EP1208107A2 - Ligand et complexe servant a blanchir un substrat selon un procede catalytique - Google Patents

Ligand et complexe servant a blanchir un substrat selon un procede catalytique

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Publication number
EP1208107A2
EP1208107A2 EP00969243A EP00969243A EP1208107A2 EP 1208107 A2 EP1208107 A2 EP 1208107A2 EP 00969243 A EP00969243 A EP 00969243A EP 00969243 A EP00969243 A EP 00969243A EP 1208107 A2 EP1208107 A2 EP 1208107A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
optionally substituted
group selected
ligand
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP00969243A
Other languages
German (de)
English (en)
Inventor
Adrianus C. M. Unilever Res. Vlaardingen Appel
Ronald Unilever Research Vlaardingen Hage
David Unilever Research Port Sunlight TETARD
Robin Stefan Unilever Res. Vlaardingen Twisler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/GB1999/002876 external-priority patent/WO2000012667A1/fr
Priority claimed from GBGB0004854.6A external-priority patent/GB0004854D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP1208107A2 publication Critical patent/EP1208107A2/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/55—Acids; Esters
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • This invention relates to ' a class of ligand or complex useful as catalysts for catalytically bleaching substrates with atmospheric oxygen, and as catalysts in the treatment of textiles such as laundry fabrics whereby bleaching by atmospheric oxygen is catalysed after the treatment.
  • Peroxygen bleaches are well known for their ability to remove stains from substrates.
  • the substrate is subjected to hydrogen peroxide, or to substances which can generate hydroperoxyl radicals, such as inorganic or organic peroxides.
  • these systems must be activated.
  • One method of activation is to employ wash temperatures of 60°C or higher. However, these high temperatures often lead to inefficient cleaning, and can also cause premature damage to the substrate.
  • a preferred approach to generating hydroperoxyl bleach radicals is the use of inorganic peroxides coupled with organic precursor compounds. These systems are employed for many commercial laundry powders. For example, various European systems are based on tetraacetyl ethylenediamine (TAED) as the organic precursor coupled with sodium perborate or sodium percarbonate, whereas in the United States laundry bleach products are typically based on sodium nonanoyloxybenzenesulfonate (SNOBS) as the organic precursor coupled with sodium perborate.
  • TAED tetraacetyl ethylenediamine
  • SNOBS sodium nonanoyloxybenzenesulfonate
  • Precursor systems are generally effective but still exhibit several disadvantages. For example, organic precursors are moderately sophisticated molecules requiring multi-step manufacturing processes resulting in high capital costs.
  • precursor systems have large formulation space requirements so that a significant proportion of a laundry powder must be devoted to the bleach components, leaving less room for other active ingredients and complicating the development of concentrated powders.
  • precursor systems do not bleach very efficiently in countries where consumers have wash habits entailing low dosage, short wash times, cold temperatures and low wash liquor to substrate ratios .
  • hydrogen peroxide and peroxy systems can be activated by bleach catalysts, such as by complexes of iron and the ligand N4Py (i.e. N, N- bis (pyridin-2-yl-methyl) -bis (pyridin-2-yl)methylamine) disclosed in 095/34628, or the ligand Tpen (i.e. N, N, N' , N' -tetra (pyridin-2-yl-methyl) ethylenediamine) disclosed in 097/48787.
  • ligand N4Py i.e. N, N- bis (pyridin-2-yl-methyl) -bis (pyridin-2-yl)methylamine
  • the ligand Tpen i.e. N, N, N' , N' -tetra (pyridin-2-yl-methyl) ethylenediamine
  • aldehydes A broad range of aliphatic, aromatic and heterocyclic aldehydes is reported to be useful, particularly para-substituted aldehydes such as 4-methyl-, 4-ethyl- and 4-isopropyl benzaldehyde, whereas the range of initiators disclosed includes N-hydroxysuccinimide, various peroxides and transition metal coordination complexes.
  • the aldehyde component and radical initiators such as peroxides are consumed during the bleaching process.
