EP2117700A1

EP2117700A1 - Use of porous organometallic skeleton materials for colored identification of filters

Info

Publication number: EP2117700A1
Application number: EP07857677A
Authority: EP
Inventors: Markus Schubert; Ulrich Müller; Christoph Kiener; Marcus Guzmann; Jürgen HUFF; Jörg PASTRE
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-12-27
Filing date: 2007-12-17
Publication date: 2009-11-18
Also published as: US8563464B2; DE102006061587A1; US20100331176A1; WO2008080813A1

Abstract

The present invention relates to the use of a porous organometallic skeleton material comprising at least one at least bidentate organic compound bound coordinatively to at least one metal ion, wherein the at least one metal ion, the at least one at least bidentate organic compound or, if present, a further component is a coloring component, as an adsorbent and for permanent colored identification of a filter.

Description

Use of porous organometallic frameworks for color coding of filters

description

The present invention relates to the use of a porous organometallic framework material for permanent color coding of a filter.

Filters play an important role in daily life as well as in industrial processes.

In this case, filters are often only a part of devices, housings or the like. Typically, the filters are media for cleaning air or exhaust air. In the process, the substances contained in the air or exhaust air which are to be filtered out are brought into contact with the filter, the substances being adsorbed accordingly.

These substances can be a wide variety of substances. Naturally of special interest here are pollutants and odors.

The filters themselves contain a corresponding adsorption material which has the property of adsorption of the substance to be filtered out. Common adsorbents are activated carbon or zeolites.

The porous organometallic framework materials known in the prior art are also suitable as adsorbents. In WO-A 2006/122920, for example, the separation of odors from gases is described, organometallic frameworks are used as sorbent.

Frequently it is necessary to color filter to avoid swapping filters, highlighting their presence or even adapting them to the color scheme of the environment, such as a housing.

Typically, only components of the filter or housing are used, wherein it is avoided to color-code the sorbent itself, in order to avoid that the adsorption properties of the sorbent is affected by the color coding. This approach limits the ability to color-filter filters. Therefore, there is a need to provide alternative applications that allow the color coding of filters.

An object of the present invention is thus to provide such alternative Kenn-drawing possibilities.

The object is achieved by the use of a porous organometallic framework material comprising at least one coordinating at least one metal ion bound at least bidentate organic compound, wherein the at least one metal ion, the at least one at least bidentate organic compound or optionally a further component is a coloring component, as Sorbent and for permanent color coding of a filter.

In fact, it has been found that porous organometallic frameworks can be used as sorbents in a filter, these also serving for color identification. It has been found that the adsorptive property of the framework material is not or not significantly adversely affected.

The porous organometallic framework material for the use according to the invention contains at least one at least one metal ion coordinated, at least bidentate organic compound.

Such organometallic frameworks (MOF) are known in the art and are described, for example, in US Pat. No. 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 et al., Topics in Catalysis 9 (1999), pages 105 to 11, Chen et al., Science 29J (2001), pp. 1021 to 1023 and DE-A-101 1 1 230.

The organometallic frameworks according to the present invention contain pores, in particular micro and / or mesopores. Micropores are defined as those having a diameter of 2 nm or smaller and mesopores are defined by a diameter in the range of 2 to 50 nm, each according to the definition as described by Pure & Applied Chem. 57 (1983), 603-619, in particular on page 606. The presence of micro- and / or mesopores can be checked by means of sorption measurements, these measurements determining the MOF's absorption capacity for nitrogen at 77 Kelvin according to DIN 66131 and / or DIN 66134.

Preferably, the specific surface area - calculated according to the Langmuir model (DIN 66131, 66134) for a MOF in powder form is more than 5 m ² / g, more preferably more than 10 m ² / g, more preferably more than 50 m ² / g , more preferably more as 500 m ² / g, more preferably more than 1000 m ² / g and particularly preferably more than 1500 m ² / g.

Shaped bodies containing organometallic frameworks may have a lower active surface area; but preferably more than 10 m ² / g, more preferably more than 50 m ² / g, even more preferably more than 500 m ² / g.

The metal component in the framework of the present invention is preferably selected from Groups Ia, IIa, IIIa, IVa to Villa and Ib to VIb. Particularly preferred are Mg, Ca, Sr, Ba, Sc, Y, Ln, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir , Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi, where Ln is lanthanides. Lanthanides are La, Ce, Pr, Nd, Pn, Sm, En, Gd, Subrange, Dy, Ho, Er, Tm, Yb. With respect to the ions of these elements, mention should particularly be made of Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ln ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ⁴⁺ , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ³⁺ , Re ²⁺ , Fe ³⁺ , Fe ²⁺ , Ru ³⁺ , Ru ²⁺ , Os ³⁺ , Os ²⁺ , Co ³⁺ , Co ²⁺ , Rh ²⁺ , Rh ⁺ , Ir ²⁺ , Ir ⁺ , Ni ²⁺ , Ni ⁺ , Pd ²⁺ , Pd ⁺ , Pt ²⁺ , Pt ⁺ , Cu ²⁺ , Cu ⁺ , Ag ⁺ , Au ⁺ , Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Si ⁴⁺ , Si ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Pb ⁴⁺ , Pb ²⁺ , As ⁵⁺ , As ³⁺ , As ⁺ , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ and Bi ⁺ .

