, tetrafluoroethylene. Also, cyclic or linear acétales can be used. The monomers can be used to produce homopolymers or copolymers. In addition, epoxides can be used as monomers, such as ethylene oxide, propylene oxide or butylene oxide. In addition, there is the possibility of selecting the monomers in such a way that they can undergo polycondensation. Said reaction can be carried out, for example, starting from diols and diacids, or diamines and diacids. Also, polyols and also polyacids, in particular polycarboxylic acids, can be used. Lactams and lactones such as caprolactam or caprolactone can also be used as polycondensation monomers, if appropriate in combination with other suitable bifunctional compounds. Preferably, the polymer is a styrene-based polymer.

In the context of the present invention, a styrene-based polymer is present when at least one monomer participating in the formation of the polymer is styrene or a styrene derivative. In the following, more polymers are listed that are suitable for absorbing the at least one substance.

Generally, polycarbonates can be used. The polycarbonates can be obtained by polycondensation of carbonic acid with diols or polyols. Suitable diols or polyols have already been listed above. In addition, polyoxymethylene copolymers can be used. Polyoxymethylene homopolymers or copolymers (POM) are known as such and are commercially available. They are commonly produced by polymerization of formaldehyde or, preferably, trioxane; in the production of copolymers, in addition, comonomers are co-used. Preferably, the monomers are selected from trioxane and other cyclic or linear formal or other sources of formaldehyde. Very generally, said POM polymers have at least 50 mol% repeating units -CH2O- in the main polymer chain. Suitable polyoxymethylene copolymers are in particular those which, in addition to the CH2O repeating units, comprise up to 50 mol%, preferably 0.01 to 20 mol%, in particular 0.1 to 10 mol%, and very particularly preferably 0.5 to 6 mol% of repeater units R1 to R4 independently of one another being an atom of hydrogen, a C1-C4 alkyl group or a halogen-substituted alkyl group having 1 to 4 carbon atoms and R5 being a -CH2-, -CH2O-, a methylene group substituted with C to C alkyl or C haloalkyl: to C4 or a corresponding oxymethylene group, and n having a value on the scale from 0 to 3. Advantageously, these groups can be introduced into the ring-opening copolymers of cyclic ethers. Preferred cyclic ethers are those of the formula R1 to R5 and n having the meanings given above. By way of example only, mention may be made of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,3-dioxane, 1,3-dioxolane. and 1,3-dioxepane (= butanediolformal, BUFO) as cyclic ethers, and also linear oligo- or polyformals such as polydioxolane or polydioxepane as comonomers. 1,3-Dioxolane and 1,3-dioxepane are particularly preferred comonomers. Also suitable are the oxymethylene terpolymers which are produced, for example, by reacting trioxane, one of the cyclic ethers described above, with a third monomer, preferably bifunctional compounds of the formula I Z being a chemical bond, -O-, -ORO- (R equals alkylene from Ci to C8 or cycloalkylene from C3 to C8). Preferred monomers of this type are eti, diglycidyl and formaldehyde ethers and diethers, dioxanes or trioxane in the molar ratio 2: 1, and also diethers of 2 mol of glycidyl compound and 1 mol of an aliphatic diol having 2 to 8 carbon atoms, for example, ethers of diglycidyl of ethylene glycol, 1,4-butanediol, 1,3-butanediol, cyclobutane-1,3-diol, 1,2-propanediol and cyclohexane-1,4-diol, to name a few examples. In general, polyesters based on dicarboxylic acids having an aromatic or aliphatic part or both an aliphatic and an aromatic part and an aliphatic or aromatic dihydroxy compound comprising an aliphatic part and an aromatic part can be used. Also, polyesters and polyalcohols can be used. In addition, monocarboxylic acids and monooles can be used. Likewise, hydroxycarboxylic acids can be used. Obviously, In addition to acids as a monomer, their derivatives, such as esters, anhydrides or halides, can also be used. Diols or polyols which may be mentioned by way of example are ethylene glycol, 1,2- and / or 1,3-propanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, 1,2- and / or 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, biphenol A, B, C, F, norbonylene glycol, 1,4-benzyldimethanol and or 1,4-benzyldiethanol, 2,4-dimethyl-2-ethylhexane-1,3-diol, cyclohexanedimethanol, dicidol, hexanediol, neopentyl glycol, trimethylolpropane, trimethylol ethane, 1,2,6-trihydroxyhexaerythritol, glycerol, trihydroxyethyl isocyanurate , pentaerythritol, sorbitol, xylitol, mannitol. Examples of di-, tri- and tetracarboxylic acids have already been described in connection with the structure of the structure material. In this case, mention is made in particular of 1,2-cyclohexanedicarboxylic acid, methyltetrahydrophthalic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, malonic acid, maleic acid, sebacic acid, dodecanedioic acid, acid Adipic acid, azeleic acid, pyromellitic acid, trimellitic acid, isononanoic acid, 2-ethylhexanoic acid. As a first group of preferred polyesters, mention may be made of polyalkylene terephthalates having, in particular, 2 to 10 carbon atoms in the alcohol moiety.

