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WO1993017966A1 - Tamis moleculaires contenant des colorants a base d'indigo - Google Patents

Tamis moleculaires contenant des colorants a base d'indigo Download PDF

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Publication number
WO1993017966A1
WO1993017966A1 PCT/EP1993/000460 EP9300460W WO9317966A1 WO 1993017966 A1 WO1993017966 A1 WO 1993017966A1 EP 9300460 W EP9300460 W EP 9300460W WO 9317966 A1 WO9317966 A1 WO 9317966A1
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molecular sieve
molecular sieves
indigo
zeolites
dye
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PCT/EP1993/000460
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German (de)
English (en)
Inventor
Guenter Lauth
Wolfgang Hoelderich
Gerhard Wagenblast
Ernst Schefczik
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Basf Aktiengesellschaft
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Priority to EP93904030A priority Critical patent/EP0630353A1/fr
Publication of WO1993017966A1 publication Critical patent/WO1993017966A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/04—Aluminophosphates [APO compounds]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/065—Aluminophosphates containing other elements, e.g. metals, boron the other elements being metals only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B63/00—Lakes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes

Definitions

  • the present invention relates to new crystalline molecular sieves containing one or more chromophores from the class of indigo dyes and their use as colorants.
  • Molecular sieves are generally used as adsorbents and as catalysts or as catalyst supports (review article: L. Puppe and. Büchner: "Zeolites - structures, syntheses, applications *, Naturwissenschaften 71, (1984), 192).
  • the adsorption properties of molecular sieves have mainly been used for smaller molecules.
  • the adsorption of water, nitrogen or even benzene is used to characterize molecular sieves.
  • the adsorption of water, nitrogen or even benzene is used to characterize molecular sieves.
  • the nature of the adsorbed molecule and the shape of the adsorption isotherm the size and shape of the micropores, pore volume, phase purity or presence of mesopores (description, for example, in D. Breck: "Zeolite Molecular Sieves, Structure, Chemistry and Use *, J. Wiley , New York, 1974).
  • the adsorption of the molecules mentioned is reversible, i.e. by appropriate treatment, e.g. Increasing the temperature, lowering the pressure or using a solvent can desorb the molecules bound to the molecular sieve again undamaged. This fact is used in the separation of material mixes.
  • the selective adsorption properties of aluminophosphates are e.g. used in EP-A-130 740 to separate ortho-substituted aromatics from a mixture of isomers.
  • Zeolites are known from US Pat. No. 4,018,870 which contain basic dyes from the class of the triarylmethane dyes.
  • DE-A-3 625 693 proposes acidic dyes with reactive components in the presence of acid-binding agents, e.g. of zeolites to condense.
  • the object of the present invention was to store dyes based on indigo so firmly in a molecular sieve framework that a stable inclusion compound with pigment properties arises from the originally soluble organic dyes, in order to obtain new colorants with advantageous performance properties.
  • Suitable indigo dyes are known per se and are described in large numbers, e.g. in üllmann's Encyclopedia of Industrial Chemistry, Vol. A14, pages 149 to 156, or in J. Am. Chem. Soc. Vol. 78, pp. 1251 to 1252, 1956.
  • Suitable indigo dyes obey e.g. of the formula
  • R 1 , R 2 , R 3 , R 4 , R 5 , R e , R 7 and R 8 are the same or different and each independently represent hydrogen, chlorine or bromine.
  • NZMS non-zeolitic molecular sieves
  • Zeolites are crystalline aluminosilicates, which have a highly ordered structure with a rigid three-dimensional network of Si0 4 and A10 4 tetrahedra, which are connected by common oxygen atoms.
  • the ratio of silicon and aluminum atoms to oxygen is 1: 2 (see Ulimann's Encyclopedia of Industrial Chemistry, 4th edition, volume 24, page 575).
  • the electrovalence of the tetrahedra containing aluminum is balanced by the inclusion of cations in the crystal, for example an alkali or hydrogen ion. A cation exchange is possible.
  • the spaces between the tetrahedra are occupied by drying or calcining water molecules before dehydration.