More preferred metals are Zn, Cu, Al, V, Mn, Ln, Y, Sc, Mg. Zr, Ti, Fe, Co, Ni, In, Ga, Ca. Further more preferred are Al, Zn, Cu, Zr.

The term "at least bidentate organic compound" refers to an organic compound containing at least one functional group capable of having at least two coordinative bonds to a given metal ion, and / or to two or more, preferably two, metal atoms each having a coordinative bond train.

Examples of functional groups which can be used to form the abovementioned coordinative bonds are, for example, the following functional groups: -CO ₂ H, -CS ₂ H, -NO ₂ , -B (OH) ₂ , -SO ₃ H, - Si (OH) ₃ , -Ge (OH) ₃ , -Sn (OH) ₃ , -Si (SH) ₄ , -Ge (SH) ₄ , -Sn (SH) ₃ , -PO ₃ H, -AsO ₃ H , -AsO ₄ H, -P (SH) ₃ , -As (SH) ₃ , -CH (RSH) ₂ , -C (RSH) ₃ -CH (RNH ₂ ) ₂ -C (RNH ₂ ) ₃ , -CH (ROH) ₂ , -C (ROH) ₃ , -CH (RCN) ₂ , -C (RCN) ₃ where, for example, R preferably represents 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 an aryl group containing 1 or 2 aromatic nuclei such as 2 C ₆ rings, the may optionally be condensed and may be independently substituted with at least one substituent, and / or independently of each other at least one heteroatom wie beispielsw may contain N, O and / or S. According to likewise preferred embodiments, functional groups are to be mentioned where the above R is not present. In this regard, inter alia, -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 To name.

The at least two functional groups can in principle be bound to any suitable organic compound, as long as it is ensured that the organic compound containing these functional groups is capable of forming the coordinate bond and for preparing the framework material.

Preferably, the organic compounds containing the at least two functional groups are derived from a saturated or unsaturated aliphatic compound or an aromatic compound or an aliphatic as well as an aromatic compound.

The aliphatic compound or the aliphatic portion of the both aliphatic and aromatic compound may be linear and / or branched and / or cyclic, wherein also several cycles per compound are possible. More preferably, the aliphatic compound or the aliphatic portion of the both aliphatic and aromatic compound contains 1 to 15, more preferably 1 to 14, further preferably 1 to 13, further preferably 1 to 12, further preferably 1 to 11 and particularly preferably 1 to 10 C atoms such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 C atoms. Methane, adamantane, acetylene, ethylene or butadiene are particularly preferred in this case.

The aromatic compound or the aromatic part of both aromatic and aliphatic compound may have one or more cores, such as two, three, four or five cores, wherein the cores may be separated from each other and / or at least two nuclei in condensed form. Most preferably, the aromatic compound or the aromatic moiety of the both aliphatic and aromatic compounds has one, two or three nuclei, with one or two nuclei being particularly preferred. Independently of each other, furthermore, each nucleus of the named compound may contain at least one heteroatom, such as, for example, N, O, S, B, P, Si, Al, preferably N, O and / or S. More preferably, the aromatic compound or the aromatic part of both the aromatic and aliphatic compound contains one or two Cβ cores, the two being present either separately or in condensed form. In particular, benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl may be mentioned as aromatic compounds.

More preferably, the at least bidentate organic compound, an aliphatic or aromatic, acyclic or cyclic hydrocarbon having 1 to 18, preferably 1 to 10 and in particular 6 carbon atoms, which additionally has only 2, 3 or 4 carboxyl groups as functional groups.

For example, the at least bidentate organic compound is derived from a dicarboxylic acid, such as oxalic, succinic, tartaric, 1,4-butanedicarboxylic, 1,4-butenedicarboxylic, 4-oxo-pyran-2,6-dicarboxylic, 1 , 6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1, 9-heptanecanedicarboxylic acid, heptadecane dicarboxylic acid, acetylenedicarboxylic acid, 1, 2-benzenedicarboxylic acid, 1, 3-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3 - dicarboxylic acid, 1, 3-butadiene-1, 4-dicarboxylic acid, 1, 4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2 , 4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro 4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dic arbonic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylenedicarboxylic acid, pluriol E 200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3, 5-cyclohexadiene-1,2-dicarboxylic acid, octadicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3, 3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis (phenylamino) benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyldicarboxylic acid, 7-chloro-8-methylquinoline-2 , 3-dicarboxylic acid, 1 -anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis (carboxymethyl) -piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1 - (4-carboxy) -phenyl-3- (4-chloro) -phenyl-pyrazoline-4,5-dicarboxylic acid, 1, 4,5,6,7,7, -hexa-chloro-5-norbornene-2,3 dicarboxylic acid, phenylindane dicarboxylic acid, 1, 3-dibenzyl-2-oxo-imidazolidine-4,5-dicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, naphthalene-1, 8-dicarboxylic acid, 2-benz oylbenzene-1, 3-dicarboxylic acid, 1, 3-dibenzyl-2-oxoimidazolidine-4,5-cis dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3, 6,9-trioxaundecanedicarboxylic 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-pyrazine dicarboxylic acid, 5,6-dimethyl-2,3-dicarboxylic acid pyrazine dicarboxylic acid, 4,4'-diaminodiphenyl ether diimide dicarboxylic acid, 4,4'-diaminodiphenylmethanediimide dicarboxylic acid, 4,4'-diaminodiphenylsulfonediimide dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid , 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenecarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2 ', 3' -Diphenyl-p-terphenyl-4,4 "-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4 (1H) -oxothiochromene-2,8-dicar Biconic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptadicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, 2,5-di- hydroxy-1, 4-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosendicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, i-amino-methyl-Θ-dioxo-Θ, O-dihydroanthracene-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorubin 4.1 dicarboxylic 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-dicarboxylic acid, 1-benzyl-1 H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1, 5-dicarboxylic acid, 3,5-pyrazoldicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptene-1, 7-dicarboxylic acid, cyclobutane-1, 1-dicarboxylic acid 1, 14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid or campestericarboxylic acid,

