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WO1995024267A1 - Composition catalytique metallomacrocyclique - Google Patents

Composition catalytique metallomacrocyclique Download PDF

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Publication number
WO1995024267A1
WO1995024267A1 PCT/US1995/001880 US9501880W WO9524267A1 WO 1995024267 A1 WO1995024267 A1 WO 1995024267A1 US 9501880 W US9501880 W US 9501880W WO 9524267 A1 WO9524267 A1 WO 9524267A1
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WO
WIPO (PCT)
Prior art keywords
metallomacrocycle
composition according
transition metal
catalyst composition
catalyst
Prior art date
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Ceased
Application number
PCT/US1995/001880
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English (en)
Inventor
Robert A. Walker Johnstone
Paul Anthony Stocks
Frederick Edward Hardy
Johan Gerwin L. Pluyter
Anthony Joseph Simpson
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Procter and Gamble Co
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Procter and Gamble Co
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Publication date
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Priority to MX9603972A priority Critical patent/MX9603972A/es
Priority to JP7523464A priority patent/JPH09509886A/ja
Publication of WO1995024267A1 publication Critical patent/WO1995024267A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/12—Reserving parts of the material before dyeing or printing ; Locally decreasing dye affinity by chemical means
    • 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
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • 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
    • 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
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation
    • 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
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • 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
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • 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
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • 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
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56—Vanadium
    • 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
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • 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
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Definitions

  • the present invention relates to a composition which is capable of enhancing the half life in aqueous media, containing a source of hydrogen peroxide, of a metallomacrocycle catalyst composition; to a Dye Transfer Inhibiting (DTI) composition and its process for inhibiting dye transfer between fabrics during washing.
  • DTI Dye Transfer Inhibiting
  • Suspended or solubilised dyes can to some degree be oxidised in solution by employing known bleaching agents.
  • European Patent 538228 describes a DTI composition comprising a metallo catalyst, a polymer and an enzymic system capable of generating hydrogen peroxide wherein said polymer reduces the deposition of the metallo catalyst onto fabrics.
  • European Patent 553608 describes a DTI composition comprising a metallo catalyst, an amine base catalyst stabiliser, and an enzymic system capable of generating hydrogen peroxide wherein said amine base is capable of binding the 5th ligand of the metallo catalyst.
  • the addition of said polymer reduces the rate of self destruction of the transition metal catalyst, resulting in improved through-the-wash stability of the transition metal catalyst and enables the use of a wider range of transition metal catalyst compounds.
  • a dye transfer inhibiting composition which exhibits optimum dye transfer inhibiting properties.
  • the invention provides an efficient process for laundering operations involving coloured fabrics.
  • the present invention relates to a metallomacrocycle catalyst composition
  • transition metal catalyst selected from: a-a transition metal porphin and mixtures thereof; b-a transition metal phthalocyanine and mixtures thereof; c-mixtures of transition metal porphin and transition metal phthalocyanine; and (ii)-an amphiphilic polymer and mixtures thereof; the complex increasing the half life of the catalyst by a factor of at least 1.1.
  • the half life of the catalyst is defined as the half life of the oxidative stability of the catalyst in aqueous media, containing a source of peroxide.
  • a dye transfer inhibiting composition its process and also an epoxidation process is provided.
  • Figure 1 shows the general formula for porphin compounds wherein the transition metal is in the oxidation state (II).
  • Figure 2 shows the general formula for porphin compounds wherein the transition metal is in the oxidation state (III).
  • Figure 3 shows the corresponding formula of phthalocyanine compounds wherein the transition metal is in the oxidation state (II).
  • Figure 4 shows the corresponding formula of phthalocyanine compounds wherein the transition metal is in the oxidation state (III).
  • metallo catalysts e.g. metallo porphins are susceptible to self-destruction .
  • the level of added catalyst should be such that sufficient active catalyst is present to bleach the dyes throughout the total wash cycle.
  • the life time of the metallo catalyst in aqueous media is enhanced by adding a polymer which forms a complex with the catalyst and also solubilises it.
  • a polymer which forms a complex with the catalyst and also solubilises it is provided by a micellar polymer or polymeric pseudomicelle which are capable of self-organisation due to hydrophobic interactions.
  • the hydrophobic 'microdomain' created by this class of amphiphilic polymer solubilises the hydrophobic catalyst.
  • the present invention provides a complex comprising two elements :
  • transition metal catalyst selected from: a-a transition metal porphin and mixtures thereof, b-a transition metal phthalocyanine and mixtures thereof, c-mixtures of transition metal porphin and transition metal phthalocyanine, and (ii)-an amphiphilic polymer and mixtures thereof; the complex increasing the half life of the catalyst by a factor of at least
  • the essential transition metal porphin structure may be visualised as indicated in Figure 1 and/or Figure 2 in the separate sheet.
  • Figure land 2 the atom positions are numbered conventionally and the double bonds are put in conventionally.
  • Porphin and porphyrin in the literature, are used as synonyms, but conventionally porphin stands for the simplest porphyrin without any substituents; wherein porphyrin is a sub-class of porphin.
  • the references to porphin in this application will include porphyrin.
  • Transition metal porphin structures are those substituted at one or more of the 5, 10, 15 and 20 carbon positions of formula 1 (Meso positions) with substituents selected from hydrogen, alkyl groups such as methyl, ethyl, propyl, t-butyl group, and aromatic ring systems selected from substituted or unsubstituted pyridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties.
  • substituents selected from hydrogen, alkyl groups such as methyl, ethyl, propyl, t-butyl group, and aromatic ring systems selected from substituted or unsubstituted pyridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties.
  • Preferred transition metal porphin structures are those substituted at one or more of the 5, 10, 15 and 20 carbon positions of formula 1 (Meso positions), with an aromatic ring system selected from substituted or unsubstituted phenyl, pyridyl, pyridyl-N-oxide, naphthyl and anthracyl substituent.
  • a more preferred metallo porphin is one in which the molecule is substituted at the 5,10,15 and 20 carbon positions with a pyridyl substituent selected from:
  • each X ⁇ independently, is selected from H, F, CI, Br, NO2, alkyl, alkoxy, cycloalkyl, aralkyl, aryl, alkaryl and heteroaryl; preferably H, CI or F; and X2 is selected from O", OH, H, alkyl, alkoxy, cycloalkyl, aralkyl, aryl, alkaryl and heteroaryl, preferably O".