  • These components must therefore be included in the composition in relatively high amounts so as not to become depleted before completion of the bleaching process in the wash cycle.
  • the spent components represent a waste of resources as they can no longer participate in the bleaching process.
  • the present invention provides of the general formula: wherein
  • Q independently represents a group selected from C 2 - 3 - alkylene optionally substituted by H, benzyl or C ⁇ _ 8 -alkyl;
  • Qi, Q 2 and Q 3 independently represent linking groups, further specified below, provided that two of Ri, R 2 and R 3 are coordinating groups and one of Ri, R 2 and R 3 is a non-coordinating group, and with the proviso that the following ligands are excluded:
  • the present invention provides a complex of the ligand and a transition metal.
  • An advantage of the class of ligand and complex according to the present invention is that the complex can catalyse bleaching of a substrate by atmospheric oxygen, thus permitting its use in a medium such as an aqueous medium that is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system.
  • complexes of this class are surprisingly effective in catalysing bleaching of the substrate by atmospheric oxygen after treatment of the substrate.
  • the ligand or complex according to the present invention permits all or the majority of the bleaching species in the medium (on an equivalent weight basis) to be derived from atmospheric oxygen.
  • the medium can be made wholly or substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system.
  • the complex is a catalyst for the bleaching process and, as such, is not consumed but can continue to participate in the bleaching process.
  • the ligand or complex can provide a catalytically activated bleaching system which is based on atmospheric oxygen, is therefore both cost-effective and environmentally friendly.
  • a bleaching system can be provided that is operable under unfavourable wash conditions which include low temperatures, short contact times and low dosage requirements.
  • the catalyst is effective in an aqueous medium and is therefore particularly applicable to bleaching of laundry fabrics. Therefore, whilst the catalyst according to the present invention may be used for bleaching any suitable substrate, the preferred substrate is a laundry fabric. Bleaching may be carried out by simply leaving the substrate in contact with the medium for a sufficient period of time. Preferably, however, the aqueous medium on or containing the substrate is agitated.
  • a further advantage is that, by enabling a bleaching effect even after the textile has been treated, the benefits of bleaching can be prolonged on the textile. Furthermore, since a bleaching effect is conferred to the textile after the treatment, the treatment itself, such as a laundry wash cycle, may for example be shortened. Moreover, since a bleaching effect is achieved by atmospheric oxygen after treatment of the textile, hydrogen peroxide or peroxy-based bleach systems can be omitted from the treatment substance.
  • the present invention also extends to a commercial package comprising a bleaching composition comprising a ligand or complex as defined below together with instructions for its use .
  • the present invention also extends to use of a ligand or complex as defined below in the manufacture of a bleaching composition, the bleaching composition substantially devoid of peroxygen bleach or a peroxy-based or peroxy-generating bleach system.
  • the catalyst may be used as a preformed complex of the ligand and a transition metal.
  • the catalyst may be formed from the free ligand that complexes with a transition metal already present in the water or that complexes with a transition metal present in the substrate.
  • the composition may also be formulated as a composition of the free ligand or a transition metal-substitutable metal- ligand complex, and a source of transition metal, whereby the complex is formed in si tu in the medium.
  • the ligand forms a complex with one or more transition metals, in the latter case for example as a dinuclear complex.
  • Suitable transition metals include for example: manganese in oxidation states II-V, iron II-V, copper I-III, cobalt I-III, titanium II-IV, tungsten IV-VI, vanadium II-V and molybdenum II-VI.