More preferably, the at least bidentate organic compound is one of the above-exemplified dicarboxylic acid as such.

For example, the at least bidentate organic compound may be derived from a tricarboxylic acid, such as

2-Hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,3-, 1,4-benzene tricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono 1, 2,4-butanetricarboxylic acid, 1, 3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-

Dihydro-4,5-dioxo-1H-pyrrolo [2,3-F] quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1, 2,4-tricarboxylic acid, 3 -Amino-5-benzoyl-6-methylbenzene-1, 2,4-tricarboxylic

+ acid, 1,2,3-propanetricarboxylic acid or aurintricarboxylic acid,

Furthermore, more preferably, the at least bidentate organic compound is one of the above-exemplified tricarboxylic acids as such.

Examples of an at least bidentate organic compound derived from a tetracarboxylic acid are

1, 1-Dioxidperylo [1, 12-BCD] thiophene-3,4,9,10-tetracarboxylic acid, perylenetetracarboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid or perylene-1,12-sulfone-3, 4,9,10-tetracarboxylic acid, butanetetracarboxylic acids such as 1, 2,3,4-butanetetracarboxylic acid or meso-1,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1, 4, 7, 10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1, 2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecantetracarboxylic acid, 1, 2,5,6-hexane-tetracarboxylic acid, 1, 2,7,8-octanetetracarboxylic acid, 1, 4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decantetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3 ', 4,4'-benzophenetetracarboxylic acid, Tetrahydrofurantetracarboxylic acid or cyclopentanetetracarboxylic acids such as cyclopentane-1, 2,3,4-tetracarboxylic acid. More preferably, the at least bidentate organic compound is one of the above exemplified tetracarboxylic acids as such.

Very particular preference is given to using at least mono-, di-, tri-, tetra- or higher-nuclear aromatic di-, tri- or tetracarboxylic acids, where each of the cores can contain at least one heteroatom, where two or more nuclei have identical or different heteroatoms may contain. For example, preference is given to monocarboxylic dicarboxylic acids, monocarboxylic tricarboxylic acids, monocarboxylic tetracarboxylic acids, dicerate dicarboxylic acids, dicercaric tricarboxylic acids, dicerous tetracarboxylic acids, tricyclic dicarboxylic acids, tricarboxylic tricarboxylic acids, tricarboxylic tetracarboxylic acids, tetracyclic dicarboxylic acids, tetracyclic tricarboxylic acids and / or tetracyclic tetracarboxylic acids. Suitable heteroatoms are, for example, N, O, S, B, P. Preferred heteroatoms here are N, S and / or O. A suitable substituent in this regard is, inter alia, -OH, a nitro group, an amino group or an alkyl or alkoxy group.

Particularly preferred as at least bidentate organic compounds are imidazolates, such as 2-methylimidazolate, acetylenedicarboxylic acid (ADC), camphericarboxylic acid, fumaric acid, succinic acid, benzenedicarboxylic acids, such as phthalic acid,

Isophthalic acid, terephthalic acid (BDC), aminoterephthalic acid, triethylenediamine (TE-

DA), naphthalene dicarboxylic acids (NDC), biphenyl dicarboxylic acids such as

4,4'-biphenyldicarboxylic acid (BPDC), pyrazine dicarboxylic acids, such as 2,5-pyrazine dicarboxylic acid, bipyridine dicarboxylic acids, for example 2,2'-bipyridine dicarboxylic acids, such as, for example, 2,2'-bipyridine-5,5'-dicarboxylic acid, benzene tricarboxylic acid. acids such as 1,2,3-, 1, 2,4-benzenetricarboxylic acid or 1,3,5-benzenetricarboxylic acid (BTC), benzene tetracarboxylic acid, adamantane tetracarboxylic acid (ATC), adamantane dibenzoate (ADB) benzene tribenzoate (BTB), methanetetrabenzoate (MTB), adamantane tetrabenzoate or dihydroxyterephthalic acids such as 2,5-dihydroxy- terephthalic acid (DHBDC).