Said polyalkylene terephthalates are known per se and are described in the literature. In the main chain they may comprise an aromatic ring originating from the aromatic dicarboxylic acid. The aromatic ring can also be substituted, for example, by halogen such as chlorine and bromine, or by C?-C 4 alkyl groups such as methyl, ethyl, isopropyl or n-propyl groups, and n-butyl, isobutyl or t- butyl. These polyalkylene terephthalates can be produced by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds in a manner known per se. Preferred dicarboxylic acids that may be mentioned are 2,6-naphthalene dicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 30 mol%, preferably not more than 10 mol%, of the dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids. Of the aliphatic dihydroxy compounds, preference is given to diols having 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4- hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof. Preferred polyesters that may be mentioned are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 carbon atoms. Of these, in particular, preference is given to polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof. In addition, preference is given to PET and / or PBT comprising up to 1% by weight, preferably up to 0.75% by weight, of 1, 6-hexanediol and / or 2-methyl-1,5-pentanediol as additional monomer units. As another group, mention is made of fully aromatic polyesters which are derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds. Suitable aromatic dicarboxylic acids are the compounds already described for polyalkylene terephthalates. Preference is given to using mixtures of 5 to 100 mole% of isophthalic acid and 0 to 95 mole% of terephthalic acid, in particular mixtures of about 80% terephthalic acid with 20% softgel acid to approximately equivalent mixtures of these two acids . The aromatic dihydroxy compounds preferably have the general formula wherein Z is an alkylene or cycloalkylene group having up to 8 carbon atoms, an arylene group having up to 12 carbon atoms carbon, a carbonyl group, a sulfonyl group, an oxygen atom or sulfur atom or a chal bond and wherein m has the value 0 to 2. The compounds can also carry Ci-Cß or alkoxy and fluorine alkyl groups, chloro or bromine as substitutes in the phenylene groups. As the original bodies of these compounds, the following may be mentioned by way of example, dihydroxybiphenyl, di- (hydroxyphenyl) alkane, di- (hydroxyphenyl) cycloalkanes, di- (hydroxyphenyl) sulfide, di- (hydroxyphenyl) ether, di- ( hydroxyphenyl) ketone, di- (hydroxyphenyl) sulfoxide, alpha, alpha'-di- (hydroxyphenyl) dialkylbenzene, di- (hydroxyphenyl) sulfota, di- (hydroxybenzoyl) benzene, resorcinol and hydroquinone, and also their nuclear or halogenated alkylated derivatives nuclear Of these, preference is given to 4,4'-dihydroxybiphenyl, 2,4-di- (4'-hydroxyphenyl) -2-methylbutane, alpha, alpha'-di- (4-hydroxyphenyl) -p-diisopropyl-benzene, 2,2-di- (3'-methyl-4'-hydroxyphenyl) propane and 2,2-di- (3'-chloro-4'-hydroxyphenyl) propane, and also, in particular, 2,2-di- (4'-hydroxyphenyl) propane, 2,2-di- (3 ', 5-dichlorodihydroxyphenyl) propane, 1,1-di- (4' -hydroxyfe nyl) cyclohexane, 3,4'-dihydroxybenzophenone, 4 , 4'-dihydroxydiphenyl sulfota and 2,2-di- (3,5'-dimethyl-4'-hydroxy fe nil) pro cloth or mixtures thereof. Of course, mixtures of polyalkylene terephthalates and fully aromatic polyesters and / or polycarbonates can also be used. These generally comprise 20 to 98% by weight, preferably 80 to 96% by weight, of the polyalkylene terephthalate and 2 to 80% by weight, preferably 4 to 50% by weight, of the fully aromatic polyester and / or the polycarbonate. In addition, preferably halogen-free polycarbonates are used. Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula wherein Q is an individual bond, an alkylene group of CrC8, a C2-C3 alkylidene group, a C3-C6 cycloalkylidene group, a C6-C12 arylene group and also -O-, -S- or -SO2- and m is an integer from 0 to 2. Diphenols may also have substitutes such as CrC6 alkyl or alkoxy in the phenylene radicals. Preferred diphenols of the formula are, for example, hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 2,2-bi- (4-hydroxy-phen i) propane, 2,4-bi- (4-hydroxyphenyl) -2-methylbutane, 1,1-bi- (4-hydroxy-phenyl) cyclohexane. Particular preference is given to 2,2-bi- (4-hydroxyphenyl) propane and 1,1-bi- (4-hydroxyphenyl) cyclohexane, and also 1,1-bi- (4-hydroxyphenyl) -3,3,5 -trimethylcyclohexane. Both the homopolycarbonates and the copolycarbonates may be suitable, biphenol A-homopolymer is furthermore preferred to the copolycarbonates of biphenol A.