  • the zeolites are mostly used in the acidic H form or neutral alkali form.
  • other elements such as boron, gallium, iron, chromium, vanadium, arsenic, antimony, bismuth, beryllium or mixtures thereof can be built into the lattice instead of aluminum, or the silicon can be replaced by another tetravalent element such as Germanium, titanium, zirconium or hafnium can be replaced.
  • zeolites are divided into different groups.
  • mordenite group chains or in the case of the chabasite group
  • layers of tetrahedra form the zeolite structure
  • the tetrahedra are grouped into polyhedra, for example in the form of a cubo-ctahedron made of four rings or six rings.
  • zeolites of type A, L, X or Y are grouped into polyhedra, for example in the form of a cubo-ctahedron made of four rings or six rings.
  • the molecular sieves on which the substances according to the invention are based are, in particular, zeolites from the mordenite group or zeolites of the faujasite type, for example Y-, X- or L-zeolites.
  • This group of zeolites also includes the so-called "ultra-stable * zeolites of the faujasite type, ie dealuminized zeolites. Methods for producing such zeolites are described, for example, in” Catalysis by Zeolites “Volume 5 from” Studies in Surface Science and Catalysis "ed. B Imelik et al. Elsevier Scientific Publishing Comp. 1980, p. 203; "Crystal Structures of Ultra-stable Faujasites” Advances in Chemistry Series No. 101, American Chemical Society Washington, DC, p. 226 ff (1971) or in US-A-4 512 961.
  • Zeolites of the pentasil type are also advantageously used.
  • these are made up of Si0 4 tetrahedra
  • zeolites can have different chemical compositions. This is to aluminosilicate, borosilicate, iron, beryllium, gallium, chromium, arsenic, antimony or Wismutsili- 'katzeolithe or mixtures thereof or aluminosilicate, borosilicate, or iron germanate or their Gallium ⁇ Mixtures.
  • the aluminosilicate zeolite is composed, for example, of an aluminum compound, preferably aluminum hydroxide or aluminum sulfate and a silicon component, preferably highly disperse silicon dioxide, in an aqueous amine solution, in particular in polyamines, such as 1,6-hexanediamine, 1,3-propanediamine or triethylenetetrain Solution, with or in particular without addition of alkali or alkaline earth at 100 to 220 ° C under autogenous pressure.
  • This also includes the isotactic zeolites according to EP-A-34 727 or EP-A-46 504.
  • the aluminosilicate zeolites obtained have an SiO 2 / Al 2 O ratio of 10: 1 to 40,000, depending on the amount of starting material selected : 1 on.
  • Such aluminosilicate zeolites can also be used in an ethereal medium, for example in diethylene glycol dimethyl ether, in an alcoholic medium, for example in methanol, ethanol, propanol, isopropanol, butanol, ethane-1,2-diol, butane-1,4-diol, hexane-1 , 6-diol or polyols, or synthesize in water.
  • Iron silicate zeolites are obtained, for example, from an iron compound, preferably iron (III) sulfate and a silicon compound, preferably highly disperse silicon dioxide, in aqueous amine solution, in particular 1,6-hexanediamine, with or without addition of alkali metal or alkaline earth metal at 100 to 220 ° C. under autogenous pressure.
  • the silicon-rich zeolite Si0 2 / Al 2 0> 10: 1) the so-called ZSM-type, ferrierite, Nu-1 or silicalite ® (Union Carbide / UOP) include a molecular sieve, a so--called silica polymorph.
  • Zeolite powder can be subjected to a deformation step after its production. This gives shaped articles of various shapes, tablets, rings, strands, stars or cloverleaf shapes.
  • zeolites can be dried at 100 to 160 ° C., preferably 110 ° C., and calcined at 450 to 550 ° C., preferably 500 ° C., with a binder in a ratio of 90: 10 to 40: 60% by weight Strands or tablets are deformed.
  • Various aluminum oxides in particular boehmite, amorphous aluminosilicates with an SiO 2 / Al 2 O 3 weight ratio of 25:75 to 90: 5, in particular 75:25, silicon dioxide, in particular highly disperse silicon dioxide, are suitable as binders mix of highly disperse silicon dioxide and highly disperse aluminum oxide, titanium dioxide, zirconium (IV) oxide and clay.
  • the extrudates of the compacts are dried at 110 ° C. for 16 hours and calcined at 500 ° C. for 16 hours.
  • Suitable moldings are also obtained if the isolated zeolites are deformed directly after drying and are only subjected to calcination after the deformation.