Amongst others, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,3,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1, 3, 5-benzenetricarboxylic acid, 1, 2,4,5-benzenetetracarboxylic acid, aminoBDC, TEDA, fumaric acid, 2-methylimidazolate, biphenyldicarboxylate.

In addition to these at least bidentate organic compounds, the organometallic framework material may also contain one or more monodentate ligands and / or one or more at least bidentate ligands that are not derived from a di-, tri- or tetracarboxylic acid.

In addition to these at least bidentate organic compounds, the MOF may also comprise one or more monodentate ligands.

Suitable solvents for the preparation of the MOF include i.a. Ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethylsulfoxide, water, hydrogen peroxide, methylamine, caustic soda, N-methylpolydonether, acetonitrile, benzylchloride, triethylamine, ethylene glycol and mixtures thereof. Other metal ions, at least bidentate organic compounds and solvents for the production of MOF include i.a. in US Pat. No. 5,648,508 or DE-A 101 11 230.

The pore size of the organometallic framework can be controlled by choice of the appropriate ligand and / or the at least bidentate organic compound. Generally, the larger the organic compound, the larger the pore size. The pore size is preferably from 0.2 nm to 30 nm, more preferably the pore size is in the range from 0.3 nm to 3 nm, based on the crystalline material.

However, in a shaped body containing an organometallic framework material, larger pores also occur whose size distribution can vary. Preferably, however, more than 50% of the total pore volume, in particular more than 75%, of pores having a pore diameter of up to 1000 nm is formed. Preferably, however, a majority of the pore volume is formed by pores of two diameter ranges. It is therefore further preferred if more than 25% of the total pore volume, in particular more than 50% of the total pore volume, is formed by pores which are in a diameter range of 100 nm to 800 nm and if more than 15% of the total pore volume, in particular more than 25% of the total pore volume is formed by pores ranging in diameter or up to 10 nm. The pore distribution can be determined by means of mercury porosimetry.

The following are examples of organometallic frameworks. In addition to the identification of the framework material, the metal and the at least bidentate ligands, the solvent and the cell parameters (angles α, β and γ as well as the distances A, B and C in A) are also indicated. The latter were determined by X-ray diffraction.

MOF-n Ingredients Solvent α ß b C Room a

TPDC

0.025 mmol

IRMOF-Zn (NO ₃ ) ₂ -4H ₂ O DEF 90 90 90 21.49 21.49 21.49 Pm-3m

16 0.0126 mmol NMP

TPDC

0.05 mmol

ADC acetylenedicarboxylic acid

NDC naphthalene dicarboxylic acid

BDC benzene dicarboxylic acid

ATC adamantane tetracarboxylic acid

BTC benzene tricarboxylic acid

BTB benzene tribenzoic acid

MTB Methanetetrabenzoic acid

ATB adamantane tetrabenzoic acid

ADB adamantane dibenzoic acid

Other organometallic frameworks are MOF-2 to 4, MOF-9, MOF-31 to 36, MOF-39, MOF-69 to 80, MOF103 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 which are described in the literature.

Particularly preferred organometallic frameworks are Al-BDC, MOF-5, IR-MOF-8, Cu-BTC, Al-NDC, Al-AminoBDC, Cu-BDC-TEDA, Zn-BDC-TEDA, Al-BTC, Al-NDC , Mg-NDC, Al-fumarate, Zn-2-aminoimidazolate, Cu-biphenyldicarboxylate-TEDA, MOF-177, MOF-74. Further more preferred are Al-BDC and Al-BTC.

In addition to the conventional method for producing the MOF, as described for example in US 5,648,508, they can also be prepared by electrochemical means. In this regard, reference is made to DE-A 103 55 087 and WO-A 2005/049892. The organometallic frameworks prepared in this way have particularly good properties in connection with the adsorption and desorption of chemical substances, in particular of gases.

Irrespective of its production, the organometallic framework material precipitates in a powdery or crystalline form. This can be used as such as a sorbent in the process according to the invention alone or together with other sorbents or other materials. This is preferably done as bulk material, in particular especially in a fixed bed. Furthermore, the organometallic framework material can be converted into a shaped body. Preferred methods here are the extrusion or tableting. In the molding production, other materials such as binders, lubricants or other additives may be added to the organometallic framework. It is likewise conceivable for mixtures of framework material and other adsorbents, for example activated carbon, to be produced as a shaped body or to give moldings separately, which are then used as shaped-body mixtures.

There are essentially no restrictions with regard to the possible geometries of these shaped bodies. For example, pellets such as disc-shaped pellets, pills, spheres, granules, extrudates such as strands, honeycomb, mesh or hollow body may be mentioned.

In principle, all suitable processes are possible for producing these shaped bodies. In particular, the following procedures are preferred:

Kneading the framework material alone or together with at least one binder and / or at least one pasting agent and / or at least one template compound to obtain a mixture; Shaping the resulting mixture by at least one suitable method such as extrusion; optionally washing and / or drying and / or calcining the extrudate; optional assembly.