  • the ligand forms a complex of the general formula (Al) :
  • M represents a metal selected from Mn (II ) - (III) - (IV) - (V), Cu(I)-(II)-(III), Fe(II)-(III)-(IV)-(V) , Co(I)-(II)- (III), Ti(II)-(III)-(IV), V(II)-(III)-(IV)-(V), Mo(II)- (III)-(IV)-(V)-(VI) and (IV) - (V) - (VI) , preferably selected from Fe(II)-(III)-(IV)-(V) ;
  • L represents a ligand as herein defined, or its protonated or deprotonated analogue
  • X represents a coordinating species selected from any mono, bi or tri charged anions and any neutral molecules able to coordinate the metal in a mono, bi or tridentate manner, preferably selected from O 2" , RB0 2 2” , RCOO “ , RCONR “ , OH “ , N0 3 “ , NO, S 2” , RS “ , P0 4 3” , P0 3 OR 3” , H 2 0, C0 3 2” , HC0 3 “ , ROH, N(R) 3 , ROO “ , 0 2 2” , 0 2 “ , RCN, CI “ , Br “ , OCN “ , SCN “ , CN “ , N 3 “ , F “ , I “ , RO “ , C10 “ , and CF 3 S0 3 “ , and more preferably selected from O 2” , RB0 2 2” , RCOO “ , OH “ , N0 3 “ , S 2” ,
  • Y represents any non-coordinated counter ion, preferably selected from C10 " , BR 4 " , [MX 4 ] “ , [MX 4 ] 2" , PF 6 “ , RCOO “ , N0 3 “ , RO “ , N + (R) 4 , ROO “ , 0 2 2 ⁇ , 0 2 " , CI “ , Br “ , F “ , I “ , CF 3 S0 3 “ , S 2 0 6 2” , OCN “ , SCN “ , H 2 0, RB0 2 2” , BF 4 “ and BPh “ , and more preferably selected from C10 4 " , BR 4 “ , [FeCl ] “ , PF 6 “ , RCOO “ , N0 3 “ , RO “ , N + (R) 4 , CI “ , Br “ , F “ , I “ , CF 3 S0 3 “ , S 2 0 6 2”
  • the ligand L is of the general formula (I) :
  • Q independently represent a group selected from C 2 - 3 - alkylene optionally substituted by H, benzyl or C ⁇ _ 8 -alkyl;
  • Qi, Q 2 and Q 3 independently represent a group of the formula:
  • Y independently represents a group selected from -0-, S-, -SO-, -S0 2 -, -C(O)-, arylene, alkylene, heteroarylene, heterocycloalkylene, -(G)P-, -P(O)- and -(G)N- , wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E; and R5, R6, R7, R8 independently represent a group selected from hydrogen, hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or R5 together with R6, or R7 together with R8 , or both, represent oxygen, or R5 together with R7 and/or independently R6
  • Ri, R 2 and R 3 are coordinating groups and one of Ri, R 2 and R 3 is a non-coordinating group
  • Two of Ri, R 2 and R 3 independently represent a group preferably selected from carboxylate, amido, -NH-C (NH) NH 2 , hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole.
  • Ri, R 2 , R 3 each independently represent a coordinating group selected from optionally substituted pyridin-2-yl, optionally substituted imidazol-2- yl, optionally substituted imidazol-4-yl, optionally substituted pyrazol-1-yl, and optionally substituted quinolin-2-yl .
  • substituents for groups Ri, R 2 , R 3 when representing a heterocyclic or heteroaromatic ring, are selected from C ⁇ _ 4 -alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl .
  • the groups R5, R6, R7 , R8 preferably independently represent a group selected from -H, hydroxy-C 0 -C 20 -alkyl, halo-Co-C 2 o _ alkyl, nitroso, formyl-Co-C 20 -alkyl, carboxyl-C 0 -C 2 o-alkyl and esters and salts thereof, carbamoyl-Co-C 20 -alkyl, sulfo-C 0 - C 20 -alkyl and esters and salts thereof, sulfamoyl-C 0 -C 20 - alkyl, amino-C 0 -C 2 o-alkyl, aryl-Co-C 2 o-alkyl, C 0 -C 20 -alkyl, alkoxy-C 0 -C 8 -alkyl, carbonyl-C 0 -C 6 -alkoxy, and C 0 -C 20 - al
  • the groups Qi, Q 2 and Q 3 independently represent a group selected from -CH 2 - and - CH 2 CH 2 — .
  • Group Q is preferably a group selected from -CH 2 CH 2 - and - CH 2 CH 2 CH 2 -.