  • the zeolites produced can also be used in pure form, without binders, as strands or tablets, with extrusion or peptization aids, e.g. Ethyl cellulose, potato starch, stearic acid, formic acid, oxalic acid, acetic acid, nitric acid, ammonia, amines, silicon esters, graphite or mixtures thereof can be used.
  • the zeolites are particularly used in powder form.
  • the zeolites are not in the acidic H form due to the type of production, but e.g. in the alkali or alkaline earth form, then this can be obtained by ion exchange, e.g. with ammonium ions and subsequent calcination or by treatment with acids completely or partially converted into the desired H form.
  • Phosphates are also used as molecular sieves for the production of the new colorants according to the invention. Phosphates synthesized under hydrothermal conditions are used. These phosphates have a zeolite structure. A distinction is made between Al-PO's, SAPO'S, ELAPO's, ELSAPO's and MeAPO's as well as VPI-5 and Cloverite. Such phosphates are described in the review article EM Flanigen et al .: "Alumophosphate molecular sieves and the periodic table" Pure & Appl. Chem. Vol 58, pp. 1351 to 1358 (1986).
  • a large number of microporous aluminum phosphates are known from US Pat. No. 4,310,440. Then they are produced by using so-called templates (structure formers) as starting components in addition to phosphorus and aluminum-containing compounds.
  • templates structure formers
  • organic nitrogen compounds e.g. amines, ammonium compounds or nitrogen heterocycles
  • many different aluminum phosphate structures can be produced, which are characterized by their different X-ray diffraction data.
  • aluminophosphates differ in their structure of the cavity system, ie in pore size, pore volume and surface area. These differences require different properties, such as adsorption capacities, the ability to separate certain substances or catalytic activity.
  • Alumophosphates consist of a crystal lattice, which is made up of T ⁇ 4 tetrahedra, with T phosphorus and aluminum occurring as tetrahedral atoms.
  • the number of AIO 4 and P0 4 tetrahedra are the same, so that the crystal lattice carries no charge and therefore no charge-balancing cations are present.
  • Microporous aluminophosphates are used as adsorbents, as catalysts or as catalyst supports (review article: EM Flanigen et al .: "Structural, synthetic and physicochemical concepts in aluminophosphate-based molecular sieves" in "Innovation in Zeolite Materials Science” PJ Grobet et al. (Ed.), Elsevier, 1988, pp. 13 to 27).
  • the aluminum phosphates produced under hydrothermal conditions are e.g. ALP0-5, ALP0-8, ALP0-9, ALPO-11, ALPO-12, ALPO-14, ALPO-21, ALPO-25, ALPO-31 and ALPO-33 or MCM9. Syntheses of these compounds are e.g. in EP-A-132 708, US-A-4 310 440, or in J. Am. Chem. Soc. 104, (1982), 1146.
  • the AIPO 4 -5 (APO-5) is synthesized by homogeneously mixing orthophosphoric acid with pseudoboehmite in water, adding tetrapropylammonium hydroxide to this mixture and then the reaction mixture at about 150 ° C. for 20 to 60 hours under autogenous Pressure in an autoclave.
  • the filtered AIPO 4 is dried at 100 to 160 ° C and calcined at 450 to 550 ° C.
  • microporous aluminophosphate referred to as ALPO-11 is described in US Pat. No. 4,310,440, Examples 32 to 36.
  • the compound is then synthesized by using phosphoric acid, an aluminum compound and a dialkylamine, e.g. Di-n-propylamine or diisopropylamine can be used.
  • the mixture is treated hydrothermally.
  • a microporous aluminophosphate is initially produced as the product, the pores of which are filled with the template.
  • the template can be removed by calcining this compound.
  • AIPO 4 -9 (APO-9) is also made from orthophosphoric acid and pseudo-boehmite but in aqueous DABCO solution (1,4-diazabicyclo- (2,2,2) octane) at approx. 200 ° C under autogenous pressure synthesized for 200 to 400 hours.
  • AIPO 4 -21 (APO-21) is synthesized from orthophosphoric acid and pseudoboehmite in aqueous pyrrolidone solution at 150 and 200 ° C. under autogenous pressure for 50 to 200 h.
  • the synthesis of the SAPOs is analogous to that of the ALPOs, with an additional silicon source being added to the synthesis batch.
  • the charge of the AIO 4 , PO 4 and SiO tetrahedra contained in the crystal lattice of the SAPOs generally does not compensate, so that a charged crystal lattice results, the charge of which must be balanced by counterions.
  • SAPOs can be used as ion exchangers in addition to the applications already mentioned for the ALPOs.
  • SAPOs are solid acids in their H form, so they can e.g. be used as Bronsted acidic catalysts.