- Applying the framework material on at least one optionally porous support material. The material obtained can then be further processed according to the method described above to give a shaped body.

Applying the framework material to at least one optionally porous substrate.

Kneading and molding may be done according to any suitable method as described, for example, in Ullmanns Enzyklopadie der Technischen Chemie, 4th Edition, Volume 2, pp. 313 et seq. (1972), the contents of which are incorporated by reference in the context of the present application in its entirety ,

For example, kneading and / or shaping by means of a piston press, roller press in the presence or absence of at least one binder material, compounding, pelleting, tabletting, extrusion, coextrusion, foaming, spinning, coating, granulation, preferably spraying granulating, spraying, spray-drying or a combination of two or more of these methods.

In particular, pellets and / or tablets are produced.

Kneading and / or shaping may be carried out at elevated temperatures, for example in the range from room temperature to 300 ^° C. and / or at elevated pressure, for example in the range from atmospheric pressure to several hundred bar and / or in a protective gas atmosphere such as in the presence of at least one E- delgases, nitrogen or a mixture of two or more thereof.

The kneading and / or shaping is carried out according to a further embodiment with the addition of at least one binder, wherein as a binder in principle any chemical compound can be used which ensures the kneading and / or deformation desired viscosity of the kneading and / or deforming mass. Accordingly, for the purposes of the present invention, binders may be both viscosity-increasing and viscosity-reducing compounds.

Preferred binders include, for example, alumina or alumina-containing binders such as those described in WO 94/29408, silica such as described in EP 0 592 050 A1, mixtures of silica and alumina, such as those described in U.S. Pat WO 94/13584, clay minerals, as described, for example, in JP 03-037156 A, for example montmorillonite, kaolin, bentonite, halloysite, dickite, nacrit and anauxite, alkoxysilanes, as described for example in EP 0 102 544 B1, for example tetraalkoxysilanes such as, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or trialkoxysilanes such as trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane, alkoxy titanates, for example tetraalkoxytitanates such as tetramethoxytitanate, tetraethoxytitanate, tetrapropoxytitanate, tetrabutoxy titanate, or, for example trial- koxytitanate such as trimethoxytitanate, triethoxytitanate, tripropoxytitanate, tributoxytitanate, alkoxyzirconates, for example tetraalkoxyzirconates such as tetramethoxyzirconate, tetraethoxyzirconate, tetrapropoxyzirconate, nat Tetrabutoxyzirko-, for example, trialkoxyzirconates such as trimethoxyzirconate, triethoxyzirconate, tripropoxyzirconate, tributoxyzirconate, silica sols, to name amphiphilic substances and / or graphites. Particularly preferred is graphite. As a viscosity-increasing compound, for example, optionally in addition to the above-mentioned compounds, an organic compound and / or a hydrophilic polymer such as cellulose or a CeIIU losederivat such as 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 a pasting agent, inter alia, preferably water or at least one alcohol such as a monoalcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-1 - propanol or 2-methyl-2-propanol or a mixture of water and at least one of said alcohols or a polyhydric alcohol such as a glycol, preferably a water-miscible polyhydric alcohol, alone or in admixture with water and / or at least one of said monohydric alcohols are used.

Other additives that can be used for kneading and / or shaping include amines or amine derivatives such as tetraalkylammonium compounds or amino alcohols, and carbonate containing compounds such as calcium carbonate. Such further additives are described for example in EP 0 389 041 A1, EP 0 200 260 A1 or WO 95/19222.

The order of the additives such as template compound, binder, pasting agent, viscosity-increasing substance in the molding and kneading is basically not critical.

According to a further preferred embodiment, the molding obtained according to kneading and / or molding is subjected to at least one drying, which generally takes place at a temperature in the range from 25 to 300 ^° C., preferably in the range from 50 to 300 ^° C. and more preferably in the range from 100 to 300 ⁰ C is performed. It is also possible to dry in vacuo or under a protective gas atmosphere or by spray drying.

According to a particularly preferred embodiment, as part of this drying process, at least one of the compounds added as additives is at least partially removed from the shaped body.

The porous organometallic framework described above is useful as a sorbent in a filter.

In addition, according to the present inventive use, the organometallic porous framework must have a coloring component. In the context of the present invention, the term "coloring component" is understood here to mean a component which lends a color to the organometallic framework by corresponding adsorption of wavelengths of the visible light spectrum.

This can be achieved by various components, wherein, of course, a coloring component is indeed sufficient, but also several coloring components may be present, which are jointly responsible for the coloring of the organometallic framework material.

On the one hand, the at least one metal ion can be the coloring component.

In this case, the at least one metal ion is involved in the construction of the framework of the porous organometallic framework material.

If the porous organometallic framework material is composed only of metal ions of a metal, this is responsible for the coloring. In this case, metal ions are used which have a corresponding color.

Suitable metal ions are transition metal ions, such as Fe "'Fe ¹ ", Co ", Co ¹ ", Ni ", Mo ^v , Mo ¹ ", Cr ¹ ", Cr ^vι , V ¹ ", V ^ιv , V ^v , Mn ¹ " or Mn ^v ".