Suitable polycarbonates can be branched in a known manner, more precisely preferably by incorporation of 0.05 to 2.0 mole%, based on the total of the diphenols used, of at least trifunctional compounds, for example those having three or more than three phenolic OH groups. The diphenols of the general formula are known per se or can be produced by known methods. The polycarbonates can be produced, for example, by reacting the diphenols with phosgene by the phase-limit method or with phosgene by the method in a homogeneous phase (which is called the pyridine method), the molecular weight to be established in each case being achieved in a manner known per se by an appropriate amount of known chain terminators. (With respect to polycarbonates comprising polydiorganosiloxane, see DE-A 3334 782, for example). Suitable chain terminators are, for example, phenol, p-tert-butylphenol or else long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) phenol according to DE-A 28 42 005 or monoalkylphenols or dialkylphenols. having a total of 8 to 20 carbon atoms in the alkyl substitutes according to DE-A 35 06 472, such as p-nonylphenol, 3,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol , 2- (3,5-dimethylheptyl) phenol and 4- (3,5-dimethyl-heptyl) phenol. Halogen-free polycarbonates in the context of the present invention mean that polycarbonates are made from halogen-free diphenols, halogen-free chain terminators and, if appropriate, halogen-free branching points, the content of lower ppm chlorine quantities that can be converted into soap, resulting, for example, from the production of the polycarbonates used phosgene by the phase limit method, not being considered as comprising halogen within the meaning of the invention. Said polycarbonates having ppm contents of chlorine that can be converted to soap are halogen-free polycarbonates in the context of the present invention. Also mentioned as amorphous polyestercarbonates, phosgene, having been replaced in production by aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units. For further details reference can be made at this point to EP-A 711 810. More suitable polycarbonates having cycloalkyl radicals as monomer units are described in EP-A 365 916. In addition, biphenol A can be replaced by biphenol TMC. Vinylaromatic polymers are also suitable. Mention may be made here only as representative of vinylaromatic polymers of styrene, chlorostyrene, alpha-methylstyrene and p-methylstyrene; in addition, comonomers such as (meth) acrylonitrile or (meth) acrylic esters can also participate in the structure. The vinylaromatic polymers in particular Preferred are polystyrene and modified impact polystyrene. Of course, mixtures of these polymers can also be used. Preferably they are produced by the method described in EP-A 302 485. The preferred ASA polymers are made of a plasticized or rubberized phase from a graft polymer of: Ai 50 to 90% by weight of a graft substrate based in A, 95 to 99.9% by weight of a C2-C10 alkylacrylate and A12 0.1 to 5% by weight of a difunctional monomer having two olefinic non-conjugated double bonds and A210 to 50% by weight of a graft superstrate A21 20 to 50% by weight of styrene or substituted styrenes or mixtures thereof and A22 10 to 80% by weight of acrylonitrile, methacrylonitrile, acrylic esters or methacrylic esters or mixtures thereof, in a mixture with a hard matrix based on a SAN copolymer A3) of: A3? 50 to 90% by weight, preferably 55 to 90% by weight, and in particular 65 to 85% by weight, styrene and / or substituted styrenes and A32 10 to 50% by weight, preferably 10 to 45% by weight, and in particular 15 to 35% by weight, acrylonitrile and / or methacrylonitrile. For the production of the elastomer, as main monomer An), use is made of esters of acrylic acid having 2 to 10 carbon atoms, in particular 4 to 8 carbon atoms. As particularly preferred monomers, mention can be made herein of tert-butyl, isobutyl and n-butyl acrylate, and also 2-ethylhexyl acrylate, of which the last two mentioned are particularly preferred. In addition to these acrylic acid esters, use is made of 0.1 to 5% by weight, in particular 1 to 4% by weight, based on the total weight An + A12, of a polyfunctional monomer having at least two non-conjugated double bonds olefinic Of these, difunctional compounds are preferably used, ie, having two non-conjugated double bonds. Examples that may be mentioned herein are divinylbenzene, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate and dihydrodicyclopentadienyl acrylate, of which the last two mentioned are particularly preferred. The methods for producing the AT grafting substrate are known per se and are described, for example, in DE-B 12 60 135. In some cases, production by emulsion polymerization has proven to be particularly advantageous. The exact polymerization conditions, in particular type, measurement and amount of the emulsifier, are preferably selected in such a way that the acrylic ester latex which at least is partially entangled has an average particle size (average d50) on the scale of approximately 200 to 700, in particular from 250 to 600 nm. Preferably, the latex has a narrow particle size distribution, i.e., the quotient ^ • = • 4 l, e it is preferably less than 0.5, in particular less than 0.35. The fraction of the graft substrate AT to graft polymer AT + A2 is 50 to 90% by weight, preferably 55 to 85% by weight, and in particular 60 to 80% by weight, based on the total weight of AT + A2 . The graft substrate Ai is grafted with a graft cover A2 obtainable by copolymerization of A2? 20 to 90% by weight, preferably 30 to 90% by weight, and in particular 30 to 80% by weight, of styrene or substituted styrenes of the general formula R being alkyl radicals having 1 to 8 carbon atoms, hydrogen atoms or halogen atoms and R being alkyl radicals having 1 to 8 carbon atoms or halogen atoms and n having the value 0, 1, 2 or 3, and k22 10 to 80% by weight, preferably 10 to 70% by weight, and in particular 20 to 70% by weight, of acrylonitrile, methacrylonitrile, acrylic esters or methacrylic esters or mixtures thereof. Examples of substituted styrenes are alpha-methylstyrene, p-methylstyrene, p-chlorostyrene and p-chloro-alpha-methylstyrene, of which styrene and alpha-methylstyrene are preferred. Preferred acrylic and methacrylic esters are those whose homopolymers or copolymers with the other monomers of component A22) have glass transition temperatures of more than 20 ° C; however, in principle, other acrylic esters can also be used, preferably in quantities such that in total for the component A2 a transition temperature vitre Tg results above 20 ° C. Particular preference is given to esters of acrylic or methacrylic acid with C 1 -C 8 alcohols and epoxy containing esters such as glycidyl acrylate and glycidyl methacrylate. Particularly preferred examples that may be mentioned are methyl methacrylate, tert-butyl methacrylate, glycidyl methacrylate and n-butyl acrylate, the latter preferably being used in a not very large fraction due to its property of forming polymers having very low Tg. The cover of the graft A2) can be produced in one or more, for example two or three, process steps, thus the net composition remaining unaffected. Preferably, the graft cover is produced in emulsion, as described, for example, in DE-C 12 60 135, DE-A 32 27 555, DE-A 31 49357 and DE-A 34 14 118. Depending on the selected conditions, in the graft copolymerization a certain amount of form is formed. fraction of styrene-free copolymers or substituted (meth) acrylonitrile styrene derivatives or (meth) acrylic esters. The AT + A2 graft copolymer generally has an average particle size of 100 to 1000 nm, in particular of 200 to 700 nm, (heavy average d50). The conditions in production of the elastomer DT) and in grafting are therefore preferably selected in such a manner as to result in particle sizes in this range. Measures for this are known and described, for example, in DE-C 12 60 135 and DE-A 28 26 925, and also in Journal of Applied Polvmer Science, vol. 9 (1965), pp. 2929 to 2938. The particle size increase of the elastomer latex can be realized, for example, by agglomeration means. The graft polymer (AT + A2), in the context of this invention, also encompasses the free, non-grafted homo- and copolymers formed in the graft copolymerization to produce component A2). In the following, some preferred graft polymers can be listed: 1: 60% by weight of TA graft substrate of AT T 98% by weight of n-butyl acrylate and 2% by weight of dihydrodicyclopentadienyl acrylate and 40% by weight of graft cover A2 of A21 75% by weight of styrene and A22 25% by weight of acrylonitrile 2: graft substrate as in 1 having 5% by weight of a first graft cover of styrene and 35% by weight weight of a second grafting stage of A21 75% by weight of styrene and A22 25% by weight of acrylonitrile 3: grafting substrate as in 1 having 13% by weight of a first grafting stage and 27% by weight of a second grafting stage grafting stage of styrene and acrylonitrile in the weight ratio 3: 1. The products present as components A3) can be produced, for example, by the method described in DE-B 10 01 001 and DE-B 1003436. The ABS polymers exhibit the same structure as described above for ABS polymers. Instead of the acrylonitrile rubber A1) of the grafting substrate, in the ASA polymer, customary use is made of conjugated dienes, so that preferably the following composition results for the grafting substrate A4: A41 70 to 100% by weight of a conjugated diene and A 2 0 to 30% by weight of a difunctional monomer having two non-conjugated olefinic double bonds. The graft substrate A2 and the hard matrix of the SAN copolymer A3) remain unchanged in the composition. These products They are commercially available. The production methods are known to those skilled in the art, so additional statements on this matter are superfluous. The weight ratio of (A4 + A2): A3 is in the range of 3: 1 to 1: 3, preferably 2: 1 to 1: 2. Particularly preferred compositions of the inventive molding compounds comprise a mixture of: AT) 10 to 90% by weight of a polybutylene terephthalate A2) 0 to 40% by weight of a polyethylene terephthalate A3) 1 to 40% by weight of an ASA or ABS polymer or mixtures thereof Further preferred compositions of component A) comprise AT) 10 to 90% by weight of a polycarbonate A2) 0 to 40% by weight of a polyester, preferably polybutylene terephthalate, A3) 1 to 40 % by weight of a polymer of ASA or ABS or their mixtures.