  • the ligand L is of the general formula (II):
  • two of RI, R2, R3 each independently represent a coordinating group selected from optionally substituted pyridin-2-yl, optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl, optionally substituted pyrazol-1-yl, and optionally substituted quinolin-2-yl; and one of RI, R2, R3 represents a group selected from hydrogen, C ⁇ _ ⁇ 0 optionally substituted alkyl, C ⁇ _ 5 -furanyl, C ⁇ - 5 optionally substituted benzylalkyl, benzyl, C 1 - 5 optionally substituted alkoxy, and C ⁇ _ 2 o optionally substituted N + Me 3 .
  • a particularly preferred ligand is 1, 4-bis (5-methyl-pyridin- 2-ylmethyl) -7-ethyl-l, 4 , 7-triazacyclononane .
  • the counter ions Y in formula (Al) balance the charge z on the complex formed by the ligand L, metal M and coordinating species X.
  • Y may be an anion such as RCOO “ , BPh 4 " , C10 4 " , BF 4 “ , PF 6 “ , RS0 3 “ , RS0 4 “ , S0 4 2” , N0 3 ⁇ , F “ , CI “ , Br “ , or I " , with R being hydrogen, optionally substituted alkyl or optionally substituted aryl.
  • Y may be a common cation such as an alkali metal, alkaline earth metal or (alkyl) ammonium cation.
  • Suitable counter ions Y include those which give rise to the formation of storage-stable solids.
  • Preferred counter ions for the preferred metal complexes are selected from R 7 COO ⁇ , C10 4 " , BF “ , PF 6 " , RS0 3 “ (in particular CF 3 S0 3 “ ) , RS0 4 “ , S0 4 2” , N0 3 “ , F “ , CI “ , Br “ , and I “ , wherein R represents hydrogen or optionally substituted phenyl, naphthyl or C ⁇ -C 4 alkyl.
  • the complex (Al) can be formed by any appropriate means, including in si tu formation whereby precursors of the complex are transformed into the active complex of general formula (Al) under conditions of storage or use.
  • the complex is formed as a well-defined complex or in a solvent mixture comprising a salt of the metal M and the ligand L or ligand L-generating species.
  • the catalyst may be formed in si tu from suitable precursors for the complex, for example in a solution or dispersion containing the precursor materials.
  • the active catalyst may be formed in si tu in a mixture comprising a salt of the metal M and the ligand L, or a ligand L-generating species, in a suitable solvent.
  • an iron salt such as FeS0 4 can be mixed in solution with the ligand L, or a ligand L-generating species, to form the active complex.
  • the ligand L, or a ligand L-generating species can be mixed with metal M ions present in the substrate or wash liquor to form the active catalyst in si tu .
  • Suitable ligand L-generating species include metal-free compounds or metal coordination complexes that comprise the ligand L and can be substituted by metal M ions to form the active complex according the formula (Al) .
  • the catalysts according to the present invention may be used for laundry cleaning, hard surface cleaning (including cleaning of lavatories, kitchen work surfaces, floors, mechanical ware washing etc.).
  • bleaching compositions are also employed in waste-water treatment, pulp bleaching during the manufacture of paper, leather manufacture, dye transfer inhibition, food processing, starch bleaching, sterilisation, whitening in oral hygiene preparations and/or contact lens disinfection.
  • bleaching should be understood as relating generally to the decolourisation of stains or of other materials attached to or associated with a substrate.
  • the present invention can be applied where a requirement is the removal and/or neutralisation by an oxidative bleaching reaction of malodours or other undesirable components attached to or otherwise associated with a substrate.
  • bleaching is to be understood as being restricted to any bleaching mechanism or process that does not require the presence of light or activation by light.
  • the level of the catalyst is such that the in-use level is from 0.05 ⁇ M to 50mM, with preferred in-use levels for domestic laundry operations falling in the range 0.5 ⁇ M to 100 ⁇ M, more preferably from 1 ⁇ M to 10 ⁇ M. Higher levels may be desired and applied in industrial bleaching processes, such as textile and paper pulp bleaching.