In addition, however, metal ions of several different metals or metal ions of a metal having different oxidation states may also be involved in the construction of the framework of the porous organometallic framework. In this case, all metal ions can serve as coloring components. However, only one of the different metal ions preferably represents the coloring component. In this case, it is particularly preferred that the porous organometallic framework material is a doped framework material, wherein the doping metal is the coloring component. Methods for producing such doped organometallic frameworks are described in the European patent application with the application number 06123650.1. Reference is made in the examples to framework materials which contain aluminum as the framework-forming metal and molybdenum as the doping metal. Such doped organometallic frameworks have a coloring, so that due to the molybdenum a coloring component in the organometallic framework material is present.

Metals useful as a dopant metal having a coloring property are those listed above. In addition, the scaffold-forming metal from the above generally selected selection of metals for the construction of a porous organometallic framework material.

Additionally or alternatively, the at least one at least bidentate organic compound, which also participates in the framework construction of the porous organometallic framework, may constitute the constituent component.

In this case, the at least one bidentate organic compound beyond its suitability as a scaffold-forming component must also have a chromophore that gives color. If only one at least bidentate organic compound is involved in the construction of the framework material, this represents the coloring component. If several at least bidentate organic compounds are used for the construction of the organometallic framework, all or only some of these compounds can additionally serve as a coloring component.

Typical chromophoric radicals here are, for example, the nitrose group -N = O, the azo group -N = N-, the carbonyl group C =O, the thiocarbonyl group C =S and the azomethine group C =N- and also extended aromatic systems.

Such groups may be introduced into the above-mentioned at least bidentate organic compounds suitable for the construction of the organometallic framework. In this case, the preferences described above for at least bidentate organic compounds apply correspondingly.

A particularly preferred coloring, at least bidentate organic compound is aminoterephthalic acid, which forms an isostructural lattice to frameworks based on terephthalic acid and therefore is easy to mix.

Additionally or alternatively, the organometallic framework may also have another component that is colorant. This further component may be inorganic or organic in nature. In addition, if it is an organic compound, it may also have an inorganic content such as a metal. However, this additional compound is neither the at least one metal ion, nor the at least one at least bidentate organic compound. Of course, such a compound or more of such compounds may be present in the organometallic framework. These may be adsorptively or coordinately connected to the porous organometallic framework, wherein in a coordinate binding, this additional compound does not contribute to the skeleton structure. This may in particular be an inorganic colored, white or black pigment or an organic pigment which has at least partially an organic dye.

This further component can bind to it by simply contacting it with the porous organometallic framework material on adsorptive or coordinative pathways. Examples of such frameworks are described by H.K. Chae et al., Nature 427 (2004), 523-527.

The organic pigments (dyes) are usually organic color, white and black pigments (color pigments). Inorganic pigments may also be color pigments and luster pigments and the inorganic pigments commonly used as fillers.

Examples include anthanthrone, anthraquinone, anthrapyrimidine, azo, quinacridone, quinophthalone, diketopyrrolopyrrole, dioxazine, flavanthrone, indanthrone, isoin-dolphin, isoindolinone, isoviolanthrone, metal complex, perinone , Perylene, phthalocyanine, pyranthrone, pyrazoloquinazolone, thioindigo and triarylcarbonium pigments

The following may be mentioned in particular as examples of suitable organic color pigments:

Monoazo pigments: C.I. Pigment Brown 25; C.I. Pigment Orange 5.13, 36.38, 64 and 67; CI Pigment Red 1, 2, 3, 4, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 51 : 1, 52: 1, 52: 2, 53, 53: 1, 53: 3, 57: 1, 58: 2, 58: 4, 63, 1 12, 146, 148, 170, 175, 184, 185, 187, 191: 1, 208, 210, 245, 247 and 251; C.I. Pigment Yield Iow 1, 3, 62, 65, 73, 74, 97, 120, 151, 154, 168, 181, 183 and 191; C.I. Pigment Vetoel 32;

Disazo pigments: C.I. Pigment Orange 16, 34, 44 and 72; C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188; Disazocondensation pigments: C.I. Pigment Yellow 93, 95 and 128; C.I. Pigment Red 144, 166, 214, 220, 221, 242 and 262; C.I. Pigment Brown 23 and 41;

Anthanthrone pigments: C.I. Pigment Red 168;

Anthraquinone pigments: C.I. Pigment Yellow 147, 177 and 199; C.I. Pigment Violet 31; Anthrapyrimidine pigments: C.I. Pigment Yellow 108;

Quinacridone pigments: C.I. Pigment Orange 48 and 49; C.I. Pigment Red 122, 202, 206 and 209; C.I. Pigment Violet 19;

Quinophthalone pigments: C.I. Pigment Yellow 138;

Diketopyrrolopyrrole pimgente: C.I. Pigment Orange 71, 73 and 81; C.I. Pigment Red 254, 255, 264, 270 and 272;

Dioxazine pigments: CI Pigment Violet 23 and 37; CI Pigment Blue 80; Flavanthrone pigments: CI Pigment Yellow 24;

Indanthrone pigments: C.I. Pigment Blue 60 and 64;