  • Another highly preferred metallo porphin is one in which the molecule is substituted at the 5,10,15 and 20 carbon positions with a phenyl substituent selected from:
  • each X independently, is selected from H, F, CI, Br, -SO3H, SO2NR2 where R is selected from H, alkyl, and hydroxyalkyl,-C ⁇ 2H, alkyl, alkoxy, cycloalkyl, aralkyl, aryl, alkaryl and heteroaryl, preferably H, CI or F;
  • This preferred compound is known as transition metal tetraphenylporphin.
  • the compound of Figure 1 and/or Figure 2 may be substituted at one or more of the remaining carbon positions by substituents selected from F, CI, Br and Ci-C ⁇ o alkyl.
  • the compound of Figure 1 and/or Figure 2 may be substituted at one or more of the 2,3,7,8, 12,13, 17, 18 carbon positions by a substituent selected from F, CI, Br, alkyl, alkylcarboxy, alkylhydroxyl, vinyl, alkenyl and aryl.
  • the transition metals which can be used are selected from Cu, Fe, Mn, Co, Cr, Ti, V or other transition metals, preferably Mn.
  • the symbol X ⁇ of Figure 2 represents an anion, preferably OH- or CI- when the oxidation state is (III).
  • the transition metal of the porphin is in the oxidation state (III).
  • Porphin derivatives also include chlorophylls, chlorins and bacteriochlorins.
  • Transition metal phthalocyanines and their derivatives have the structure indicated in Figure 3 and/or Figure 4, wherein the atom positions of the phthalocyanine structure are numbered conventionally.
  • Transition metal phthalocyanine structures are those substituted at one or more of the 1-4, 6, 8-11 , 13, 15-18, 20, 22-25, 27 atom positions of Figure 3 and/or Figure 4 with substituents selected from hydrogen, alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, phenyl, naphthalene and anthracene groups.
  • a preferred transition metal phthalocyanine is non-substituted phthalocyanine.
  • the transition metals which can be used are selected from Cu, Fe, Mn, Co, Cr, Ti, V or other transition metals, preferably Mn.
  • the symbol X ⁇ of Figure 4 represents an anion, preferably OH- or Cl- when the oxidation state is (III).
  • the transition metal of the phthalocyanine is in the oxidation state (II).
  • the second element of the invention is a polymer comprising at least one hydrophilic group and at least one hydrophobic group, such that the ratio of hydrophilic group and hydrophobic groups lies in the range from 1:10 to 10:1 ; preferably from 1:3 to 3: 1.
  • hydrophobic moieties interact with the insoluble catalyst through hydrophobic interactions such as 11-11 interactions, and/or charge transfer interactions, and/or Van der Waals interactions which stabilise the composition in a polymeric pseudo micelle while the hydrophilic group(s) of the polymer solubilise the composition.
  • hydrophobic interactions such as 11-11 interactions, and/or charge transfer interactions, and/or Van der Waals interactions which stabilise the composition in a polymeric pseudo micelle while the hydrophilic group(s) of the polymer solubilise the composition.
  • charge transfer interactions an electron donor-acceptor complex is formed.
  • Preferred polymeric structures for solubilisation of oxidative catalysis are structures of the formula :
  • a and B can be selected from : -CH2-, NH ,0 , ketone, an ester linkage, an amide linkage, an imine linkage;
  • n,m,p,r,s,t can independently be any entire number as long as (n + m+p)v- (r-r-s- ⁇ L t)w range from 1-1000 , preferably from 1-500 and such that the ratio v/w varies between 0.1 and 1 ; where the values of q and u, independently lie in the range from 1-10.
  • Each R independently, can be selected from H, alkyl, haloalkyl, alkenyl, alkynyl; preferably H or CH3.
  • Rl is selected from (partially) hydrophobic moieties containing aromatic hydrocarbon rings derived from compounds such as toluene, methyl styrene, stilbene, pyridine, naphthalene, anthracene, phenanthrene, phenyl, histidine, tryptophan, phenyl alanine, tyrosine, alkyl benzene, xylenes, carbazoles, xanthenes, acridines, purines, pyridazines and indoles.
  • aromatic hydrocarbon rings derived from compounds such as toluene, methyl styrene, stilbene, pyridine, naphthalene, anthracene, phenanthrene, phenyl, histidine, tryptophan, phenyl alanine, tyrosine, alkyl benzene, xylenes, carbazoles, xanthenes, acrid
  • R2 is selected to provide water-solubility and these substituents are therefore hydrophilic in nature such as -OH, hydroxyalkyl such as hydroxy methyl and hydroxyethyl; polyoxyethylene, hydroxyphenyl and derivatives thereof, moieties derived from pyrrolidone, pyridine-N-oxide, N-oxide derivatives of histidine, tryptophan, phenyl alanine, tyrosine; phenyl sulphonate, naphthalene sulphonate, imidazole, water-soluble salt derivatives of naphthalene, anthracene, phenanthrene, phenyl, carbazoles, xanthenes, acridines, purines, pyridazines, indoles, -COOH, -COOM, -SO3M where M is an alkali metal ion ; -NR2, -NR3 " * " X ⁇ where X is
  • Rl and R2 independently, can be substituents on the moieties A and B in the event that A and/or B are not an ether, ketone, amide, imine, or ester linkage.
  • Another class of polymer suitable for the present invention are the substituted polysaccharides of the unit structure:
  • Rl R2 where C and D are oligosaccharide units and where oligosaccharide units comprise the product of polycondensation of monosaccharides by O- glycosidic linkage containing up to 10 such residues selected from hexose, pentose and deoxyhexose residues; where the values of q and u, independently, lie in the range from 1 to 10; and where the substituents Rl and R2 remain the same as mentioned before.
  • a third class of polymers that has been identified as suitable for this invention has the unit structure:
  • E and F are di-substituted aromatic moieties such as phenylene, naphthalene, phenanthroline, anthracene, thiophene; where the values of q and u, independently, lie in the range from 1 to 10; where the substituents Rl and R2 remain the same as mentioned before.
  • the molecular weight of the polymer is in the range of from 500 to 1000000 and preferably from 1000 to 500000.
  • the polymeric systems described can be random, graft, or block polymers.