  • the aqueous medium has a pH in the range from pH 6 to 13, more preferably from pH 6 to 11, still more preferably from pH 8 to 11, and most preferably from pH 8 to 10, in particular from pH 9 to 10.
  • the bleaching catalyst of the present invention has particular application in detergent formulations, especially for laundry cleaning.
  • the detergent bleach composition may for example contain a surface-active material in an amount of from 10 to 50% by weight.
  • the surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof.
  • suitable actives are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • Typical synthetic anionic surface-actives are usually water- soluble alkali metal salts of organic sulfates and sulfonates having alkyl groups containing from about 8 to about 22 carbon atoms, the term "alkyl” being used to include the alkyl portion of higher aryl groups.
  • suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulfates, especially those obtained by sulfating higher (C 8 -C ⁇ 8 ) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (Cg- C 20 ) benzene sulfonates, particularly sodium linear secondary alkyl (C ⁇ 0 -C 15 ) benzene sulfonates; sodium alkyl glyceryl ether sulfates, especially those ethers of the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium and ammonium salts of sulfuric acid esters of higher (C 9 -C ⁇ 8 ) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of fatty acid fatty
  • nonionic surface-active compounds which may be used, preferably together with the anionic surface- active compounds, include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 6 -C 22 ) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; and the condensation products of aliphatic (C 8 -C ⁇ 8 ) primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO.
  • alkyl polyglycosides sugar esters, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulfoxides .
  • Amphoteric or zwitterionic surface-active compounds can also be used but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.
  • the detergent bleach composition will preferably comprise from 1 to 15 % wt of anionic surfactant and from 10 to 40 % by weight of nonionic surfactant.
  • the detergent active system is free from C ⁇ -C ⁇ 2 fatty acid soaps.
  • the bleach composition may also contains a detergency builder, for example in an amount of from about 5 to 80 % by weight, preferably from about 10 to 60 % by weight.
  • Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water- soluble salts; the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and polyacetal carboxylates as disclosed in US-A-4, 144,226 and US-A-4, 146, 495.
  • alkali metal polyphosphates such as sodium tripolyphosphate
  • nitrilotriacetic acid and its water- soluble salts the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid
  • polyacetal carboxylates as disclosed in US-A-4, 144
  • precipitating builder materials examples include sodium orthophosphate and sodium carbonate.
  • Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P) , zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0, 384, 070.
  • zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P) , zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0, 384, 070.
  • compositions may contain any one of the organic and inorganic builder materials, though, for environmental reasons, phosphate builders are preferably omitted or only used in very small amounts.
  • Typical builders usable in the present invention are, for example, sodium carbonate, calcite/carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyloxy malonate, carboxymethyloxy succinate and water-insoluble crystalline or amorphous aluminosilicate builder materials, each of which can be used as the main builder, either alone or in admixture with minor amounts of other builders or polymers as co-builder.
  • the composition contains not more than 5% by weight of a carbonate builder, expressed as sodium carbonate, more preferably not more than 2.5 % by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.
  • the bleach composition can contain any of the conventional additives in amounts of which such materials are normally employed in fabric washing detergent compositions.
  • these additives include buffers such as carbonates, lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids; lather depressants, such as alkyl phosphates and silicones; anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; stabilisers, such as phosphonic acid derivatives (i.e.
  • Dequest® types fabric softening agents; inorganic salts and alkaline buffering agents, such as sodium sulfate and sodium silicate; and, usually in very small amounts, fluorescent agents; perfumes; enzymes, such as proteases, cellulases, lipases, amylases and oxidases; germicides and colourants.
  • Transition metal sequestrants such as EDTA, and phosphonic acid derivatives such as EDTMP (ethylene diamine tetra (methylene phosphonate) ) may also be included, in addition to the ligand specified, for example to improve the stability sensitive ingredients such as enzymes, fluorescent agents and perfumes, but provided the composition remains bleaching effective.