Isoindoline pigments: C.I. pigments Orange 61 and 69; C.I. Pigment Red 260; C.I. Pigment Yellow 139 and 185; Isoindolinone pigments: C.I. Pigment Yellow 109, 110 and 173;

Isoviolanthrone pigments: C.I. Pigment Violet 31;

Metal complex pigments: C.I. Pigment Red 257; C.I. Pigment Yellow 117, 129, 150, 153 and 177; C.I. Pigment Green 8;

Perinone pigments: C.I. Pigment Orange 43; C.I. Pigment Red 194; Perylene pigments: C.I. Pigment Black 31 and 32; C.I. Pigment Red 123, 149, 178, 179, 190 and 224; C.I. Pigment Violet 29;

Phthalocyanine pigments: C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; C.I. Pigment Green 7 and 36;

- Pyranthrone pigments: C.I. Pigment Orange 51; C.I. Pigment Red 216; Pyrazoloquinazolone pigments: C.I. Pigment Orange 67; C.I. Pigment Red 251;

Thioindigo pigments: C.I. Pigment Red 88 and 181; C.I. Pigment Violet 38;

Triaryl carbonium pigments: C.I. Pigment Blue 1, 61 and 62; C.I. Pigment Green 1; C.I. Pigment Red 81, 81: 1 and 169; C.I. Pigment Violet 1, 2, 3 and 27;

C.I. Pigment Black 1 (aniline black); C.I. Pigment Yellow 101 (aldazingelb);

C.I. Pigment Brown 22.

Suitable inorganic color pigments are

White pigments: titanium dioxide (C.I. Pigment White 6), zinc white, colored zinc oxide; Zinc sulphide,

lithopone;

Black pigments: iron oxide black (CI Pigment Black 1 1), iron manganese black, spinel black (CI Pigment Black 27); Carbon black (CI Pigment Black 7); Colored pigments: chromium oxide, chromium oxide hydrate green; Chrome green (CI Pigment Green 48); Cobalt green (CI Pigment Green 50); Ultramarine green; Cobalt blue (CI Pigment Blue 28 and 36; CI Pigment Blue 72); Ultramarine blue; Manganese blue; Ultramarine violet; Cobalt and manganese violet; Iron oxide red (CI Pigment Red 101); Cadmium sulphoselenide (CI Pigment Red 108); Cerium sulphide (CI Pigment Red 265); Molybdate red (CI Pigment Red 104); ultramarine; Iron oxide brown (CI Pigment Brown 6 and 7), moch brown, spinel and corundum phases (CI Pigment Brown 29, 31, 33, 34, 35, 37, 39 and 40), chrome titanium yellow (CI Pigment Brown 24), chrome orange; Cerium sulphide (CI Pigment Orange 75); Iron oxide yellow (CI Pigment Yellow 42); Nickel titanium yellow (CI Pigment Yellow 53; CI Pigment Yellow 157, 158, 159, 160, 161, 162, 163, 164 and 189); Chromium titanium yellow; Spinel phases (CI Pigment Yellow 119); Cadmium sulfide and cadmium zinc sulfide (CI Pigment Yellow 37 and 35); Chrome yellow (CI Pigment Yellow 34); Bismuth vanadate (CI Pigment Yellow 184). Natural or nature-identical dyes, such as, for example, carotenoids, are of particular interest in the case of filters in the medical use and beverage sector.

The filter is preferably an air or exhaust filter.

The shape and nature of the filter can be chosen arbitrarily and adapted to the appropriate use. Applicable filter systems are known to the person skilled in the art. As a simple example of a filter, a plastic bag having pores or small holes and permeable to gas may serve, which is filled with the MOF material, preferably present as a shaped body. Likewise, common air or exhaust air filters can be used. Even filters, such as those used in cooker hoods, air conditioning units, circulation systems, exhaust systems, vacuum cleaners but also in industrial plants can be used. The MOF material can also be filled in cartridges, preferably with a cylindrical shape, which are closed at the end with porous, gas-permeable material and can be flowed through by the medium to be cleaned. The material used for packaging should preferably be thermally stable, so that the filter or the filter unit can be cleaned, for example by thermal desorption, for example for recycling. For this purpose, offer glass, metal, such as aluminum, or known in the art plastics such as polyvinyl chloride, polystyrene, polymethyl methacrylate, polycarbonate, polyvinylpyrrolidone, polyethersulfone, polyester, epoxy resins, polyacetal, etc. on. The MOF material is suitable for passive application (contact with the gas by convection or existing flows) and for active use (contact with the gas intensified by pumps, pressure differences, etc.). It can be used for the pretreatment of indoor air in means of transport such as vehicles, aircraft, rail vehicles, ships, but also in exhaust air filters in internal combustion engines, electrical and electronic equipment. It is also used for cleaning the air in commercial, residential and storage rooms, gas masks, shelters, extractor hoods, in nuclear facilities, for example for radioactive materials, containers, containers, refrigerators, vehicles, etc. as well as semi-finished rubber products, tobacco products and finished parts.

Of particular interest are filters for cooker hoods, air conditioning units, exhaust systems, vacuum cleaners, the interior of rooms, containers, containers, equipment or means of transport, gas masks and tobacco products.