  • Suitable silicon aluminum phosphates are, for example, SAPO-5, SAPO-8, SAPO-11, SAPO-31 or SAPO-34. The synthesis of these compounds is described, for example, in EP-A-103 117 or US-A-4 440 871. These silicon aluminum phosphates have a zeolite structure. SAPOs are produced by crystallization from an aqueous mixture at 100 to 250 ° C. and autogenous pressure for 2 hours to 2 weeks, the reaction mixture consisting of a silicon, Aluminum and phosphorus component is implemented in aqueous amino organic solutions.
  • SAPO-5 for example, is obtained by mixing silicon dioxide - suspended in aqueous tetrapropylammonium hydroxide solution - with an aqueous suspension of pseudoboehmite and orthophosphoric acid and then reacting it at 150 to 200 ° C. for 20 to 200 hours under autogenous pressure in a stirred autoclave .
  • the filtered powder is dried at 110 to 168 ° C and calcined at 450 to 550 ° C.
  • SAPO-11 microporous silicoaluminophosphate referred to as SAPO-11 is described in US Pat. No. 4,440,871, Examples 15 to 22, and is carried out in a manner analogous to that described for ALPO-11, with only a reactive silicon source being added to the reaction mixture .
  • ALPO-11 and SAPO-11 are identical and was described, for example, by Bennett et al. (Zeolites, Vol.7, (1987) p. 160).
  • the structure is classified under the name AEL as a crystal structure by Meier and Olson ("Atlas of Zeolite Structure Types" 2nd Ed., Butterworths, London, 1987).
  • silicon aluminum phosphates are e.g. ZYT-5, ZYT-6, ZYT-7, ZYT-9, ZYT-11 or ZYT-12 are suitable (JP-A-217 619/1984).
  • non-zeolitic molecular sieves also include the phosphates e.g. Aluminum phosphate and silicon aluminum phosphate with VPI-5 structure and the cloverite (gallium phosphate).
  • phosphates e.g. Aluminum phosphate and silicon aluminum phosphate with VPI-5 structure and the cloverite (gallium phosphate).
  • the aluminum phosphate VPI-5 is a molecular sieve with uniform one-dimensional channels and extra large pores with 18 tetrahedral atoms and a freely accessible diameter of about 12 A.
  • the preparation of this substance is described, for example, by ME Davis et al. ACS Symp. Ser. 398 (1989) pp. 291-304.
  • aqueous phosphoric acid is added to boehmite suspended in water, and after an aging phase of 1.5 to 2 hours with stirring, n-dipropylamine is added. This reaction mixture is stirred at 142 ° C. for 20 to 24 hours.
  • the properties and characteristics of these materials are described, for example, in J. Phys. Chem.
  • the silicon-containing aluminum phosphate with VPI-5 structure is also known and can also be used for the preparation of the compounds according to the invention.
  • the Cloverite is a cubic gallium phosphate molecular sieve with a pore opening formed from 20 tetrahedral atoms and a three-dimensional channel system. The maximum pore diameter is approx. 14 A. The supercage at the intersections of the channels has a diameter of 29 to 30 A. The manufacture and structure of this material is described in Nature 352 (1991) p. 320 and p. 281. Also this gallium phosphate with a microporous crystal structure is suitable for the production of the dyes according to the invention, in particular for the incorporation of bulky molecules.
  • the phosphates with zeolite structure thus prepared can be dried at 100 to 160 ° C., preferably 110 ° C., and calcined at 450 to 550 ° C., preferably 500 ° C., with a binder in a ratio of 90: 10 to 40:60 % By weight to form strands, tablets, clover leaves, rings, wheels or monoliths.
  • Various aluminum oxides, preferably boehmite, amorphous aluminosilicates with a SiO 2 / Al 0 3 weight ratio of 25:75 to 90: 5, preferably 75:25, silicon dioxide, preferably highly disperse silicon dioxide, mixtures of highly disperse silicon dioxide and highly disperse are suitable as binders Alumina and clay.
  • the extrudates or compacts are dried at 110 ° C. for 16 hours and calcined at 500 ° C. for 16 hours.
  • Moldings of the molecular sieves used are also advantageously obtained if the isolated phosphate is deformed directly after drying and is only subjected to calcination after the shaping.
  • the phosphates produced can be used in pure form, without binders, as strands or tablets, with extruding or peptizing aids e.g. Ethyl cellulose, potato starch, stearic acid, formic acid, oxalic acid, acetic acid, nitric acid, ammonia, amines, silicon esters, graphite or mixtures thereof are used.