  • the polymeric system can also contain more than two different monomers as long as the ratio of hydrophilic and hydrophobic groups lies in the range from 1 :10 to 10: 1; preferably from 1 :3 to 3:1.
  • Preferred polymers are aromatic amphiphilic polymers selected from: polystyrene sodium sulphonate-co-vinyl naphthalene, poly vinyl pyrrolidone-co- vinyl imidazol, polynaphthalene sulphonate (TAMOL®).
  • a more preferred copolymer is polystyrene sodium sulphonate-co-vinyl naphthalene.
  • the polymeric system can be a homopolymer which exhibits amphiphilic character such as partially neutralised polymethacrylic acid.
  • saccharides that are suitable for the solubilisation of oxidative catalysts which are the cyclic polysaccharides such as natural cyclodextrins and modified cyclodextrins. Where the polymer is a cyclodextrin, an inclusion complex is formed with the transition metal catalyst.
  • the process for making a metallomacrocycle catalyst composition which is a transition metal porphin catalyst composition in solid form comprises the following steps: a-dissolving said metallomacrocycle catalyst in a water miscible organic material; b-dissolving said polymer in H2O; c-adding said predissolved polymer to the predissolved catalyst; d-adding at least 25 % of distilled water slowly with stirring; and e-removing the water miscible organic material by evaporation and the water by freeze drying.
  • the water miscible organic material may be any material in which the organo metallic catalyst is soluble.
  • a suitable material is a water-miscible organic solvent selected from methanol, ethanol, isopropanol, n-propanol, acetone, N- Methylpyrrolidone and Dimethylformamide, preferably methanol, ethanol, isopropanol, n-propanol or acetone.
  • a particularly preferred water miscible material for the production of the catalyst complex in liquid form is a nonionic surfactant of formula
  • R is a C8-C22 alkyl; where n lies in the range from 2 to 24, preferably 7.
  • the synthesis comprises the following steps: i)-Transition metal phthalocyanine catalyst is dissolved in a water- miscible organic solvent, preferably Dimethylsulfoxide (DMSO). ii)- Addition of solid polymer to this solution, and iii)- Addition of a small amount of water while the mixture is stirred continuously.
  • a water- miscible organic solvent preferably Dimethylsulfoxide (DMSO).
  • Transition metal phthalocyanine catalyst is dissolved in melted polymer and stirred for half an hour.
  • the solution is mixed with an excess of acetone. During 2-4 hours a coloured precipitate is formed which is isolated using suction filtration followed by vacuum drying.
  • the complex in the aqueous solution is extracted with underivatized silica gel (containing hydroxyl groups) until the solution is colourless.
  • the silica is collected after suction filtration and dried under vacuum.
  • the principal use of the invention relates to a DTI composition and also to an epoxidation process.
  • This first form relates to a detergent additive composition adapted to provide Dye Transfer Inhibition, when added to an aqueous wash liquor containing a surfactant and a source of active oxygen, further comprising enzymes, builders and other conventional detergent ingredients.
  • the addition of the complex can be by itself or with other additives.
  • a process for inhibiting dye transfer between fabrics during laundering operations involving coloured fabrics, said process comprising contacting said fabrics with a laundering solution containing a detergent additive composition together with a source of available oxygen.
  • the source of available oxygen will be more fully described hereinafter.
  • the second form relates to a Dye Transfer Inhibiting composition
  • a Dye Transfer Inhibiting composition comprising an organometallic composition, described hereinbefore, together with a source of available oxygen.
  • a process for inhibiting dye transfer between fabrics during laundering operations involving coloured fabrics, said process comprising contacting said fabrics with a laundering solution containing a dye transfer inhibiting composition together with a source of available oxygen.
  • the source of available oxygen will be more fully described hereinafter.
  • the complex is normally at a level from 0.0001 % to 0.1 % by weight of the detergent composition, preferably from 0.0005% to 0.01 % , more preferably 0.002% .
  • This is designed to provide a complex at a level, in the wash, from 1*10" 8 molar to 1*10 ⁇ 3 molar, preferably from 1*10" ⁇ molar to 1*10 ⁇ 4 molar.
  • Detergent compositions in accordance with the invention also comprise in general items those ingredients commonly found in detergent products which may include organic surfactants, additional detergent builders, oxygen bleach systems and ancillary materials such as anti-redeposition and soil suspension agents, suds suppressors, additional heavy metal ion chelating agents, enzymes, optical brighteners, photoactivated bleaches, perfumes and colours. Some products also include fabric softening and antistatic agents.
  • Oxygen bleach system can be selected from:
  • ⁇ -conventional bleaches which can comprise:
  • Hydrogen peroxide itself organic peroxy carboxylic acids, inorganic peroxy bleaches selected from persulphate, inorganic perhydrate such as perborate, percarbonate, perpolyphosphates, and combination of said inorganic peroxy bleaches with organic peroxyacid precursors where the bleach activator is selected from N-acyl compounds such as tetraacetylethylenediamine (TAED), O-acyl compounds such as Nonanoyl Oxy Benzene Sulphonate (NOBS, described in US 4,412,934), 3,5,- trimethylhexanoyl Oxy Benzene Sulphonate ( ISONOBS, described in EP 120,591 ), Benzoyl caprolactam, Phenol sulphonate ester of acylaminocaproic acid.
  • N-acyl compounds such as tetraacetylethylenediamine (TAED)
  • O-acyl compounds such as Nonanoyl Oxy Benzene Sulphonate (
  • the bleach level in the wash lies in the range from 100 to 10000 ppm, preferably from 100 to 1000 ppm.
  • the precursor-to-bleach ratio lies in the range from 0.05 to 0.8, preferably from 0.1 to 0.6.
  • a suitable enzyme is an oxidase such as urate oxidase, galactose oxidase, alcohol oxidase, amine oxidase, amino acid oxidase, cholesterol oxidase and glucose oxidase, malate oxidase, glycollate oxidase, hexose oxidase, aryl alcohol oxidase, L-gulonolactose oxidase, pyranose oxidase, L- sorbose oxidase, pyridoxine 4-oxidase, 2-2-hydroxyacid oxidase, choline oxidase, ecdysone oxidase.
  • an oxidase such as urate oxidase, galactose oxidase, alcohol oxidase, amine oxidase, amino acid oxidase, cholesterol oxidase and glucose oxid
  • the preferred enzymatic systems are alcohol oxidase, aldehyde oxidase and glucose oxidase.
