Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
  • C07F13/005—Compounds without a metal-carbon linkage
• • 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
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
  • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
  • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
  • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
• • 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
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/2208—Oxygen, e.g. acetylacetonates
• • 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
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0213—Complexes without C-metal linkages
  • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp

Definitions

• the invention relates to a process for the preparation of sparingly soluble, crystalline metal complex compounds which are used as bleach catalysts in detergents and cleaners.
• the bleaching component has long been based on bleaching agents that release peroxide compounds during washing. These strongly oxidizing compounds very effectively remove the
• Decanoyloxybenzoic acid find for cleaning hard surfaces, such. B. in dishwashing detergents in addition to bleach activators bleach catalysts reinforced use. This is especially a good
• bleach catalysts are also being used to a greater extent in textile and paper bleaching as well as in chemical synthesis (oxidation reactions).
• bleach catalysts are usually metal-containing
• Coordination compounds such as cobalt pentamine acetates in use, on the other hand are transition metal complexes with open-chain or cyclic ligands of Of particular interest, since they exceed the bleaching performance of simple systems many times over.
• manganese or iron complexes containing ligands based on triazacyclononane and derivatives thereof have particular bleach-active activity or high oxidizing power from the series of the latter catalysts.
• Hexafluorophosphat, perchlorate or tetraphenylborate included.
• WO-A-93/25562 describes a process for preparing effective manganese complex catalysts comprising the following steps:
• Counterion salt such as KPF 6 in an aqueous-alcoholic medium to form a manganese coordination compound
• the manganese coordination compound with an oxidizing agent while maintaining a pH of at least 12, to form the desired manganese complex, wherein the manganese is preferably in the +3 and / or +4 oxidation state,
• step ii) the reaction mixture obtained in step ii) is adjusted to a pH of 7 to 9, then the manganese oxides formed filtered off and the manganese complex isolated by evaporation of the solvent mixture.
• the yields achieved are 59 to 73%.
• WO 96/06145 discloses an ethyl bridged one
• working is carried out in a non-aqueous solvent (acetonitrile), a manganese (III) salt in turn in the presence of the ligand and of the
• the solvent mixture water / alcohol (ethanol) is used in large quantities to achieve solubility of the manganese complex. This results in small space-time yields (0.05 kg / l), furthermore, large amounts of solvent must be evaporated to isolate the complex.
• the manganese complex is often contaminated with an undesirable by-product. This is the salt formed from the ligand (triazacyclononane / derivative) and the counterion (eg PF 6 -).
• manganese complexes which may optionally contain iron as another metal, which leads to an improved space-time yield and manages with few purification steps.
• an organic ligand such as the tricyclononane ligand with a metal salt such as. B.
• Manganese salt implemented the later required counterion is not present.
• the metal ion of the complex formed is at elevated pH to
• the present invention provides a gentle process for the preparation of metal complexes, which works without organic solvent, can be converted to the industrial scale and provides high-purity products in high space-time yield and purity.
• the product is free of by-products such as manganese oxides and ligand salts, so that it is possible to dispense with a further purification step after the synthesis.
• the present invention relates to a process for the preparation of manganese complex compounds of the general formula (1) wherein
• M is selected from manganese and iron in the III or IV oxidation state, but at least one M is a manganese in the III or IV oxidation state,
• X is independently a coordinating or bridging species selected from H 2 O, O 2 2 “ , O 2 “ , O 2 OH, HO 2 ⁇ SH “ , S 2 ⁇ SO, CI “ , N 3 ⁇ SCN ⁇ N 3 _ , RCOO “ , NH 2 " and NR 3 , wherein R is a radical selected from H, alkyl and aryl,