In addition, polyamides may be suitable. Examples of these are polyamides which are derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycaprylolactam and polylaurolactam, and also polyamides which are obtained by reacting dicarboxylic acids with diamines. As the dicarboxylic acids, use can be made of alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms, and aromatic dicarboxylic acids. Here, as acids, mention may be made merely of adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic acid and / or isophthalic Suitable diamines are, in particular, alkanediamines having 6 to 12, in particular 6 to 8, carbon atoms, and also m-xylylenediamine, di- (4-aminophenyl) methane, di- (4-aminocyclohexyl) -methane, 2, 2-di- (4-aminophenyl) propane or 2,2-di- (4-aminocyclohexyl) -propane. Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and also copolyamides 6/66, in particular having a fraction from 5 to 95% by weight of caprolactam units. In addition, mention may also be made of polyamides which are obtainable, for example, by condensation of 1,4-diaminobutane with adipic acid at elevated temperature (nylon 4.6). The production methods for polyamides of this structure are described, for example, in EP-A 38094, EP-A 38582 and EP-A 39524. Furthermore, polyamides are suitable which are obtainable by copolymerization of two or more of the monomers before mentioned, or mixtures of a plurality of polyamides, the mixing ratio being optional. In addition, those partially aromatic copolyamides such as nylon 66 / 6T whose triamine content is less than 0.5% by weight, preferably less than 0.3% by weight have proved to be particularly advantageous (see EP-A 299444). In addition, polyphenylene ethers can be used which are known per se and are preferably produced by oxidizing coupling of o-disubstituted phenols. Examples of substitutes that may be mentioned are halogen atoms such as chlorine or chromium and alkyl radicals having 1 to 4 carbon atoms which preferably do not have a tertiary hydrogen atom in alpha position, for example, methyl, ethyl, propyl radicals or butyl. The alkyl radicals in turn can be replaced by halogen atoms such as chlorine or bromine or by a hydroxyl group. More possible substitute examples are alkoxy radicals, preferably having up to 4 carbon atoms, or if appropriate phenyl radicals substituted by halogen atoms and / or alkyl groups. Also suitable are copolymers of various phenols, for example, copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol. Of course, mixtures of different polyphenylene ethers can also be used. The polyphenylene ethers used, if appropriate, can comprise sites absent from the specific method, as described, for example, in White et al., Macromolecules 23, 1318-1329 (1990). Preferably, use is made of those polyphenylene ethers that are compatible with vinylaromatic polymers, ie, fully or substantially soluble in these polymers (see A. Noshay, Block Copolymers, pp. 8 to 10, Academic Press, 1977 and O. Olabisi , Polymer-Polymer Miscibility, 1979, pp. 117 to 189). Examples of polyphenylene ethers are poly (2,6-dilauryl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6- dimethoxy-1,4-phenylene), poly (2,6-diethoxy-1,4-phenylene) ether, poly (2-methoxy-6-ethoxy-1,4-phenylene) ether, poly (2-methoxy) ether -ethyl-6-stearyloxy-1,4-phenylene), poly (2,6-dichloro-1,4-phenylene) ether, poly (2-methyl-6-phenyl-1,4-phenylene) ether, poly (2,6-dibenzyl-1,4-phenylene) ether, poly (2-ethoxy-1,4-phenylene) ether, poly (2-chloro-1,4-phenylene) ether, poly ether (2,5-dibromo-1,4-phenylene). Preferably, use is made of polyphenylene ethers wherein the substitutes are alkyl radicals having 1 to 4 carbon atoms, such as poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-ether, 6-diethyl-1,4-phenylene), poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, ether of poly (2,6-dipropyl-1, 4-phenylene) and poly (2-ethyl-6-propyl-1,4-f in ether). In addition, polyphenylene ether graft copolymers and vinylaromatic polymers such as styrene, alpha-methylstyrene, vinyltoluene and chlorostyrene are suitable. The functionalized or modified polyphenylene ethers are known per se, for example, from WO-A 86/02086, WO-A 87/00540, EP-A 222 246, EP-A 223 116 and EP-A 254 048 and preferably used for blends with PA or polyester. Usually, an unmodified polyphenylene ether is modified by the incorporation of at least one carbonyl group, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic ester, carboxylate, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl, so that sufficient compatibility is ensured, for example, with the polyamide.

The modification is usually carried out by reacting an unmodified polyphenylene ether with a modifying agent comprising at least one of the aforementioned groups and at least one double CC bond or triple CC bond, in solution ( WO-A 86/2086), in aqueous dispersion, in a gas phase method (EP-A 25 200) or in the melt, if appropriate in the presence of suitable vinylaromatic polymers or impact modifiers, with it being optionally possible that free radical inhibitors are present. Suitable modifying agents are, for example, maleic acid, methylmaleic acid, itaconic acid, tetrahydrophthalic acid, their anhydrides and imides, fumaric acid, the monoethers and diesters of these acids, for example, of C.sub.2 and C.sub.2 -C8 alkanes, monoamines or diamides of these acids, such as N-phenylmaleimide, maleic hydrazine. In addition, mention may be made of, for example, N-vinylpyrrolidone and (meth) acryloylcaprolactam. Preferably, use is made of a modified polyphenylene ether obtainable by reacting T) 70 to 99.95% by weight, preferably 76.5 to 99.94% by weight, of an unmodified polyphenylene ether, a2) 0 to 25% by weight. weight, preferably 0 to 20% by weight, of a vinylaromatic polymer, a3) 0.05 to 5% by weight, preferably 0.05 to 2.5% by weight, of at least one compound from the group formed of a31) an alpha dicarbonyl compound .beta-unsaturated, a32) a monomer comprising amide having a polymerizable double bond and a32) a monomer comprising lactam having a polymerizable double bond, a) 0 to 5% by weight, preferably 0.01 to 0.09% by weight, of a free radical initiator, the percentages by weight are based on the sum of ai) to a4) in the course of 0.5 to 15 minutes at 240 to 375 ° C in suitable mixing and kneading units such as double screw extruders. The vinylaromatic polymer a2) should preferably be compatible with the polyphenylene ether used, as described under 2. Examples of preferred vinylaromatic polymers compatible with polyphenylene ethers should be taken from the aforementioned monograph by Olabisi, pp. 224 to 230 and 245. As free radical initiators a4), mention may be made of: Di- (2,4-dichlorobenzoyl) peroxide, tert-butyl peroxide, di- (3,5,5-trimethylhexanol) peroxide ), dilauroyl peroxide, didecanoyl peroxide, dipropionyl peroxide, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexoate, tert-butyl peroxydiethyl acetate, tert-butyl peroxyisobutyrate, peroxy-3,3,5-trimethyl- 1,1-di-tert-butyl cyclohexane, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxy-3,3,5-trimethylhexoate, tert-butyl peracetate butyl, tert-butyl perbenzoate, butyl 4,4-di-tert-butylperoxyvalerate, 2,2-di-tert-butylperoxybutane, dicumyl peroxide, tert-butyl-cumyl peroxide, 1,3-di- (ter- butylperoxyisopropyl) benzene and di-tert-butyl peroxide. Mention may also be made of organic hydroperoxides such as diisopropylbenzene monohydroperoxide, eumenohydroperoxide, tert-butyl hydroperoxide, p-methyl hydroperoxide and pinanohydroperoxide and also highly branched alkanes of the general structure C ^ R a R being alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, aryl groups such as phenyl, naphthyl or 5- or 6-membered heterocycles having an electron and nitrogen, oxygen or sulfur system as heteroatoms. Substitutes R1 to R6 may comprise functional groups as substitutes, such as carboxyl, carboxyl, hydroxyl, amino, thiol or epoxide groups. Examples are 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane and 2,2,3,3-tetraphenylbutane. Particularly preferred polyphenylene ethers are obtained by modification using maleic acid, maleic anhydride and acid fumaric Said polyphenylene ethers preferably have an acid number of 1.8 to 3.2, in particular 2.0 to 3.0. More suitable thermoplastics that may be mentioned are thermoplastic polyurethanes (TPU), as described, for example, in EP-A 115846 and EP-A 115 847 and also EP-A 117664. More suitable polymers that may be mentioned are polyolefins such as homopolymers or copolymers of polyethylene and / or polypropylene, and also polyketones, polyarylene ethers (so-called HT thermoplastics), in particular polyethersulfones, polyvinyl chlorides, poly (meth) acrylates and also mixtures of all the thermoplastics listed above. In addition, elastomers can be used, such as, for example, ethylene-propylene monomer (EPM) rubbers or ethylene-propylene-diene monomer (EPDM). EPM rubbers usually have almost no more double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms. The diene monomers for EPDM rubbers that may be mentioned are, for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1,4-diene, hexa-1,4. diene, hexa-1, 5-diene, 2,5-dimethylhexa-1, 5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene and also alkenylnorbornenes such as 5-ethylidene -2-norbornene and tricyclodienes such as 3- methyltrichloride (5.2. 1 .0.2.6) -3,8-decanediene and mixtures thereof. Preference is given to hexa-1,5-diene, 5-ethylidene norbornene and dicyclopentadiene. The diene content of the EPDM rubbers is preferably 0.5 to 50% by weight, in particular 1 to 8% by weight, based on the total weight of the rubber. The EPM and EPDM rubbers can also be grafted preferably to reactive carboxylic acids or their derivatives. Here, mention is made, for example, of acrylic acid, methacrylic acid and derivatives thereof, for example, glycidyl (meth) acrylate, and also maleic anhydride. Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids. In addition, the rubbers may comprise dicarboxylic acids such as maleic acid and fumaric acid, or derivatives of these acids, for example, esters and anhydrides, and / or monomers comprising epoxy. These dicarboxylic acid derivatives of monomers comprising dicarboxylic acid or comprising epoxy of the general formulas I or I I or I I I or IV to the monomer mixture ? i CHR¿: CR- - COO RT to R9 being hydrogen or alkyl groups having 1 to 6 carbon atoms and m being an integer from 0 to 20, g an integer from 0 to 10, and p an integer from 0 to 5. Preferably, the radicals R1 to R9 are hydrogen, m being 0 or 1, and g being 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether. Preferred compounds of formulas I, II and IV are maleic acid, maleic anhydride and esters comprising epoxy of acrylic acid and / or methacrylic acid such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as acrylate. t-butyl. Although the latter do not have free carboxyl groups, they resemble free acids in their behavior and are therefore called latent carboxyl group monomers.