  • the phosphate is e.g. Silicon aluminum phosphate does not exist in the acidic H form due to the nature of its production, but e.g. in the Na form or in another alkali or alkaline earth form, this can then be replaced by ion exchange e.g. with ammonium ions and subsequent calcination or by treatment with acids or partially converted into the desired H form.
  • ion exchange e.g. with ammonium ions and subsequent calcination or by treatment with acids or partially converted into the desired H form.
  • the pore size of the crystalline molecular sieves is usually 4 to 14 A, preferably 5 to 12 A and in particular 5 to 8 A.
  • the maximum diameter of the supercages of the molecular sieves is 29 to 30 A.
  • the incorporation of the indigo dyes does not constitute a normal adsorption in which the adsorbent is reversibly bound to the adsorbate.
  • indigo dye and molecular sieve The connection between indigo dye and molecular sieve is usually so strong that when energy is supplied, e.g. Heat treatment, practically no desorption of the dye takes place. At most, the indigo dye decomposes at relatively high temperatures. This results from the favorable choice of the dimensions of the indigo dye and molecular sieve pores and the chemical properties of the indigo dye and molecular sieve (e.g. hydrophilicity or polarity), which leads to very stable inclusion compounds.
  • Indigo dye and molecular sieve can be selected so that they fit together in terms of their steric and electronic properties.
  • a very large indigo dye is e.g. cannot penetrate into the pore system of a narrow-pore molecular sieve at all.
  • the dye would at most adsorb on the outer surface of the molecular sieve, from where it is sublimed away at the end temperature of the treatment and / or washed off during the solvent treatment.
  • a very small dye molecule will fit well into a wide-pore molecular sieve; in this case the interaction between dye and molecular sieve will be so weak that the indigo dye, e.g. through a Soxhlet extraction, will be relatively easy.
  • the molecular sieve immobilizes the originally soluble dye, so that the intercalation compound has improved stability against solvents.
  • the molecular sieve grid, in which the indigo dye is enclosed, can also offer better protection against acidic and alkaline solutions, as well as increased resistance to temperature and radiation influences.
  • the substances according to the invention generally contain 0.01 to 20% by weight, preferably 0.5 to 15% by weight and in particular 1 to 5% by weight, of indigo dye, in each case based on the weight of the molecular sieve.
  • the indigo dyes can be incorporated in several ways. One possibility is to treat a mixture of usually calcined molecular sieve and indigo dye at a higher temperature. The prerequisite is usually a steric and electronic matching of the dye molecule and the pore system of the molecular sieve.
  • Treatment of the mixture can be accomplished by adding a solvent, e.g. N, N-dimethylformamide, N-methylpyrrolidinone, nitrobenzene or trichlorobenzene, the indigo dye, can be lightened.
  • a solvent e.g. N, N-dimethylformamide, N-methylpyrrolidinone, nitrobenzene or trichlorobenzene, the indigo dye
  • the mixture of indigo dye, molecular sieve and optionally solvent is brought to a temperature of 50 to 300 ° C. at a pressure of less than 1 bar, preferably less than 50 mbar, in particular less than 10 mbar and very particularly less than 1 mbar , preferably 100 to 250 ° C, heated. The temperature is held for 0.1 to 100 minutes. After this treatment, excess, i.e. Dye not bound in the molecular sieve by a suitable treatment, e.g. using Soxhlet extraction.
  • indigo dyes via the leuco form, which is soluble, for example, in water, alcohol or ether in the presence of calcined molecular sieve and subsequent oxidation.
  • the size of the reactant molecules must be chosen so that they fit into the cavities of the molecular sieves.
  • the reaction conditions in this synthesis are to be selected so that the structure of the molecular sieve is not destroyed.
  • indigo dye formed outside the pores is treated by a suitable treatment, e.g. with a solvent.
  • the inclusion compound is the synthesis of the molecular sieve in the presence of the indigo dye.
  • the indigo dye and, if appropriate, a further template are added to a conventional molecular sieve synthesis mixture which consists, for example, of a silicon and, if appropriate, an aluminum source.
  • the mixture is treated hydrothermally in an autoclave at a temperature of 100 to 250 ° C.