• L is an organic ligand that contains at least two manganese
• z is an integer from -4 to +4,
• Y is a mono- or multivalent counterion from the group
• Hexafluorophosphate, perchlorate or tetraphenylborate is the
• q is an integer from 1 to 4, characterized by the following process steps:
• step a) reacting one or more divalent metal salts, wherein the one or more divalent metal salts are selected from divalent manganese and iron salts and at least one divalent metal salt is a divalent manganese salt, with the ligand L in water as a solvent to form a coordination compound from the one or more divalent metal salts and the ligand L, b) oxidation of the coordination compound from step a) with a
• Oxidizing agent wherein at the same time a pH of 11 to 14 and preferably 12 to 14 is maintained, for the conversion of the metal M from the bivalent to the trivalent and / or tetravalent stage, c) lowering the pH of the reaction mixture to a pH of 4 to 9, preferably from 5 to 8, and separating any metal oxides or hydroxides of the metal M and formed
• Me is an alkali metal ion, an ammonium ion or an alkanolammonium ion and Y, z and q have the meanings indicated, at a pH of 4 to 9 and preferably from 5 to 8 ,
• radical R is preferably C 1 to C 4 -alkyl and the aryl group called radical R is preferably CeH 5 (phenyl).
• the crystalline manganese complex compound of the general formula (1) is isolated in a step e), preferably by filtration or centrifugation.
• Reaction mixtures can be carried out and in particular the fact that the counterion salt Me z Y q only after the oxidation step and the
• step a) of the process according to the invention a water-soluble organic compound
• Manganese (II) salt and optionally additionally a water-soluble iron (II) salt preferably from the group of acetates, carbonates, halides, nitrates and sulfates, for example manganese diacetate, manganese dichloride, manganese dibromide, manganese sulfate, manganese nitrate, iron chloride, iron sulfate or iron nitrate reacted with a ligand compound L, preferably in a molar ratio of 4: 1 to 1: 2, more preferably in a molar ratio of 2: 1 to 1: 1 and particularly preferably in a molar ratio of 1, 5: 1 to 1: 1.
• a water-soluble iron (II) salt preferably from the group of acetates, carbonates, halides, nitrates and sulfates, for example manganese diacetate, manganese dichloride, manganese dibromide, manganese sulfate, manga
• metal (II) salt and the ligand compound are used in a total amount of at least 15 parts by weight per 100 parts by weight of water.
• metal (II) salt and the ligand compound are used in a total amount of at least 15 parts by weight per 100 parts by weight of water.
• All M in the general formula (1) manganese in the III or IV oxidation state and all divalent metal salts from step a) divalent manganese salts.
• the divalent metal salt from step a) is particularly preferably manganese dichloride 4-hydrate.
• organic ligand L preferred is one which is an at least nine-membered ring in which at least two, preferably three or four, nitrogen atoms are involved in the ring and coordinate with the manganese.
• examples include: 1, 4,7-triazacyclononane (TACN), 1, 4,7-trimethyl-1, 4,7-triazacyclononane (1, 4,7-Me3-TACN), 1, 5,9-triazacyclododecane (TACD)
• Particularly preferred from this group are 1, 4,7-trimethyl-l, 4,7-triazacyclononane (1, 4,7-Me3-TACN) and 1, 2-bis- (4,7-dimethyl-1, 4, 7-triazacyclon-1-yl) -ethane (Me 4 -DTNE).
• Especially preferred from this group is
• Iron (II) salt with the ligand L in step a) is carried out according to the invention in water as the sole solvent. It is preferably used only so much water that the divalent metal salt or the metal (II) salt (ie the sum of manganese (II) salt and optionally additionally iron (II) salt) and the ligand compound together in an amount of at least 15 parts by weight, per 100 parts by weight of water.
• the upper limit of the concentration of metal (II) salt and ligand compound can be very high because these and the other reactions can be carried out both in solution and in suspension (dispersion). The upper concentration limit is therefore in
• the metal (II) salt and the ligand are thus combined in an amount of preferably 5 to 55 parts by weight and more preferably from 20 to
• Step a) of the process according to the invention leads to the formation of a coordination compound dissolved in the solvent mixture from the etall (II) salt and the ligand compound.
• the water of crystallization optionally contained in the metal (II) salt is added to the solvent water.