Advantageously, the copolymers comprise 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers comprising epoxy and / or methacrylic acid and / or monomers comprising acid anhydride and also the remaining amount of esters (met) Acrylics Particular preference is given to copolymers of 50 to 98% by weight, in particular 55 to 95% by weight, ethylene, 0.1 to 40% by weight, in particular 0.3 to 20% by weight, glycidyl acrylate and / or glycidyl methacrylate , (meth) acrylic acid and / or maleic anhydride, and 1 to 45% by weight, in particular 10 to 40% by weight, n-butyl acrylate and / or 2-ethylhexyl acrylate. More preferred esters of acrylic acid and / or methacrylic acid are the esters of methyl, ethyl, propyl and isobutyl and t-butyl. In addition, vinyl esters and vinyl ethers can also be used as comonomers. The above-described ethylene copolymers can be produced by methods known per se, preferably random copolymerization at high pressure and elevated temperature. The corresponding methods are generally known. Preferred elastomers are also emulsion polymers whose production is described, for example, by Blackley in the monograph "Emulsion Polymerization". The emulsifiers and catalysts that can be used are known per se. In principle, it is possible to make use of homogenously structured elastomers, or else those having a framework structure. The framework structure is determined by the sequence of addition of the individual monomers; the morphology of the polymers is also affected by this addition sequence.