  • the more preferred systems for granular detergent application would have solid alcohols, e.g. glucose whose oxidation is catalysed by glucose oxidase to glucuronic acid with the formation of hydrogen peroxide.
  • solid alcohols e.g. glucose whose oxidation is catalysed by glucose oxidase to glucuronic acid with the formation of hydrogen peroxide.
  • liquid alcohols which could for example, also act as solvents.
  • An example is ethanol/ethanol oxidase.
  • compositions are conveniently used as detergent additive products to conventional detergent compositions.
  • Such additive products are intended to implement or boost the performance of conventional detergent compositions.
  • the present invention also encompasses dye transfer inhibiting compositions which will contain other detergent ingredients and thus serve as detergent compositions.
  • a wide range of surfactants can be used in the detergent compositions.
  • a list of suitable cationic surfactants is given in U.S. P. 4,259,217 issued to Murphy on March 31, 1981.
  • Mixtures of anionic surfactants are suitable herein, particularly blends of sulphate, sulphonate and/or carboxy late surfactants.
  • Mixtures of sulphonate and sulphate surfactants are normally employed in a sulphonate to sulphate weight ratio of from 5: 1 to 1 :2, preferably from 3: 1 to 2:3, more preferably from 3: 1 to 1 : 1.
  • Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a Ci2 _ Cl8 fatty source, preferably from a C16-C18 f attv source.
  • the cation is an alkali metal, preferably sodium.
  • Preferred sulphate surfactants in such sulphonate sulphate mixtures are alkyl sulphates having from 12 to 22, preferably 16 to 18 carbon atoms in the alkyl radical.
  • Another useful surfactant system comprises a mixture of two alkyl sulphate materials whose respective mean chain lengths differ from each other.
  • One such system comprises a mixture of C1 -C15 alkyl sulphate and C16-C18 alkyl sulphate in a weight ratio of C14-C15: Ci6-C ⁇ g of from 3: 1 to 1 : 1.
  • the alkyl sulphates may also be combined with alkyl ethoxy sulphates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6.
  • the cation in each instance is again an alkali metal, preferably sodium.
  • Another highly preferred anionic surfactant system comprises a mixture of a C12-C2O alkyl sulfate salt with a water soluble Cn_Ci8 alkyl ethoxysulfate salt containing an average of from 1 to 7 ethoxy groups per mole wherein the weight ratio of alkyl sulfate to alkyl ethoxysulfate salt lies in the range from 2 : 1 to 19 : 1 , more preferably from 3 : 1 to 12 : 1 and most preferably from 3.5 : 1 to 10 : 1.
  • the alkyl sulfate salts may be derived from natural or synthetic hydrocarbon sources.
  • Preferred examples of such salts include the substantially branched C14-C15 alkyl sulfate salts, that is where the degree of branching of the C14-C15 alkyl chain is greater than about 20% .
  • Such substantially branched C14-C15 alkyl sulfate salts are usually derived from synthetic sources.
  • C16-C20 alkyl sulfate salts which are usually derived from natural sources such as tallow fat and marine oils.
  • the C11-C18 alkyl ethoxysulfate salt comprises a primary alkyl ethoxysulfate which is derived from the condensation product of a C ⁇ - Ci8 alcohol condensed with an average of from one to seven ethylene oxide groups, per mole.
  • C11-C18 alcohol itself can be obtained from natural or synthetic sources.
  • C H-CJ S alcohols derived from natural fats, or Ziegler olefin build-up, or OXO synthesis can form suitable sources for the alkyl group.
  • synthetically derived materials include Dobanol 25 (RTM) sold by Shell Chemicals (UK) Ltd which is a blend of C12-C15 alcohols, Ethyl 24 sold by the Ethyl Corporation, a blend of C13.C15 alcohols in the ratio 67% C13, 33% C15 sold under the trade name Lutensol by BASF GmbH and Synperonic (RTM) by ICI Ltd. , and Lial 125 sold by Liquichimica Italiana.
  • Examples of naturally occurring materials from which the alcohols can be derived are coconut oil and palm kernel oil and the corresponding fatty acids.
  • the level of CJ I-CJS alkyl ethoxysulfate is preferably from 0.5% to 10% more preferably from 0.5% to 5 % and most preferably from 1 % to 3 % by weight of the composition.
  • anionic surfactants suitable for the purposes of the invention are the alkali metal sarcosinates of formula
  • R-CON (R 1 ) CH2 COOM wherin R is a C5-C17 linear or branched alkyl or alkenyl group, R is a C1-C4 alkyl group and M is an alkali metal ion.
  • Preferred examples are the lauroyl, Cocoyl (C12-C14), myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
  • One class of nonionic surfactants useful in the present invention comprises condensates of ethylene oxide with a hydrophobic moiety, providing surfactants having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5.
  • HLB hydrophilic-lipophilic balance
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing an average of from 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 primary alcohols containing an average of from 6-8 moles of ethylene oxide per mole of alcohol and the C12-C15 primary alcohols containing an average of from 3-5 moles of ethylene oxide per mole of alcohol.
  • Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
  • RO C n H 2n O
  • t Z
  • x Z x
  • Z is a moiety derived from glucose
  • R is a saturated hydrophobic alkyl group that contains from 6 to 18 carbon atoms
  • t is from 0 to 10 and n is 2 or 3
  • x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and
  • Another preferred nonionic surfactant is a polyhydroxy fatty acid amide surfactant compound having the structural formula:
  • Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably Cj or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R ⁇ is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or mixture thereof: and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxlylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH2-(CHOH) n -CH2 ⁇ H, -CH(CH2 ⁇ H)-(CHOH) n . r CH2OH, -CH2-(CHOH)2(CHOR')(CHOH)-CH2 ⁇ H, where n is an integer from 3 to 5, inclusive, and R 1 is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2 ⁇ H.
  • R can be, for example, N-methyl, N-ethyl, N-propyl, N- isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R2-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymalto- triotityl, etc.
  • Preferred compound are N-methyl N-ldeoxyglucityl C14- Ci8 fatty acid amides.
  • a further class of surfactants suitable for the purposes of the invention are the gemini polyhydroxyfatty acid amide more fully disclosed in US Patent Application No 08/187251.
  • a further class of surfactants are the semi-polar surfactants such as amine oxides.