  • the resulting product is filtered off and suitable solvents for the removal of unreacted starting materials.
  • the inclusion compounds often differ in color from the original indigo dye and the molecular sieve.
  • the X-ray diffractogram of the inclusion compound usually shows the lines of the original molecular sieve.
  • the exact location and intensity of the diffraction lines of the inclusion compound often deviate somewhat from those of the untreated molecular sieve, an effect that can be seen inter alia. by a slight change in the geometry of the unit cell, caused by the embedded dye molecules.
  • Diffraction lines of the pure dye generally do not occur in the inclusion compound, since the dye adapts to the structure of the molecular sieve and loses the structure of the pure solid dye.
  • the chemical analysis of the inclusion compounds shows a carbon content of 0.1 to 20%, corresponding to the content of indigo dye.
  • the thermal stability of the inclusion compounds could be quantified by thermogravimetric experiments.
  • the new material remains unchanged up to temperatures above 400 ° C; the indigo dye enclosed in the molecular sieve only decomposes above 500 ° C.
  • the crystalline molecular sieves containing indigo dyes according to the invention are advantageously suitable as colorants, use in particular as pigments being mentioned. They have good fastness to use as well as high brilliance and temperature stability. Furthermore, they are resistant to the action of solvents.
  • the use of the new colorants for pigmenting lacquers, plastics, ceramics or materials which are produced via sol-gel products should be emphasized.
  • indigo dyes used in the examples are abbreviated below with the letters A to U for the sake of simplicity.
  • the structural formulas of these dyes are summarized in Table 1.
  • the molecular sieves used in the examples were either produced themselves according to a literature specification or are commercially available.
  • the manufacturing instructions or source of supply for the molecular sieves used are summarized in Table 2 along with their short designation.
  • 10 g of freshly calcined molecular sieve are mixed with 0.5 g of indigo dye and slowly heated at a pressure of 1 mbar. The temperature is raised at a rate of 1 ° C / min. When the sublimation temperature of the indigo dye is reached, the temperature is kept constant for about 30 minutes. hold. The indigo dye can sublime into the pores of the molecular sieve. After sublimation has ended, the temperature is increased by a further 10 to 20 degrees to the so-called final temperature, so as to sublimate away excess indigo dye or indigo dye which is located on the outer surface of the molecular sieve. The subliming dye can be collected on a cold finger.
  • the intercalation compound is checked several times with boiling solvent, e.g. As acetone, acetonitrile or ethanol treated. Alternatively, a Soxhlet extraction can also be carried out. In this treatment, with a stable intercalation compound, practically no dye passes from the molecular sieve into the solvent.
  • boiling solvent e.g. As acetone, acetonitrile or ethanol treated.
  • Soxhlet extraction can also be carried out. In this treatment, with a stable intercalation compound, practically no dye passes from the molecular sieve into the solvent.
  • the colored intercalation compound is filtered off and washed several times with pure boiling solvent, e.g. with N, N-dimethylformamide, N-methylpyrrolidinone, nitrobenzene, trichlorobenzene, xylene, ethanol, acetone, tetrahydrofuran or acetonitrile (test for resistance to solvents).
  • pure boiling solvent e.g. with N, N-dimethylformamide, N-methylpyrrolidinone, nitrobenzene, trichlorobenzene, xylene, ethanol, acetone, tetrahydrofuran or acetonitrile (test for resistance to solvents).
  • a Soxhlet extraction can also be carried out. With this treatment, with a stable intercalation compound, practically no dye passes from the molecular sieve into the solvent.
  • Example 2 2.5 g of the compound mentioned in Example 1 were mixed with 47.5 g of a commercially available stoving lacquer based on alkyd-melamine. 50 ml of glass balls (diameter: 3 to 4 mm) were added and the mixture was dispersed in a commercially available mixer for 30 minutes.
  • the resulting dispersion was applied to art paper using a 150 ⁇ m spiral doctor blade.
  • the mixture was allowed to flash off for 20 minutes, followed by baking at 130 ° C. (10 minutes).
  • the K / S spectrum of the paint spread shows a maximum at 616 nm.