• the metal (II) coordination compound is oxidized at a pH of from 11 to 14, preferably from 12 to 13, in the solution obtained in step a), the oxidizing agent and the base for adjusting the given pH preferably be introduced simultaneously.
• the oxidation is preferably carried out by simultaneously mixing an oxidizing agent selected from the group consisting of air, pure oxygen, hydrogen peroxide, alkali metal peroxide and alkali metal permanganate and an alkali metal hydroxide in the solution obtained in step a) while maintaining the indicated pH.
• the oxidation by mixing a (prepared) mixture consisting of a 0.5 to 35 wt .-%, preferably 3 to 20 wt .-%, aqueous
• Hydrogen peroxide solution and a 5 to 40 wt .-%, preferably 10 to 30 wt .-%, aqueous alkali metal (sodium or potassium) hydroxide solution performed.
• the oxidation is generally carried out at 3 to 20 ° C, preferably 5 to 15 ° C, and at atmospheric pressure.
• the divalent metal used is oxidized to the trivalent or to the preferred tri- and / or tetravalent stage.
• step c) of the process according to the invention the reaction mixture obtained in step b) is adjusted to pH 4 to 9, preferably 5 to 8, by addition of an acid, such as hydrochloric acid or sulfuric acid, and subsequently in
• step d) the counterion salt Me z Y q , where Me is a
• Alkali metal ion, ammonium ion or an alkanolammonium ion and z, q and Y have the meanings given to those obtained in step c)
• the counterion salt Me z Y q is preferably used in an amount such that the molar ratio of metal (II) salt used in step a) to Me 2 Y q salt is 4: 1 to 1: 4, particularly preferably 2: 1 to 1: 2, and more preferably 1: 1 to 1: 2.
• Suitable counterion salts are, for example, perchlorates, tetraphenylborates and hexafluorophosphates, wherein
• Hexafluorophosphate are preferred.
• Manganese complex compounds of the general formula (1) with preferably tetravalent metal produced in a gentle manner.
• Particularly preferred complexes which can be synthesized in this way are:
• the process according to the invention can be used to prepare tri- ⁇ -o-bis [(1-y-trimethyl-1-yl-triazacyclononane-1-manganese-1-bis-hexafluorophosphate monohydrate.
• a high space-time yield (about 0.2 kg / l) and a high-purity product are simultaneously achieved.
• the yields are generally over 80% and the purity at least 98.5%.
• the proportion of metal oxides and hydroxides, such as. B. Mn0 2 is less than 0.3 wt .-%.
• the metal complex is free of ligand salt (for example, salt of the monoprotonated cycloamine and PF 6 anion) whose formation is common in the prior art processes (see below
• the metal complexes prepared by the process according to the invention are used in particular as oxidation catalysts
• Bleaching component in detergents and cleaners in household or commercial laundries besides in textile and paper bleaching and in industrial oxidation reactions.
• Hydrogen peroxide solution is added under temperature control, that is, during the addition of this alkaline hydrogen peroxide solution, the temperature of the reaction mixture is maintained between 10 to 15 ° C. Thereafter, 39.4 g (0.214 mol) of potassium hexafluorophosphate at a pH> 12.5 are added in solid form and then stirring is continued for 2 to 3 hours at room temperature.
• the reaction mixture pH> 12.5
• 9.7 g of 50 wt .-% sulfuric acid is adjusted to a pH of 8 to 9 and the Suctioned solids of the reaction mixture through a paper filter.
• For complete removal of residual amounts of water-soluble, inorganic salts of the filter cake is washed twice with 70 g of ice water. After drying in a vacuum oven at 80 ° C., 64 g (79%) are obtained.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Catalysts (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Priority Applications (6)

Applications Claiming Priority (2)

Publications (1)

Family

ID=41682826

Family Applications (1)

Country Status (7)

Cited By (3)

Families Citing this family (5)

Citations (12)

Family Cites Families (7)

• 2010
  • 2010-09-10 WO PCT/EP2010/005569 patent/WO2011032666A1/de not_active Ceased
  • 2010-09-10 ES ES10760913.3T patent/ES2533072T3/es active Active
  • 2010-09-10 CN CN201080041259.0A patent/CN102510774B/zh active Active
  • 2010-09-10 US US13/394,968 patent/US9012630B2/en active Active
  • 2010-09-10 PL PL10760913T patent/PL2477740T3/pl unknown
  • 2010-09-10 EP EP10760913.3A patent/EP2477740B1/de active Active
  • 2010-09-10 JP JP2012529144A patent/JP5688413B2/ja active Active

Patent Citations (13)

Also Published As

Similar Documents

Legal Events