As monomers for the production of the rubber part of the elastomers, mention can be made here only as representative of acrylates, such as, for example, n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and also their mixtures. These monomers can be copolymerized with other monomers, for example, styrene, acrylonitrile, vinyl ethers and more acrylates or methacrylates such as methyl methacrylate, or methyl acrylate, ethyl acrylate and propyl acrylate. The plasticized or rubber phase (having a glass transition temperature of less than 0 ° C) of the elastomers can be the core, the outer shell or the central shell (in the case of elastomers having more than one shell structure); in the case of multi-frame elastomers, a plurality of frames may also comprise a rubber phase. If, in addition to the rubber phase, one or more hard components (having glass transition temperatures of more than 20 ° C) also participate in the structure of the elastomer, these are usually produced by polymerizing styrene, acrylonitrile, methacrylonitrile, alpha -methylstyrene, p-methylstyrene, acrylic esters and methacrylic esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as main monomers. In addition, smaller amounts of more comonomers can also be used here. In some cases it has turned out to be advantageous to use emulsion polymers having reactive groups on the surface. These groups they are, for example, epoxy, carboxyl, latent carboxyl, amino or amide groups, and also functional groups which can be introduced by co-use of monomers of the general formula the substitutes being able to have the following meaning: R10 hydrogen or an alkyl group of Ct-C, hydrogen R11, an alkyl group of Ct-C8 or an aryl group, in particular phenyl, hydrogen R12, a C1-C10 alkyl group , an aryl group of C6-Ct2 or -OR13 R13 an alkyl group of Ct-C8 or a C6-C12 aryl group which, if appropriate, can be replaced by groups comprising O or N, X a chemical bond, a alkylene group of Ct-C10 or arylene group of C6-C12 or And O-Z or N H-Z and Z an alkylene group of Ct-Ct or arylene group of C6-C12- The graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface. As additional examples, mention may also be made of acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid such as (N-tert-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-) acrylate. dimethylamine) methyl and (N, N-diethylamino) ethyl acrylate. In addition, the particles of the rubber phase can also be interlaced. The monomers which act as crosslinkers are, for example, buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and also the compounds described in EP-A 50 265. In addition, so-called linker monomers can also be used. grafting, ie, monomers having two or more polymerizable double bonds that react at different speeds during polymerization. Preferably, use is made of those compounds wherein at least one reactive group polymerizes at about the same rate as the remaining monomers, while the other reactive group (or reactive groups) polymerizes (polymerizes), eg, notoriously more slowly. The different polymerization rates are accompanied by a certain fraction of unsaturated double bonds in the rubber. If, later, another phase is grafted in said rubber, the double bonds present in the rubber react at least in part with the graft monomers forming chemical bonds, that is, the grafted phase is at least partly bound to the grafting substrate via chemical bonds. Examples of said graft-binding monomers are monomers comprising allyl, in particular allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate, or the compounds of corresponding monoalyl of these dicarboxylic acids. In addition, there are a multitude of more suitable graft linker monomers; for more details reference can be made here, for example, to the patent of E. U.A. No. 4 41 8 846. In general, the fraction of these corresponding monomers of the impact modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact modifying polymer. Then, some preferred emulsion polymers can be established. First, graft polymers having a core and at least one external shell having the following structure are mentioned here: Instead of graft polymers having a multi-scaffold structure, homogeneous elastomers, ie, a single shell, of buta-1, 3-diene, isoprene and n-butyl acrylate or their copolymers can also be used. These products they are also produced by co-use of interlacing monomers or monomers having reactive groups. Examples of preferred emulsion polymers are copolymers of n-butyl acrylate / (meth) acrylic acid, n-butyl acrylate / glycidyl acrylate or copolymers of n-butyl acrylate / glycidyl methacrylate, graft polymers having an inner core of n-butyl acrylate or butadiene-based acrylate and an outer shell of the aforementioned copolymers, and ethylene copolymers with comonomers giving reactive groups. The described elastomers can also be produced by other usual methods, for example, by suspension polymerization. Also preferred are silicone rubbers, as described in DE-A 3725576, EP-A 235690, DE-A 3800603, EP-A 319290. It will be appreciated that mixtures of the rubber types stated above can also be used. In addition, in the polymer formation, fillers and additives can also be used. Suitable additives are known to those skilled in the art. Examples of these are described in Hans Zweifel, Plastics Additives Handbook, 5th edition 2001, Cari Hanser Verlag. Suitable fillers are known to those skilled in the art. Examples of these are described in Katz, Harry S .; Milewski, John V. [Ed.], Handbook of Fillers for Plastics, 1987, Kluwer Academic Publishers Group. The present invention also relates to a method for producing the inventive porous metal-organic structure material comprising the steps: preparing a porous metal-organic structure material that can absorb at least one substance comprising at least one compound of at least bidentate bound by coordination to at least one ion metal; contacting the metal-organic structure material with at least one monomer that is suitable for forming a polymer that can adsorb the at least one substance; - converting the at least one monomer into the polymer. As already stated above, the polymer can be made into a single monomer or different monomers. To ensure the formation of the polymer in the pores of the metal-organic structure material, the monomer or monomers from which the polymer is formed must first make contact with the metal-organic structure material. This can proceed, for example, by simple combination of monomer, or monomers, and structure material. In order to achieve homogenous distribution of the monomers or of the monomer in the metal-organic structure material, the contact preferably proceeds with stirring, kneading or vortexing, which can be achieved, for example, by using, if appropriate, an inert gas jet. . In this case, the monomers are preferably present as pure substances. However, diluted in a preferably inert solvent may also be present. Through of the dilution, if appropriate, the fraction of the pore volume that must be occupied by the polymer can be pre-adjusted, however, it is a particular advantage in this case if the solvent is selected in such a way that it has low adsorption to the porous metal-organic structure material in this manner so as not to damage the absorption of the monomer or the monomers by the metal-organic structure material. Preferably, as a solvent, an initiator can be used for the polymer reaction. The monomer or monomers, however, can also be contacted in the gaseous state with the porous metal-organic structure material. This can occur at atmospheric pressure or in a gas atmosphere that is supersaturated with monomer. For example, it is conceivable, for example, to expose the pulverulent metal-organic structure material in a pressure chamber to a supersaturated gas atmosphere with monomers in such a manner that the metal-organic structure material is stirred, for example, stir, in this gas atmosphere, or by the metal-organic structure material being introduced from above into the pressure chamber, falling through the gas space, absorbing the monomer or monomers and subsequently being removed from the pressure chamber . The structure materials can also be contacted first with the gaseous monomers or the gaseous monomer in a pressure chamber, subsequently with a pressure rise or a temperature reduction proceeding, so that the monomer is condensed, or the monomers are condensed, and thus contacting the metal-organic structure material being ensured. For example, a pressure jump can proceed by the volume of the pressure chamber being compressed or by the gaseous monomer or monomers being forced into the pressure chamber or by an inert foreign gas being forced into the pressure chamber. Another possibility is to contact the monomer or monomers in liquid or in solution form with the metal-organic structure material and subsequently, when reducing the ambient pressure, remove non-adsorbent monomers and, if appropriate, the solvent, from the metal-organic structure material. . By the use of solvents, solid monomers at room temperature can also be contacted with the metal-organic structure material in a suitable manner. Finally, the monomers or the monomer can be contacted with the metal-organic structure material in solid form, for example in powder form, by simple mixing, and then they can be melted, which preferably proceeds by mixing for example by stirring, kneading, extrusion or with vortex. The absorption of the monomer, or monomers, may proceed batchwise or continuously. Since energy is released in the absorption of the monomers by the metal-organic structure material, the fraction of the pore volume that is then occupied by the polymer can be controlled via the temperature. A low temperature can be advantageous in order to perform the absorption of the monomers in the pores of the metal-organic structure material quickly and in a high amount. However, a higher temperature can also be advantageous if, for example, the polymerization must be