  • the composition is preferably substantially, and more preferably completely, devoid of transition metal sequestrants (other than the ligand) .
  • the present invention is based on the catalytic bleaching of a substrate by atmospheric oxygen or air, it will be appreciated that small amounts of hydrogen peroxide or peroxy-based or -generating systems may be included in the composition, if desired.
  • substantially devoid of peroxygen bleach or peroxy-based or -generating bleach systems is meant that the composition contains from 0 to 50 %, preferably from 0 to 10 %, more preferably from 0 to 5 %, and optimally from 0 to 2 % by molar weight on an oxygen basis, of peroxygen bleach or peroxy-based or - generating bleach systems.
  • the composition will be wholly devoid of peroxygen bleach or peroxy-based or -generating bleach systems.
  • At least 10 %, preferably at least 50 % and optimally at least 90 % of any bleaching of the substrate is effected by oxygen sourced from the air.
  • alkyl linear and branched Cl-C8-alkyl
  • alkenyl C2-C6-alkenyl
  • cycloalkyl C3-C8-cycloalkyl
  • alkoxy Cl-C6-alkoxy, alkylene: selected from the group consisting of: methylene; 1, 1-ethylene; 1, 2-ethylene; 1, 1-propylidene; 1, 2-propylene; 1, 3-propylene; 2, 2-propylidene; butan-2-ol-l, 4-diyl; propan- 2-ol-l, 3-diyl; 1, 4-butylene; cyclohexane-1, 1-diyl; cyclohexan-1, 2-diyl; cyclohexan-1, 3-diyl; cyclohexan-1, 4- diyl; cyclopentane-1, 1-diyl; cyclopentan-1, 2-diyl; and cyclopentan-1, 3-diyl,
  • aryl selected from homoaromatic compounds having a molecular weight under 300,
  • arylene selected from the group consisting of: 1,2- phenylene; 1, 3-phenylene; 1, 4-phenylene; 1, 2-naphtalenylene; 1, 3-naphtalenylene; 1, 4-naphtalenylene; 2, 3-naphtalenylene; l-hydroxy-2, 3-phenylene; l-hydroxy-2, 4-phenylene; 1-hydroxy- 2, 5-phenylene; and l-hydroxy-2, 6-phenylene,
  • heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl;
  • heteroarylene selected from the group consisting of: pyridindiyl; quinolindiyl; pyrazodiyl; pyrazoldiyl; triazolediyl; pyrazindiyl; and imidazolediyl, wherein the heteroarylene acts as a bridge in the compound via any atom in the ring of the selected heteroarylene, more specifically - 25 -
  • heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1, 4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1,4,7- triazacyclononanyl; 1,4,8, 11-tetraazacyclotetradecanyl; 1,4,7,10, 13-pentaazacyclopentadecanyl; 1, 4-diaza-7-thia- cyclononanyl; 1, 4-diaza-7-oxa-cyclononanyl; 1,4,7,10- tetraazacyclododecanyl; 1, 4-dioxanyl; 1, 4, 7-trithia- cyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in
  • heterocycloalkylene selected from the group consisting of: piperidin-1, 2-ylene; piperidin-2, 6-ylene; piperidin-4, 4- ylidene; 1, 4-piperazin-l, 4-ylene; 1, -piperazin-2, 3-ylene; 1, 4-piperazin-2, 5-ylene; 1, 4-piperazin-2, 6-ylene; 1,4- piperazin-1, 2-ylene; 1, -piperazin-l, 3-ylene; 1, 4-piperazin- 1,4-ylene; tetrahydrothiophen-2, 5-ylene; tetrahydrothiophen- 3, 4-ylene; tetrahydrothiophen-2, 3-ylene; tetrahydrofuran- 2, 5-ylene; tetrahydrofuran-3, -ylene; tetrahydrofuran-2 , 3- ylene; pyrrolidin-2, 5-ylene; pyrrolidin-3, 4-ylene; pyrrolidin-2, 3-ylene; pyrroli
  • each R is independently selected from: hydrogen; Cl-C6-alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R are Cl-C6-alkyl both R together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring,
  • halogen selected from the group consisting of: F; CI; Br and I,
  • sulfonate the group -S(0) 2 OR, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca,
  • sulfate the group -OS(0) 2 OR, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca,
  • sulfone the group -S(0) 2 R, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5 and amine (to give sulfonamide) selected from the group: -NR'2, wherein each R 1 is independently selected from: hydrogen; Cl-C6-alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R' are Cl-C6-alkyl both R 1 together may form an -NC3 to an - NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring,
  • carboxylate derivative the group -C(0)OR, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl- C6H5; Li; Na; K; Cs; Mg; and Ca,
