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EP2117700A1 - Utilisation de matériaux organométalliques structurels poreux pour identifier des filtres par leur couleur - Google Patents

Utilisation de matériaux organométalliques structurels poreux pour identifier des filtres par leur couleur

Info

Publication number
EP2117700A1
EP2117700A1 EP07857677A EP07857677A EP2117700A1 EP 2117700 A1 EP2117700 A1 EP 2117700A1 EP 07857677 A EP07857677 A EP 07857677A EP 07857677 A EP07857677 A EP 07857677A EP 2117700 A1 EP2117700 A1 EP 2117700A1
Authority
EP
European Patent Office
Prior art keywords
acid
dicarboxylic acid
pigment
filter
mof
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP07857677A
Other languages
German (de)
English (en)
Inventor
Markus Schubert
Ulrich Müller
Christoph Kiener
Marcus Guzmann
Jürgen HUFF
Jörg PASTRE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP2117700A1 publication Critical patent/EP2117700A1/fr
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/49—Materials comprising an indicator, e.g. colour indicator, pH-indicator

Definitions

  • 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.
  • filters are often only a part of devices, housings or the like.
  • the filters are media for cleaning air or exhaust air.
  • 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.
  • 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.
  • porous organometallic framework materials known in the prior art are also suitable as adsorbents.
  • organometallic frameworks are used as sorbent.
  • 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.
  • 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.
  • organometallic frameworks 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.
  • MOF organometallic frameworks
  • 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.
  • 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.
  • 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.
  • 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 al
  • functional groups are to be mentioned where the above R is not present.
  • -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
  • -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.
  • 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.
  • the aromatic compound or the aromatic moiety of the both aliphatic and aromatic compounds has one, two or three nuclei, with one or two nuclei being particularly preferred.
  • each nucleus of the 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.
  • the aromatic compound or the aromatic part of both the aromatic and aliphatic compound contains one or two C ⁇ cores, the two being present either separately or in condensed form.
  • benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl may be mentioned as aromatic compounds.
  • the at least bidentate organic compound an aliphatic or aromatic, acyclic or cyclic hydrocarbon having 1 to 18, preferably 1 to 10 and in particular 6 carbon atoms, which additionally has only 2, 3 or 4 carboxyl groups as functional groups.
  • the at least bidentate organic compound is derived from a dicarboxylic acid, such as oxalic, 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, 4-
  • the at least bidentate organic compound is one of the above-exemplified dicarboxylic acid as such.
  • the at least bidentate organic compound may be derived from a tricarboxylic acid, such as
  • the at least bidentate organic compound is one of the above-exemplified tricarboxylic acids as such.
  • each of the cores can contain at least one heteroatom, where two or more nuclei have identical or different heteroatoms may contain.
  • 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.
  • 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,
  • imidazolates such as 2-methylimidazolate, acetylenedicarboxylic acid (ADC), camphericarboxylic acid, fumaric acid, succinic acid, benzenedicarboxylic acids, such as phthalic acid,
  • DA naphthalene dicarboxylic acids
  • NDC naphthalene dicarboxylic acids
  • biphenyl dicarboxylic acids such as
  • BPDC 4,4'-biphenyldicarboxylic acid
  • 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.
  • BTC 1,2,3-, 1, 2,4-benzenetricarboxylic acid or 1,3,5-benzenetricarboxylic acid
  • benzene tetracarboxylic acid adamantane tetracarboxylic acid
  • ATC adamantane tetracarboxylic acid
  • ADB adamantane dibenzoate
  • BTB benzene tribenzoate
  • MTB methanetetrabenzoate
  • DHBDC 2,5-dihydroxy- terephthalic acid
  • 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.
  • 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.
  • 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.
  • larger pores also occur whose size distribution can vary.
  • more than 50% of the total pore volume, in particular more than 75%, of pores having a pore diameter of up to 1000 nm is formed.
  • a majority of the pore volume is formed by pores of two diameter ranges. It is therefore further preferred if more than 25% of the total pore volume, in particular more than 50% of the total pore volume, is formed by pores which are in a diameter range of 100 nm to 800 nm and if more than 15% of the total pore volume, in particular more than 25% of the total pore volume is formed by pores ranging in diameter or up to 10 nm.
  • the pore distribution can be determined by means of mercury porosimetry.
  • organometallic frameworks The following are examples of organometallic frameworks.
  • the metal and the at least bidentate ligands the solvent and the cell parameters (angles ⁇ , ⁇ and ⁇ as well as the distances A, B and C in A) are also indicated. The latter were determined by X-ray diffraction.
  • 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.
  • 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.
  • organometallic frameworks prepared in this way have particularly good properties in connection with the adsorption and desorption of chemical substances, in particular of gases.
  • 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.
  • the organometallic framework material can be converted into a shaped body. Preferred methods here are the extrusion or tableting.
  • other materials such as binders, lubricants or other additives may be added to the organometallic framework.
  • 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.
  • pellets such as disc-shaped pellets, pills, spheres, granules, extrudates such as strands, honeycomb, mesh or hollow body may be mentioned.
  • 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 ,
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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 glyco
  • the order of the additives such as template compound, binder, pasting agent, viscosity-increasing substance in the molding and kneading is basically not critical.
  • the molding obtained according to kneading and / or molding is subjected to at least one drying, 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.
  • At least one of the compounds added as additives is at least partially removed from the shaped body.
  • porous organometallic framework described above is useful as a sorbent in a filter.
  • the organometallic porous framework must have a coloring component.
  • 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.
  • 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.
  • the at least one metal ion can be the coloring component.
  • the at least one metal ion is involved in the construction of the framework of the porous organometallic framework material.
  • porous organometallic framework material is composed only of metal ions of a metal, this is responsible for the coloring.
  • 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 v ⁇ , V 1 “, V ⁇ v , V v , Mn 1 “ or Mn v ".
  • 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.
  • all metal ions can serve as coloring components.
  • only one of the different metal ions preferably represents the coloring component.
  • 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.
  • the scaffold-forming metal from the above generally selected selection of metals for the construction of a porous organometallic framework material.
  • 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.
  • 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.
  • Such groups may be introduced into the above-mentioned at least bidentate organic compounds suitable for the construction of the organometallic framework.
  • 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.
  • the organometallic framework may also have another component that is colorant.
  • This further component may be inorganic or organic in nature.
  • it may also have an inorganic content such as a metal.
  • this additional compound is neither the at least one metal ion, nor the at least one at least bidentate organic compound.
  • 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.
  • 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.
  • organic pigments 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
  • 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;
  • 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
  • Suitable inorganic color pigments are
  • White pigments titanium dioxide (C.I. Pigment White 6), zinc white, colored zinc oxide; Zinc sulphide,
  • 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
  • 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.
  • 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.
  • common air or exhaust air filters can be used.
  • 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.
  • 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.
  • 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.
  • the filter is regenerable. This is possible in principle because the adsorption of the odorant to the MOF material is reversible. For example, through
  • a corresponding filter material containing this organometallic framework material has a corresponding color.
  • a corresponding filter material containing this organometallic framework material has a corresponding color.
  • EXAMPLE 3 Preparation of a subsequently colored MOF structure
  • a ⁇ -carotene-containing formulation (0.5 g of lucarotene 10 CWD / 0, BASF AG, Ludwigshafen, Germany) is stirred into 50 ml of water.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne l'utilisation d'un matériau organométallique structurel poreux qui contient au moins un composé organique au moins bivalent lié par coordination à au moins un ion métallique, ledit ou lesdits ion(s) métallique(s), ledit ou lesdits composé(s) organique(s) au moins bivalent(s) ou éventuellement un autre composant étant des composants colorants, comme absorbeur et pour identifier un filtre de manière permanente par sa couleur.
EP07857677A 2006-12-27 2007-12-17 Utilisation de matériaux organométalliques structurels poreux pour identifier des filtres par leur couleur Ceased EP2117700A1 (fr)