initiated immediately after the absorption of the monomers because of the higher temperature. To allow conversion of the at least one monomer to the polymer, it is first required to initiate the polymerization. In this case, the initiation of the polymerization must be matched to the monomers to be used. The initiation step is preferably selected in such a way that no substances are required for this. Said initiation may proceed, if appropriate, by thermal effect or by radiation. The monomers can be polymerized, for example, by means of free radical or ionically or by polycondensation or polyaddition. In particular, preference is given to thermally polymerizable monomers, very particularly preferably, polymer formation is allowed by thermal self-polymerization. From the group of monomers described in more detail above, for thermal auto-polymerization, styrene, divinylbenzene and methyl methacrylate are particularly suitable. If a volatile compound is formed in the polymerization, it is preferably removed from the inventive porous metal-organic structure material by pressure reduction. This can increase production. This procedure is advantageous, particularly in polycondensations. The inventive porous metal-organic structure material present after conversion of the at least one monomer into the polymer may be present in powder form or in crystalline form. The inventive structure material can be used as such or converted into a formed body. The preferred methods in this case are strand extrusion or tablet formation. In the production of formed body, the material of inventive structure may have more materials, for example, binders, lubricants or other additives, which are added during production. Also, it is conceivable that the inventive structure material has more constituents, such as, for example, adsorbents such as activated carbon or the like. With respect to the possible geometries of the inventive porous metal-organic structure material, there are essentially no illustrations. For example, tablets should be mentioned, among other things, such as, for example, disc-shaped tablets, pills, beads, granules, extruded, for example, strands, honeycombs, meshes or hollow bodies. For the production of these shaped bodies, in principle all suitable methods are possible. In particular, the following methods are preferred: Knead the structure material alone or together with at least one binder and / or at least one bonding agent and / or at least one template compound to obtain a mixture; form the resulting mixture by means of at least one suitable method, such as, for example, extrusion; optionally washing and / or drying and / or calcination of the extrudate; optionally final processing. - Apply the structure material to at least one support material if appropriate. The resulting material can then be further processed according to the method described above to give a formed body. Apply the structure material to at least one porous substrate if appropriate. The kneading and forming can proceed according to any suitable method, such as, for example, as described in Ullmanns Enzykiopádie der Technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], 4th edition, volume 2, pp. 313 ff. (1972). For example, the kneading and / or forming can proceed by means of a piston press, roll press in the presence or absence of at least one binder material, compounding, tabletting, tabletting, extrusion, co-extrusion foaming, spinning, coating, granulation, preferably spray granulation, spraying, spray drying or a combination of two or more of these methods. Very particularly, tablets and / or tablets are produced. The kneading and / or training can proceed at temperature high, such as, for example, in the range of ambient temperature to 300 ° C and / or at elevated pressure, such as, for example, in the scale of atmospheric pressure up to several hundred bar and / or in a protective gas atmosphere such as, for example, in the presence of at least one noble gas, nitrogen, or a mixture of two or more thereof. The kneading and / or forming is carried out according to a further embodiment with the addition of at least one binder, as aginder, in principle, any chemical compound being capable of being used which ensures the desired viscosity for kneading and / or forming the compound to be kneaded and / or formed. Accordingly, binders in the context of the present invention can not only be compounds that increase viscosity, but also decrease viscosity. The binders to be mentioned, inter alia, as preferred are, for example, aluminum oxide or binders comprising aluminum oxide, as described, for example, in WO 94/29408, silicon dioxide, as described, for example. , in EP 0 592 050 A1, mixtures of silicon dioxide or aluminum oxide, as described, for example, in WO 94/13584, clay minerals, as described, for example, in JP 03-0371 56 A, for example montmorillonite, caoiin, bentonite, haloisite, dichita, nacrite and anauxite, alkoxysilanes, such as, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or, for example, trialkoxysilanes, such as, for example, trimethoxysilane, triethoxysilane, tripropoxylysilane, tributoxysilane, alkoxytitanates, for example, tetraalkoxytitanates, such as, for example, tetramethoxytitanate, tetraethoxytitanate, tetrapropoxytitanate, tetrabutoxytitanate, or, for example, trialkoxytitanates, such as, for example, trimethoxytitanate, triethoxytitanate, tripropoxytitanate, tributoxytitanate, alkoxy zirconates, for example, tetraalkoxy zirconates, such as, for example, tetramethoxy zirconate, tetraethoxy zirconate, tetrapropoxy zirconate, tetrabutoxizirconate, or, for example, trialkoxy zirconates, such as, for example, trimethoxy zirconate, triethoxy zirconate, tripropoxy zirconate, tributoxizirconate, silica sols, amphiphilic substances and / or graphites. In particular, preference is given to graphite. As the viscosity-increasing compound, it can also be used, for example, if appropriate, in addition to the aforementioned compounds, an organic compound and / or a hydrophilic polymer, such as, for example, cellulose or a cellulose derivative , such as, for example, methylcellulose 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. As the bonding agent, it is preferably possible to use, inter alia, water or at least one alcohol, such as, for example, a monoalcohol having 1 to 4 carbon atoms, such as, for example, methanol, ethanol, -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 said alcohols or an alcohol polyhydric, such as, for example, a glycol, preferably a water-miscible polyhydric alcohol, alone or as a mixture with water and / or at least one of said monohydric alcohols. More additives that can be used for kneading and / or forming are, inter alia, amines or amine derivatives such as, for example, tetraalkylammonium compounds or amino alcohols and carbonate-comprising compounds such as, for example, carbonate calcium. Such additional additives are described, for example, in EP 0 389 041 A1, EP 0 200 260 A1 or WO 95/19222. The sequence of additives such as template compound, binder, sticking agent, substance that increases viscosity during forming and kneading is not fundamentally critical. According to another preferred embodiment, the formed body obtained from kneading and / or forming is subjected to at least one drying which is generally carried out at a temperature in the range of 25 to 300 ° C, preferably on the scale from 50 to 300 ° C, and particularly preferably in the range from 100 to 300 ° C. It is also possible to dry under vacuum or under a protective gas atmosphere or by spray drying. According to a particularly preferred embodiment, in the context of this drying operation, at least one of the compounds added as an additive is at least partly removed from the formed body. The present invention also relates to a method for absorbing at least one substance comprising the step contacting the at least one substance with a structure material in accordance with the present invention. As already stated before, the at least one substance can be a gas or a liquid. Preferably, it is a gas, in particular hydrogen. The present invention further relates to the use of a material of inventive structure to absorb at least one substance for storage, separation, controlled release or chemical reaction. If the substance serves for storage, it is suitably contacted in pure form with the material of inventive structure, so that it can be absorbed by the metal-organic structure material and also the polymer. If at least one substance is absorbed for separation, the substance to be absorbed, before absorption, is present in a composition of matter. This composition of matter is also preferably a gas. Those that can be mentioned here are, for example: natural gas, biogas, exhaust gases, air, exhaust air or inert gas. If the absorption of the at least one substance serves for controlled release, the substance is preferably a fragrance, as already described above, or is an active substance or substance that must be released in a delayed manner. Also, the storage of the at least one substance it can serve for later controlled release. In this case, usually, a system is used where the storage, in particular of the gas component, proceeds by pressure increase. In this case, the system can be a pressure vessel comprising, for example, the material of inventive structure. In this case, the controlled release can proceed via valve devices. The absorption of the at least one substance can also serve for the chemical reaction of this substance. In this case, in particular, chemical reactions should be considered as being able to proceed under heterogeneous catalysis. Examples of said reactions are hydrogenation by means of hydrogen, for example, hydrogen being first absorbed in the material of inventive structure. Another example of such a reaction is alkoxylation, as described, for example, in WO-A 03/035717. The invention will be described in more detail with reference to the examples below.