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Abstract

Tamis moléculaires contenant un ou plusieurs chromophores de la classe des indigoïdes. L'invention concerne également leur utilisation en tant que colorants.
PCT/EP1993/000460 1992-03-09 1993-02-27 Tamis moleculaires contenant des colorants a base d'indigo WO1993017966A1 (fr)

Priority Applications (1)

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EP93904030A EP0630353A1 (fr) 1992-03-09 1993-02-27 Tamis moleculaires contenant des colorants a base d'indigo

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DE4207339A DE4207339A1 (de) 1992-03-09 1992-03-09 Molekularsiebe, enthaltend farbstoffe auf basis von indigo
DEP4207339.1 1992-03-09

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WO1993017966A1 true WO1993017966A1 (fr) 1993-09-16

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0849221A1 (fr) * 1996-12-19 1998-06-24 Ciba SC Holding AG Tamis moléculaire contenant un colorant
WO2006138566A3 (fr) * 2005-06-17 2007-09-20 Univ Texas Composites organiques/inorganiques a base d'acides de lewis
WO2008097837A3 (fr) * 2007-02-02 2009-05-14 Univ Texas Complexes organiques/inorganiques sous forme de compositions de couleurs

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19923959A1 (de) 1999-05-25 2000-11-30 Giesecke & Devrient Gmbh Wertdokument

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US3950180A (en) * 1974-07-02 1976-04-13 Mitsubishi Kinzoku Kabushiki Kaisha Coloring composites
DE4126461A1 (de) * 1991-08-09 1993-02-11 Rainer Hoppe Farbstoffbeladenes anorganisches molekularsieb, verfahren zu seiner herstellung und seine verwendung als pigment oder material fuer die optische datenspeicherung

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3950180A (en) * 1974-07-02 1976-04-13 Mitsubishi Kinzoku Kabushiki Kaisha Coloring composites
DE4126461A1 (de) * 1991-08-09 1993-02-11 Rainer Hoppe Farbstoffbeladenes anorganisches molekularsieb, verfahren zu seiner herstellung und seine verwendung als pigment oder material fuer die optische datenspeicherung

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Title
ANALYTICAL CHEMISTRY Bd. 63, Nr. 4, 15. Februar 1991, COLUMBUS US Seiten 348 - 351 R.D.PLACE ET AL. in der Anmeldung erwähnt *
CHEMICAL ABSTRACTS, vol. 83, no. 14, 6. Oktober 1975, Columbus, Ohio, US; abstract no. 117185u, Seite 176 ; *
CHEMICAL ABSTRACTS, vol. 83, no. 16, 20. Oktober 1975, Columbus, Ohio, US; abstract no. 133530h, Seite 119 ; *
DATABASE WPIL Week 8338, Derwent Publications Ltd., London, GB; AN 83-767250 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0849221A1 (fr) * 1996-12-19 1998-06-24 Ciba SC Holding AG Tamis moléculaire contenant un colorant
WO2006138566A3 (fr) * 2005-06-17 2007-09-20 Univ Texas Composites organiques/inorganiques a base d'acides de lewis
WO2008097837A3 (fr) * 2007-02-02 2009-05-14 Univ Texas Complexes organiques/inorganiques sous forme de compositions de couleurs

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DE4207339A1 (de) 1993-09-16
EP0630353A1 (fr) 1994-12-28

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