  • Suitable amine oxides are selected from mono C6-C20 > preferably C10-C14 N-alkyl or alkenyl amine oxides and propylene-1 ,3- diamine dioxides wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxpropyl groups.
  • Cationic surfactants can also be used in the detergent compositions herein and suitable quaternary ammonium surfactants are selected from mono C8-C16, preferably C10-C14 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Laundry detergent compositions of the present invention comprise from 3% to 30% of surfactant but more usually comprise from 5% to 20%, more preferably from 7% to 15 % surfactant by weight of the compositions.
  • Machine dishwashing detergent compositions of the present invention comprise from 0% to 10% by weight, preferably from 0.5% to 10% by weight, most preferably from 1 % to 5 % of surfactant by weight of the compositions.
  • a detergent builder system comprising one or more other non- phosphate detergent builders.
  • these can include, but are not restricted to, alkali metal aluminosilicates zeolites, amorphous and crystalline layered sodium silicates, ethylenediamine-N,N'-disuccinic acid (EDDS), carbonates borates, monomeric polycarboxylates, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms and mixtures of any of the foregoing.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • carbonates borates monomeric polycarboxylates, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms and mixtures of any of the foregoing.
  • aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28% , more preferably from 18% to 22% water in bound form.
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available and can be naturally occurring materials, but are preferably synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in US Patent No. 3,985,669.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, Zeolite MAP, Zeolite MAB and mixtures thereof.
  • the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula
  • x is from 20 to 30, especially 27.
  • Zeolite X of formula Na86 [(Al ⁇ 2)86(Si ⁇ 2)l06]- 276 H2O is also suitable, as well as Zeolite HS of formula Na6 [(Al ⁇ 2)6(Si ⁇ 2)6] 7.5 H2 O).
  • Preferred non-phosphate builder salts are the crystalline layered sodium silicates of the general formula
  • M is sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the -, ⁇ -, ⁇ - and ⁇ - forms of Na2S_2 ⁇ 5.
  • These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is ⁇ -Na2Si2 ⁇ 5, NaSKS-6.
  • the laundry detergent compositions of the present invention preferably comprise crystalline layered sodium silicate at a level of from 1 % to 80% by weight of the composition, more preferably from 5% to 40% and most preferably from 7% to 20% by weight.
  • the crystalline layered sodium silicate material is preferably present in granular detergent compositions in accord with the invention as a particulate in intimate admixture with a solid, water-soluble ionisable material.
  • the solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof.
  • Suitable organic acids include ascorbic, citric, glutaric, gluconic, glycolic, malic, maleic, malonic, oxalic, succinic and tartaric acids, 1 hydroxy ethane 1 , 1-diphosphonic acid (EHDP), amino poly methylene phosphonic acids such as NTMP, EDTMP & DETPMP, and mixtures of any of the foregoing.
  • Suitable acid salts include sodium hydrogen carbonate, sodium hydrogen oxalate, sodium hydrogen sulphate, sodium acid pyrophosphate, sodium acid orthophosphate, sodium hydrogen tartrate or mixtures of any of the foregoing.
  • the particulate mixture of crystalline layered silicate and solid water soluble ionisable material will have a pH of at least 10 (as measured on a 1 % solution in 20 °C distilled water) and more usually will have a pH of at least 11 , normally at least 11.5.
  • agglomerates may require the addition of one or more binder agents in order to assist in binding the silicate and ionisable water soluble material so as to produce particulates with acceptable physical characteristics.
  • the binder agents may be present at a level of from 0% to 20% by weight of the composition.
  • the binder agents will be in intimate admixture with the silicate and ionisable water soluble material.
  • Preferred binder agents have a melting point between 30°C-70°C.
  • the binder agents are preferably present in amounts from 1-10% by weight of the composition and most preferably from 2-5 % by weight of the composition.
  • Preferred binder agents include the C10-C20 alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole of alcohol and more preferably the C 5-C2O primary alcohol ethoxylates containing from 20-100 moles of ethylene oxide per mole of alcohol.
  • binder agents include certain polymeric materials.
  • Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols with an average weight of from 600 to 10,000 are examples of such polymeric materials.
  • Copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the polymer are further examples of polymeric materials useful as binder agents.
  • These polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C ⁇ o ⁇ C20 alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole.
  • Further examples of binder agents in accord with the invention include the C10 -C20 mono- and diglycerol ethers and also the C10-C20 fatty acids. Solutions of certain inorganic salts including sodium silicate are also of use for this purpose.
  • Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acid or their salts are other examples of binder agents in accord with the invention.
  • the particulate can also include other components that are conventional in detergent compositions, provided that these are not incompatible per se and do not interfere with the building function of the crystalline layered silicate.
  • Suitable polycarboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831 ,368, 821 ,369 and 821 ,370.
  • Polycarboxylates containing two carboxy groups include the water- soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxy lates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1 ,379,241 , lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2- oxa-l ,l ,3-propanetricarboxylates described in British Patent No.1 ,387,447.
  • Polycarboxylates containing four carboxy group include oxodisuccinates disclosed in British Patent No.1 ,261 , 829, 1 ,1 ,2,2-ethane tetracarboxy lates, 1 ,1 ,3,3-propane tetracarboxylates and 1 ,1 ,2,3-propane tetracarboxy lates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1 ,398,422 and in U.S. Patent No. 1,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane- cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxy lates, 2,3,4,5-tetrahydrofuran-cis,cis,cis-tetracarboxylates, 2,5-tetrahydrofuran- cis-dicarboxy lates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1 ,2,3,4,5,6- hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phtalic acid derivatives disclosed in British Patent No.1 ,425, 343.
  • the preferred polycarboxylates are hydro xycarboxy lates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as components of builder systems of detergent compositions in accordance with the present invention.
  • Suitable water soluble organic salts are the homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A-1 ,596,756.
  • Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000. These materials are normally used at levels of from 0.5% to 10% by weight more preferably from 0.75 % to 8 % , most preferably from 1 % to 6% by weight of the composition.
  • the detergent compositions of the present invention will comprise non- phosphate detergent builder compounds at a level of from 1 % to 80% by weight of the compositions, more preferably from 10% to 60% by weight and most preferably from 20% to 50% by weight.