EXAMPLES Example 1 Self-polymerization of free radical A solution of 23.75 g of styrene and 1.25 g of divinylbenzene is intimately mixed at room temperature and atmospheric pressure with 1 00 g of pulverulent MOF-5. The mixture is subsequently charged at atmospheric pressure in a stainless steel pump (volume = 100 ml), the stainless steel pump is sealed and heated to 140 ° C in an oil bath for 10 hours to obtain the inventive structure material.

Example 2 Polycondensation with two monomers A mixture of 2.11 g of dimethyl malonate and 2.18 g of xylylenediamine is intimately mixed with 20 g of MOF (Zn-MOF-5) at room temperature and atmospheric pressure. The mixture is subsequently stored under inert gas (nitrogen) for 2 hours at 250 ° C. The initial pressure is 10 bar, in the course of heating the pressure rises. At a pressure of 18 bar, by careful expansion, a pressure of 16 bar is established. After the expiration of 2 hours, the sample is cooled overnight.

Example 3 Polycondensation with two monomers A mixture of 5.77 g of dimethyl malonate and 2.99 g of ethylene glycol is intimately mixed with 50 g of MOF (Zn-MOF-5) at room temperature and at atmospheric pressure. The mixture is first stored at 200 ° C under ambient pressure under inert gas (nitrogen) for 70 minutes, then the pressure is reduced to 1 mbar for an additional 140 minutes.

Example 4 Polycondensation with initiator and a monomer A mixture of 15 g of caprolactam and 50 g of MOF (Zn-MOF- ) is intimately mixed at a temperature of 90 ° C. The mixture is cooled and mixed intimately with a few drops of water. The resulting mixture is stored at 270 ° C for 2 hours under inert gas (nitrogen). The initial pressure of the inert gas is 16 bar, in the course of heating the pressure increases. At a pressure of 20 bar, by careful expansion, a pressure of 19 bar is established. Subsequently, in the course of 1.5 hours, the pressure is reduced to atmospheric pressure and the sample treated with nitrogen gas for an additional hour. The sample cools during the night.

Example 5 H? Isotherms at 77 and 87 K For the metal-organic structure material that was produced in Example 3 and, in its pores, comprises at least in part a polyester, the isothermal H2 were determined at 77 K and 87 K and compared with those of pure metal-organic structure material (Zn-MOF-5). Figure 1 a shows the isotherms H2 of the structure material Zn-MOF-5 (MOF 5) known from the prior art and Figure 1 b for the material of inventive structure. The upper curve in each case corresponds to the determination at 77 K. The lower curve in each case was measured at 87 K. In Figure 2, the curves of Figures 1 a and 1 b are once again collected. a 77K MOF-5 + polyester at 87K MOF-5 + polyester at 77K MOF-5 at 87 K MOF-5 After the calculation via a Clausius-Clapeyron proposal, the following heat absorption results for hydrogen from the isotherms at 77K and 87K: -Zn-MOF5: 3.6 kJ / mol -modified with polyester: 6.6 kJ / mol These results show a markedly increased binding of H2 to the polyester-modified metal-organic structure material. In this way, it is possible to store hydrogen at a higher temperature compared to the prior art. This also shows the comparison with the evaporation heat recorded in the liquid hydrogen literature (0.9 kJ / mol).

EXAMPLE 6 Auto-polymerization of free radical A solution of X g of styrene and Y g of methyl methacrylate is intimately mixed at room temperature and under atmospheric pressure with 20 g of pulverulent Zn MOF-5. The mixture is subsequently polymerized in an autoclave under nitrogen (13 bar) at a temperature of 125 ° C in the course of 4 hours. hours.

Figure 3 shows the H2 isotherms of the experiments 6a-d each measured at 77K. In Figure 4, the curves of Figure 3 and Figure 1a are combined once again, here the Zn-MOF5 measured at 77K is shown as a continuous black line. The results show a significantly higher water absorption of the polymer-modified metal-organic structure materials in the low pressure scale. This applies in particular to experiments 6a and 6c (circular symbols), to say the smallest amounts of monomer.

Example 7 Mix material of metal-organic structure and polystyrene A solution of 10 g of polystyrene (MVR = 9.5 ml / 10 min, measured at 200 ° C / 5 kg) in 40 g of dichloromethane is intimately mixed with 50 g of Zn MOF -5 powdery in an atmosphere of nitrogen at room temperature and atmospheric pressure. The mixture is subsequently maintained for 48 hours in the nitrogen atmosphere, so that solvent residues can evaporate. In figure 5, the isotherms H2 measured at 77K of the mixture are plotted (- • -); Zn-MOF5 is shown as a solid black line. The results show a significantly higher water absorption of polymer-modified metal-organic structure materials.

Example 8 Mixture of MOF and polystyrene A solution of X g of styrene is intimately mixed with 5 g of pulverulent Zn MOF-5 under a nitrogen atmosphere at room temperature and at atmospheric pressure. The mixture is subsequently loaded in an autoclave (volume = 100 ml) under inert gas, nitrogen is forced at 10 bar, and the closed autoclave is heated for 10 hours at 125 ° C in order to obtain the structure material according to the invention. In Figure 6, the isotherms H2 measured at 77K of the mixture are plotted; the reference structure material is shown as a continuous black line.

The results show a significantly higher water absorption of polymer-modified metal-organic structure materials.

Claims (10)

REIVI NDICAC ION ES

1 .- A porous metal-organic structure material for absorbing at least one substance, the structure material comprising at least one organic compound of at least bidentate bound by coordination to at least one metal ion, and the structure material having at least in part pores comprising a polymer that is suitable for adsorbing the at least one substance.

2. The structure material according to claim 1, wherein the structure material comprises Mg, Ca, Fe, Zn, Al, Ni or Cu as the metal ion and the organic compound of at least bidentate is terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid or 1, 3, 5-benzenetricarboxylic acid.

3. The structure material according to claim 1 or 2, wherein at least 5% by weight and at most 95% by weight of the maximum possible amount absorbed in the structure material of the monomer (s) is used. polymer former

4. The structure material according to one of claims 1 to 3, wherein the at least one substance is a gas, preferably hydrogen.

5. - The structure material according to one of claims 1 to 4, wherein the polymer is an aromatic polymer and / or a polyamide and / or a polyester and / or a polyether and / or a polyacetal and / or a polycarbonate and / or a polyacrylate.

6. - The structure material according to claim 5, wherein the polymer is a styrene-based polymer.

7. A method for producing a structure material according to one of claims 1 to 6, comprising the steps preparing a porous metal-organic structure material that can absorb at least one substance comprising at least one compound of at least bidentate linked by coordination to at least one metal ion; contacting the metal-organic structure material with at least one monomer that is suitable to form a polymer that can adsorb the at least one substance; - converting the at least one monomer into the polymer.

8. A method for absorbing at least one substance comprising the step contacting the at least one substance with a structure material according to one of claims 1 to 6.

9. The method according to claim 8, in wherein the at least one substance is a source of energy, preferably a gas selected from hydrogen, natural gas, municipal gas, methane, propane or butane.

10. The use of a structure material according to one of claims 1 to 6 to absorb at least one substance for storage, separation, controlled release or chemical reaction.