Applications Claiming Priority (2)

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DE102006061587A DE102006061587A1 (de) 2006-12-27 2006-12-27 Verwendung poröser metallorganischer Gerüstmaterialien zur farblichen Kennzeichung von Filtern
PCT/EP2007/064046 WO2008080813A1 (fr) 2006-12-27 2007-12-17 Utilisation de matériaux organométalliques structurels poreux pour identifier des filtres par leur couleur

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EP2117700A1 true EP2117700A1 (fr) 2009-11-18

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PL2230288T3 (pl) * 2009-03-20 2016-12-30 Metaloorganiczne materiały szkieletowe w urządzeniach chłodzących/grzejnych
RU2532554C1 (ru) * 2013-04-18 2014-11-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Ивановский государственный химико-технологический университет" (ФГБОУ ВПО "ИГХТУ") Способ получения титансодержащего металлоорганического каркасного соединения
US9190114B1 (en) 2015-02-09 2015-11-17 Western Digital Technologies, Inc. Disk drive filter including fluorinated and non-fluorinated nanopourous organic framework materials
CN104868102B (zh) * 2015-06-10 2017-06-06 中南大学 一种钠离子电池硫化锌基负极材料及其制备方法
CN109876867A (zh) * 2019-03-05 2019-06-14 西北师范大学 一种双金属-有机骨架/钒酸铋复合光电阳极材料的制备方法
CN110394158B (zh) * 2019-07-05 2022-02-01 重庆科技学院 一种钛基金属有机骨架吸附材料及其制备方法和分离钯的应用
CN113336956B (zh) * 2021-04-12 2022-05-31 皖西学院 金属-有机孔道钴化合物、制备方法及其应用
CN113304736B (zh) * 2021-06-07 2022-03-04 浙江月旭材料科技有限公司 一种抗水型复合材料及其制备方法和用途

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WO2008080813A1 (fr) 2008-07-10
US8563464B2 (en) 2013-10-22
US20100331176A1 (en) 2010-12-30

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