  • sodium aluminosilicate such as Zeolite A will comprise from 20% to 60% by weight of the total amount of builder, a monomeric or oligomeric carboxylate will comprise from 5 % to 30% by weight of the total amount of builder and the crystalline layered silicate will comprise from 10% to 65% by weight of the total amount of builder.
  • the builder system preferably also incorporates a combination of auxiliary inorganic and organic builders such as sodium carbonate and maleic anhydride/acrylic acid copolymers in amounts of up to 35 % by weight of the total builder.
  • a suitable chelant for inclusion in the detergent composition in accordance with the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na2EDDS and Na4EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg2EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.
  • the detergent compositions may contain optional chelant ingredients.
  • optional chelants may include the organic phosphonates, including amino alkylene poly (alkylene phosphonate), alkali metal ethane 1- hydroxy diphosphonates, nitrilo tremethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
  • the phosphonate compounds may be present either in their acid form or as a complex of either an alkali or alkaline metal ion, the molar ratio of said metal ion to said phosphonate compound being at least 1 : 1.
  • the organic phosphonate compounds where present are in the form of their magnesium salt.
  • the level of phosphorus containing chelants in the compositions of the invention is preferably minimised, with their complete exclusion from the compositions being most preferred.
  • Amorphous silicates are useful components of detergent compositions. Silicates are present in the machine detergent compositions at a level of less than 10% by weight of the composition, more preferably less than 5% by weight. Whilst soluble silicates serve a variety of purposes in conventional laundry detergent formulations, their presence may be unnecessary in detergent compositions incorporating crystalline layered silicate material. However as the crystalline layered silicate, which forms part of the builder system of the detergent composition, must be added as a dry mix ingredient, soluble silicates may still be useful as structurants in the spray dried granules that normally form part of a laundry detergent composition. This is particularly desirable if the spray dried granule does not incorporate an aluminosilicate builder and would otherwise comprise only organic materials. Suitable silicates are those having an Si ⁇ 2:Na2 ⁇ ratio in the range from 1.6 to 3.4, ratios from 2.0 to 2.8 being preferred.
  • Anti-redeposition and soil-suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, homo-or co-polymeric polycarboxylic acids or their salts and ployamino compounds.
  • Polymers of this type include the polyacrylates and copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer disclosed in detail in EP-A- 137669.
  • Polyamino compounds such as those derived from aspartic acid are disclosed in EP-A-305282, EP-A-305283 and EP-A-351629. These materials are normally used at levels of from 0.5 % to 10% by weight, more preferably from 0.75 % to 8 % , most preferably from 1 % to 6% by weight of the composition.
  • polyethylene glycols particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
  • Preferred optical brighteners are anionic in character, examples of which are disodium 4,4l-bis-(2-diethanolamino-4-anilino -s- triazin-6- ylamino)stilbene-2:2l disulphonate, disodium 4,4l-bis-(2-morpholino -4- anilino-2-triazin-6-ylaminostilbene-2:2l-disulphonate, disodium 4, 4l-bis- (2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2l - disulphonate, monosodium 4 >4 l-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2- sulphonate, disodium 4,4l-bis-(2-anilino-4-(N-methyl-N-2- hydroxy ethylamino)-2-triazin-6-y lamino)stilbene-2 ,21 - disulphon
  • Soil-release agents useful in detergent compositions are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0272033. A particular preferred polymer has the formula:
  • Polyvinyl pyrrolidones typically of MWt 5000-20000, preferably 10000- 15000, also form useful agents in preventing the transfer of labile dyestuffs between fabrics during the washing process.
  • other useful agents are polyvinylimadazoline, polyvinylpyrrolidone, polyvinyl alcohol which are more fully described in EP-538,228.
  • Another optional detergent composition ingredient is a suds suppressor, exemplified by silicones, and silica-silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms, exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water- dispersible, substantially non-surface-active detergent-impermeable carrier.
  • the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • useful silicone suds controlling agents can comprise a mixture of an alkylated siloxane, of the type referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
  • a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl- silanated) silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50 m ⁇ /g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1 : 1 to about 1 :2.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. US Patent 3,933,672.
  • Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2,646, 126 published April 28, 1977.
  • An example of such a compound is DC0544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
  • the suds suppressors described above are normally employed at levels of from 0.001 % to 5% by weight of the composition, preferably from 0.1 % to 3 % by weight.
  • the preferred methods of incorporation comprise either application of the suds suppressors in liquid form by spray-on to one or more of the major components of the composition or alternatively the formation of the suds suppressors into separate particulates that can then be mixed with the other solid components of the composition.
  • the incorporation of the suds modifiers as separate particulates also permits the inclusion therein of other suds controlling materials such as C20-C24 fatty acids, microcrystalline waxes and high MWt copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix. Techniques for forming such suds modifying particulates are disclosed in the previously mentioned Bartolotta et al US Patent No. 3,933,672.
  • Another optional ingredient useful in detergent compositions is one or more enzymes. These may be incorporated at a level of from 0.1 % to 10% , more preferably 0.5% to 5% by weight of the detergent composition.
  • Preferred enzymatic materials include the commercially available amylases, neutral and alkaline proteases, Upases, esterases and cellulases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • Preferred commercially available protease enzymes include those sold under the tradenames Alcalase and Savinase by Novo Industries A/S (Denmark) and Maxatase by International Bio-Synthetics, Inc. (The Netherlands).
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniforms, described in more detail in GB-1,269,839 (Novo).
  • Preferred commercially available amylases include for example, Rapidase, sold by International Bio-Synthetics Inc, and Termamyl, sold by Novo Industries A/S.
  • An especially preferred lipase enzyme is manufactured and sold by Novo Industries A/S (Denmark) under the trade name Lipolase (Biotechnology Newswatch, 7 March 1988, page 6) and mentioned along with other suitable lipases in EP-A-0258068 (Novo).
  • a further optional ingredient useful in detergent compostions is a corrosion inhibitor.
  • C14-C20 fatty acids are preferred examples of such corrosion inhibitors.
  • Fabric softening agents can also be incorporated into laundry detergent compositions. These agents may be inorganic or organic in type. Inorganic softening agents are examplified by the smectite clays disclosed in GB-A-1 ,400,898. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A-1514276 and EP-B- 0011340.
  • Levels of smectite clay are normally in the range from 5% to 15% , more preferably from 8% to 12% by weight, with the material being added as a dry mixed component to the remainder of the formulation.
  • Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1 % to 3 % by weight, whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1 % to 2% , normally from 0.15 % to 1.5 % by weight.
  • these materials can be added to the aqueous slurry fed to the spray drying tower, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as a molten liquid on to other solid components of the composition.
  • the detergent composition according to the invention can be in liquid, paste, or granular forms.
  • Granular compositions according to the present invention can also be in "compact form" , i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/1; in such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt” , compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt.
  • the present invention also relates to a process for inhibiting dye transfer from one fabric to another of solubilised and suspended dyes encountered during fabric washing process.
  • the process comprises contacting fabrics with a laundering solution as hereinbefore described.
  • the process of the invention is conveniently carried out in the course of the washing process.
  • the washing process is preferably carried out at
  • the pH of the treatment solution is preferably from 7 to 11 , especially from 7.5 to 10.5.
  • the detergent compositions according to the present invention include compositions which are to be used for cleaning substrates, such as fabrics, fibers, hard surfaces, skin , etc., for example hard surface cleaning composition compositions (with or without abrasives), laundry detergent compositions and automatic and non automatic dishwashing compositions.
  • the second use of the invention relates to an epoxidation process. Therefore, an epoxidation process carried with the presence of imidazole is provided wherein the metallomacrocycle catalyst composition comprises a complex of
  • transition metal catalyst selected from: a-a transition metal porphin and mixtures thereof, b-a transition metal phthalocyanine and mixtures thereof, c-mixtures of transition metal porphin and transition metal phthalocyanine, and (ii)-an amphiphilic polymer and mixtures thereof; the complex increasing the half life of the catalyst by a factor of at least
  • MnTPP Tetraphenylporphyrin Manganese (III) Chloride available as Aldrich no 25,4754 and the polymer PSSSVN is polystyrene sodium sulphonate vinylnaphthalene copolymer with MW 310,000 :
  • the mix is stirred at room temperature to dissolve the solid before adding
  • this solution is added, with Sprutor agitation, by means of an automatic 10ml pipette (in 'burette' mode) to 700 ml of n-butanol.
  • the cream-coloured solid which formed is vacuum filtered, washed with ether and dried in vacuo over CaCb.
  • the dry weight at this step is 42.81g
  • the solution is thereafter freeze-dried using the Edwards EF-6 dryer.
  • the dry weight of PSSSVN obtained is 38.2g
  • the solution is then freeze-dried.
  • the dry weight of the green complex obtained is 3.16 g and contains 8% by weight of MnTPP.
  • 1-A catalyst solution comprising 10 mg MnTPP in a mixture of lg ethanol/lg water (0.5% solution)
  • PSSSVN in a mixture of 5g ethanol / 5g water (1 % MnTPP/PSSSVN solution); this solution is then lyophilised and a 0.5% solution in EtOH and water(50:50) is made.
  • 3-A buffer solution comprising 0.1M sodium carbonate at pH 10.
  • MnTPP oxidative stability method 50ml of the buffer solution is taken to which is added lOO ⁇ l of the 0.5%
  • the wavelength spectrum is scanned between 350 and 800nm wherein the major peak of MnTPP is around 472nm and is used as a reference (100%
  • MnTPP/PSSSVN solution (10 ppm MnTPP/ 115 ppm PSSSVN).
  • the wavelength spectrum is scanned between 350 and 800nm and is used as a reference (100% MnTPP/PSSSVN)
  • the peak height is proportionate to the amount of active catalyst.
  • 1-A catalyst solution comprising 10 mg MnTPP in a mixture of lg ethanol/lg water (0.5% solution)
  • PSSSVN in a mixture of 5g ethanol / 5g water (1 % MnTPP/PSSSVN solution) 3-Detergent solution: 0.7% of a commercial detergent solution in city water at pH 10.5.
  • the reflectance values (L, a, b-values) of the dry multifibers are measured by using a colorimeter (Spectraflash manufactured by ICS) in order to calculate the Delta E and then the percentage dye oxidation versus the reference multifiber (maximum Delta E).
  • the % dye oxidation relates to the % DTI.
  • the DTI performance of MnTPP-Polymer Complexes was determined with different polymers such as PSSSVN described in Example 1 , Sodium polynaphthalene sulphonate sold by BASF AG under the trade names TAMOL® NH, TAMOL® NNOK, TAMOL® NOC and also with poly vinyl (pyrrolidone-co-imidazol) (PVPVI) where the MW lies in the range from 100-1000000, said polymer being more fully described in EP-0 372 291.
  • polymers such as PSSSVN described in Example 1 , Sodium polynaphthalene sulphonate sold by BASF AG under the trade names TAMOL® NH, TAMOL® NNOK, TAMOL® NOC and also with poly vinyl (pyrrolidone-co-imidazol) (PVPVI) where the MW lies in the range from 100-1000000, said polymer being more fully described in EP-0 372 291.
  • All polymers contained 8 % in weight of MnTPP and the level of MnTPP in the wash was 2 ppm. The temperature was 30°C.
  • PVPVI 48 * Net % DTI means: % DTI of the complex - % DTI of the polymer. Except for PVPVI, none of the polymers alone provided DTI benefits.
  • the MnTPP-PSSSVN provides DTI on a variety of dyes with good performance.
  • MnPc Phthalocyanine Manganese(II) available in Aldrich no 37955-7 and the polymer PVPVI was polyvinyl (pyrrolidone-co-imidazol) where the MWt lies in the range from 100-1000000, said polymer being more fully described in EP-0 372 291.
  • MnPc 0.0361 g of MnPc is dissolved in 10 ml of dimethylsulfoxide (DMSO). To the MnPc solution is dissolved 0.0509 g of PVPVI. The mixture is then poured into an excess (200 ml) of distilled water. A bright blue colour appears and the solution is filtered to remove the excess of MnPc. The blue product in the filtrate is then collected by extraction with 0.4892 g of hydrophilic silica underivatized sold by DEGUSSA under the tradename Sipernat® D22LS. The silica becomes blue while the solution becomes colourless and the silica is then collected and dried.
  • DMSO dimethylsulfoxide
  • Atomic absorption is used to confirm the presence of the complex on the support and the silica has been found to contain 0.11 % by weight of the complex.