  • carbonyl derivative the group -C(0)R, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl- C6H5 and amine (to give amide) selected from the group: - NR'2, wherein each R 1 is independently selected from: hydrogen; Cl-C6-alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R' are Cl-C6-alkyl both R' together may form an - NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring,
  • phosphonate the group -P(O) (0R) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca,
  • phosphate the group -OP(O) (0R) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca,
  • phosphine the group -P(R) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; and Cl-C6-alkyl-C6H5,
  • phosphine oxide the group -P(0)R 2 , wherein R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; and Cl-C6-alkyl-C6H5; and amine (to give phosphonamidate) selected from the group: -NR'2, wherein each R 1 is independently selected from: hydrogen; Cl-C6-alkyl; C1-C6- alkyl-C6H5; and phenyl, wherein when both R' are Cl-C6-alkyl both R' together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring.
  • alkyl linear and branched Cl-C6-alkyl
  • alkenyl C3-C6-alkenyl
  • cycloalkyl C6-C8-cycloalkyl
  • alkoxy Cl-C4-alkoxy
  • alkylene selected from the group consisting of: methylene
  • aryl selected from group consisting of: phenyl; biphenyl; naphthalenyl; anthracenyl; and phenanthrenyl,
  • arylene selected from the group consisting of: 1,2- phenylene; 1, 3-phenylene; 1, -phenylene; 1, 2-naphtalenylene; 1, 4-naphtalenylene; 2, 3-naphtalenylene and l-hydroxy-2, 6- phenylene,
  • heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl; quinolinyl; pyrazolyl; triazolyl; isoquinolinyl; imidazolyl; and oxazolidinyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl,
  • heteroarylene selected from the group consisting of: pyridin-2, 3-diyl; pyridin-2, 4-diyl; pyridin-2, 6-diyl; pyridin-3, 5-diyl; quinolin-2, 3-diyl; quinolin-2, 4-diyl; isoquinolin-1, 3-diyl; isoquinolin-1, 4-diyl; pyrazol-3, 5- diyl; and imidazole-2, 4-diyl,
  • heterocycloalkyl selected from the group consisting of: pyrrolidinyl; morpholinyl; piperidinyl; piperidinyl; 1,4- piperazinyl; tetrahydrofuranyl; 1, 4, 7-triazacyclononanyl; 1,4,8, 11-tetraazacyclotetradecanyl; 1,4,7,10, 13- pentaazacyclopentadecanyl ; 1,4,7, 10-tetraazacyclododecanyl ; and piperazinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl,
  • heterocycloalkylene selected from the group consisting of: piperidin-2, 6-ylene; piperidin-4, 4-ylidene; 1,4- piperazin-1, 4-ylene; 1, 4-piperazin-2, 3-ylene; 1, 4-piperazin- 2, 6-ylene; tetrahydrothiophen-2, 5-ylene; tetrahydrothiophen- 3, 4-ylene; tetrahydrofuran-2, 5-ylene; tetrahydrofuran-3, 4- ylene; pyrrolidin-2, 5-ylene; pyrrolidin-2, 2-ylidene; 1,4,7- triazacyclonon-1, 4-ylene; 1, 4 , 7-triazacyclonon-2, 3-ylene; 1,4, 7-triazacyclonon-2, 2-ylidene; 1, 4, 8, 11- tetraazacyclotetradec-l, 4-ylene; 1, 4, 8, 11- tetraazacyclotetradec-l, 8-ylene; 1,4,8, ll-t
  • each R is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl,
  • halogen selected from the group consisting of: F and CI
  • sulfonate the group -S(0) 2 0R, wherein R is selected from: hydrogen; Cl-C6-alkyl; Na; K; Mg; and Ca,
  • sulfate the group -OS(0) 2 OR, wherein R is selected from: hydrogen; Cl-C6-alkyl; Na; K; Mg; and Ca,
  • sulfone the group -S(0) 2 R, wherein R is selected from: hydrogen; Cl-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl,
  • carboxylate derivative the group -C(0)OR, wherein R is selected from hydrogen; Na; K; Mg; Ca; Cl-C6-alkyl; and benzyl,
  • carbonyl derivative the group: -C(0)R, wherein R is selected from: hydrogen; Cl-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl,
  • phosphonate the group -P(0) (0R) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl; Na; K; Mg; and Ca,
  • phosphate the group -OP(0) (OR) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl; Na; K; Mg; and Ca,
  • phosphine the group -P(R) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl,
  • phosphine oxide the group -P(0)R 2 , wherein R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl.