Preferably, the filter is regenerable. This is possible in principle because the adsorption of the odorant to the MOF material is reversible. For example, through

Temperature increase or decrease in pressure a desorption. Also, the Odor are displaced by in flushing gas. The manner in which desorption can be carried out is known to the person skilled in the art. Instructions on this can be found for example in Werner Käst, "Adsorption from the gas phase", Verlag VCH, Weinheim, 1988.

Examples

Example 1: Preparation of an AI-BTC MOF with Orange Color

5 g of AlCl ₃ ^.6H ₂ O, 1, 41 g MoCI ₅ and 3.99 g of trimesic acid are suspended in 300 ml of DMF in egg nem glass flask, heated to 130 ⁰ C and stirred under reflux for 17 h under these conditions. The resulting product is filtered off and washed with 3 x 50 ml of DMF and 4 x 50 ml of methanol. Then the product in a vacuum drying cabinet is pre-dried at 200 ⁰ C for 24 hours and finally calcined in a muffle furnace for 48 hours at 330 ° C under air. It is an orange-brown colored material with a N ₂ surface (Langmuir) of 1754 m ² / g. According to elemental analysis, the material contains 37.6 wt% C, 2.1 wt% H, 12.6 wt% Al and 1.1 wt% Mo.

A corresponding filter material containing this organometallic framework material has a corresponding color.

Example 2: Preparation of an AI-BDC MOF with Yellow Staining

5 g of AlCl ₃ ^.6H ₂ O, 1, 89 g MoCI ₅ and 8.72 g of terephthalic acid are suspended in 300 ml of DMF in a glass flask, heated to 130 ⁰ C and stirred under reflux for 17 hours at these conditions,. The resulting product is filtered off and washed with 3 x 50 ml of DMF and 3 x 50 ml of methanol. The product is then predried in a vacuum drying oven at 150 ° C. for 24 h and finally calcined in a muffle oven at 330 ° C. under air for 48 h. 3.62 g of a yellow-colored material with an N ₂ surface (according to Langmuir) of 1528 m ² / g are obtained. According to elemental analysis, the material contains 44.3 wt% C, 2.7 wt% hydrogen, 12.0 wt% Al and 0.65 wt% Mo. According to XRD, it is a MIL-53 structure - the same basic structure that even without the presence of Mo under these reaction conditions would have arisen.

A corresponding filter material containing this organometallic framework material has a corresponding color. EXAMPLE 3 Preparation of a subsequently colored MOF structure A β-carotene-containing formulation (0.5 g of lucarotene 10 CWD / 0, BASF AG, Ludwigshafen, Germany) is stirred into 50 ml of water. For this purpose, 2 g of an Al terephthalate MOF (according to WO 2007/023134, Ex 26, but uncalcined; N ₂ surface 598 m ² / g according to Langmuir) are added to the colloidal solution. After a short reaction time of 5 minutes, the product is filtered off and washed with 3 x 50 ml of methanol. Finally, the product is dried at 100 ⁰ C for 16 h in the drying oven dried Vakuumtro-. The product is an orange powder with an N ₂ surface area of 607 m ² / g (according to Langmiur). The XRD indicates that the MOF scaffold is still intact after treatment.

Example 4: Preparation of a light yellow colored MOF structure 9.74 g of AlCl _3, 1, 36 g aminoterephthalic acid and 11, 24 g of terephthalic acid are suspended in a 1 I flask in 600 ml of DMF and stirring for 24 h under reflux at 130 ⁰ C held. After cooling, the precipitated MOF is filtered off, washed with 3 x 50 ml of methanol and post-treated for 16 h under reflux with methanol in a Soxhlet extractor. Finally, the product is dried in a vacuum oven at 110 ⁰ C for 16 h. There are obtained 8.1 g of a light yellow powder. The XRD shows that the MOF formed has the MIL-53 structure, which would have formed even without the addition of aminoterephthalic acid under these conditions. The N ₂ surface (according to Langmuir) is 1465 m ² / g, which also corresponds to pure terephthalate.

Claims

claims

1 . Use of a porous organometallic framework material containing at least one coordinating at least one metal ion bound at least bidentate organic compound, wherein the at least one metal ion, the at least one at least bidentate organic compound or optionally a further component is a coloring component, as a sorbent and for permanent color coding a filter.

2. Use according to claim 1, characterized in that the at least one metal ion is the coloring component.

3. Use according to claim 1 or 2, characterized in that the at least one at least bidentate organic compound is the coloring component.

4. Use according to one of claims 1 to 3, characterized in that the framework material contains a further component which is a coloring component.

5. Use according to claim 4, characterized in that the one further component is an inorganic color, white or black pigment.

6. Use according to claim 4, characterized in that the one further component is an at least partially organic dye.

7. Use according to one of claims 1 to 6, characterized in that the filter is an air or exhaust filter.

8. Use according to claim 7, characterized in that the filter is a filter for cooker hoods, air conditioners, exhaust systems, vacuum cleaners, the interior of rooms, containers, containers, equipment or means of transport, gas masks and tobacco products.