  • Tetra(para-methoxyphenyl)porphyrin is available in Aldrich No 25-288-3
  • Manganese tetra(p-methoxyphenyl)porphyrin (7.4.10 ⁇ 3mmol) incorporated into the PSSSVN polymer is dissolved in distilled water (4ml).
  • Dichloromethane (3 ml) is added to form a biphasic system, and to this mixture is added cyclooctene (lmmol), imidazole (4.4.10 ⁇ 2mmol) and finally H2O2 (3mmol).
  • the reaction is carried out in stoppered round bottom flask which is occasionally opened to release any pressure build up.
  • cyclooctene epoxide is observed by following the reaction by gas chromatography using an authentic sample of the epoxide as an external standard.
  • the gas chromatograms are obtained on a Dani 3800 machine incorporating an FFAP 30m column. After 24 hours, the analysis of the reaction by gas chromatography shows that 48% of cyclooctene epoxide has been produced relative to the starting material. % cyclooctene epoxide Blank (no complex) 8
  • reaction is carried out using the procedure described for cyclooctene but substituting 1-methyl cyclohexene in place of cyclooctene. After 48 hours, the analysis of the reaction by gas chromatography shows that 19% of 1-methyl cyclohexene epoxide has been produced relative to the starting material.
  • reaction is carried out using the procedure described for cyclooctene but substituting tetramethyl ethene in place of cyclooctene. After 48 hours, the analysis of the reaction by gas chromatography shows that 7% of tetramethyl ethene epoxide has been produced relative to the starting material.
  • Nai2(A10 2 Si0 2 )l2- 27H 2 0 having a primary particle size in the range from
  • MA/AA Maleic Acid/Acrylic Acid copolymer sodium salt sold by BASF under the trade name Sokalan ® CP 5 with a molecular weight of 90,000.
  • Lipase Lipolytic enzyme sold by Novo Industries A/S under the tradename Lipolase.
  • Silicate Amorphous Sodium Silicate 2 ratio (Si ⁇ 2:Na2 ⁇ )
  • Compositions A, B, C, D are in accordance with the present invention.
  • a detergent aditive formulation (parts by weight) in accordance with the present invention is also provided:

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Abstract

Composition catalytique métallomacrocyclique composée d'un complexe de: (1) un catalyseur d'un métal de transition choisi entre: a) une porphine de métal de transition et des mélanges en contenant, b) une phtalocyanine de métal de transition et des mélanges en contenant, c) des mélanges de porphine de métal de transition et de phtalocyanine de métal de transition; et (2) un polymère amphiphile et des mélanges en contenant. Ledit complexe accroît la demi-vie du catalyseur par un facteur d'au moins 1:1.
PCT/US1995/001880 1994-03-08 1995-02-16 Composition catalytique metallomacrocyclique Ceased WO1995024267A1 (fr)

Priority Applications (2)

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MX9603972A MX9603972A (es) 1994-03-08 1995-02-16 Composicion catalizadora metalomacrociclica.
JP7523464A JPH09509886A (ja) 1994-03-08 1995-02-16 メタロマクロサイクル触媒組成物

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EP94301641.0 1994-03-08
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5853428A (en) * 1996-07-22 1998-12-29 Carnegie Mellon University Metal ligand containing bleaching compositions
GB2329397A (en) * 1997-09-18 1999-03-24 Procter & Gamble Photo-bleaching agent
WO2000052101A1 (fr) * 1999-03-05 2000-09-08 Case Western Reserve University Composition comprenant un agent photo-oxydant et utilisations de cet agent
EP2148919A1 (fr) * 2007-04-25 2010-02-03 Reckitt Benckiser N.V. Composition
CN113338061A (zh) * 2021-05-27 2021-09-03 广州骏亚纺织科技有限公司 双氧水催化剂的组合物及其应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110559949B (zh) * 2019-08-13 2021-06-08 中北大学 酞菁衍生物修饰表面活性剂与多金属氧酸盐自组装纳米材料及其制备方法

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Publication number Priority date Publication date Assignee Title
US4800188A (en) * 1987-03-20 1989-01-24 Hoechst Celanese Corp. Method for supporting metalloporphyrins on polybenzimidazole porous articles
US4806514A (en) * 1986-10-02 1989-02-21 Canadian Patents And Development Limited -Societe Canadienne Des Brevets Et D'exploitation Limitee Composite photocatalyst for refractory waste degradation
DE3924815A1 (de) * 1989-07-27 1991-01-31 Werner Wolters Sensibilisator fuer photooxidative reaktionen und verfahren zu seiner herstellung
SU1685513A1 (ru) * 1989-12-25 1991-10-23 Всесоюзный научно-исследовательский институт углеводородного сырья Способ приготовлени катализатора дл окислени сернистых соединений

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US4806514A (en) * 1986-10-02 1989-02-21 Canadian Patents And Development Limited -Societe Canadienne Des Brevets Et D'exploitation Limitee Composite photocatalyst for refractory waste degradation
US4800188A (en) * 1987-03-20 1989-01-24 Hoechst Celanese Corp. Method for supporting metalloporphyrins on polybenzimidazole porous articles
DE3924815A1 (de) * 1989-07-27 1991-01-31 Werner Wolters Sensibilisator fuer photooxidative reaktionen und verfahren zu seiner herstellung
SU1685513A1 (ru) * 1989-12-25 1991-10-23 Всесоюзный научно-исследовательский институт углеводородного сырья Способ приготовлени катализатора дл окислени сернистых соединений

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5853428A (en) * 1996-07-22 1998-12-29 Carnegie Mellon University Metal ligand containing bleaching compositions
US5876625A (en) * 1996-07-22 1999-03-02 Carnegie Mellon University Metal ligand containing bleaching compositions
US6099586A (en) * 1996-07-22 2000-08-08 Carnegie Mellon University Metal ligand containing bleaching compositions
GB2329397A (en) * 1997-09-18 1999-03-24 Procter & Gamble Photo-bleaching agent
WO2000052101A1 (fr) * 1999-03-05 2000-09-08 Case Western Reserve University Composition comprenant un agent photo-oxydant et utilisations de cet agent
EP2148919A1 (fr) * 2007-04-25 2010-02-03 Reckitt Benckiser N.V. Composition
CN113338061A (zh) * 2021-05-27 2021-09-03 广州骏亚纺织科技有限公司 双氧水催化剂的组合物及其应用

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JPH09509886A (ja) 1997-10-07
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