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Abstract

L'invention concerne des ligands et des complexes utilisés comme catalyseurs pour blanchir des substrats selon un procédé catalytique à l'aide d'oxygène atmosphérique, et utilisés comme catalyseurs dans le traitement de textiles tels que des tissus pour blanchissage, le blanchiment par oxygène atmosphérique étant catalysé après le traitement. Le ligand est représenté par la formule générale (I), dans laquelle R1, R2 et R3 représentent indépendamment un groupe sélectionné parmi l'hydrogène, l'hydroxyle, l'halogène, -NH-C(NH)NH2, -R et -OR, où R= alkyle, alkényle, cycloalkyle, hétérocycloalkyle, aryle, hétéroaryle ou un groupe dérivé de carbonyle, R étant éventuellement substitué par un ou plusieurs groupes fonctionnels, et à condition que deux éléments parmi R1, R2 et R3 soient des groupes de coordination et qu'un élément parmi R1, R2 et R3 ne soit pas un groupe de coordination; Q représente indépendamment un groupe sélectionné parmi l'alkylène C2-3 éventuellement substitué par H, benzyle ou alkyle C1-8; et Q1, Q2 et Q3 représentent indépendamment des groupes de liaison spécifiques.
EP00969243A 1999-09-01 2000-08-17 Ligand et complexe servant a blanchir un substrat selon un procede catalytique Ceased EP1208107A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
WOPCT/GB99/02876 1999-09-01
PCT/GB1999/002876 WO2000012667A1 (fr) 1998-09-01 1999-09-01 Composition et procede de blanchiment d'un substrat
GB0004854 2000-02-29
GBGB0004854.6A GB0004854D0 (en) 2000-02-29 2000-02-29 Ligand and complex for catalytically bleaching a substrate
PCT/EP2000/008144 WO2001016272A2 (fr) 1999-09-01 2000-08-17 Ligand et complexe servant a blanchir un substrat selon un procede catalytique

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BR112013000236B1 (pt) * 2010-07-06 2018-11-13 Catexel Limited método de produzir um composto, e, sal protonado
CN108948050B (zh) * 2018-06-29 2020-11-03 浙江理工大学 一种金属配合物及其制备方法和一种漂白工作液
US20220396595A1 (en) * 2019-10-17 2022-12-15 Rhodia Operations A metal complex and use thereof
WO2021097601A1 (fr) * 2019-11-18 2021-05-27 Solvay Sa Particules de blanchiment solides
CN113321624A (zh) * 2021-06-15 2021-08-31 仪征市海帆化工有限公司 一种1,4,7-三氮环壬烷的合成方法

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WO1990009379A1 (fr) * 1989-02-10 1990-08-23 Celltech Limited Aza-macrocycles et procedes pour leur preparation
US5364613A (en) * 1989-04-07 1994-11-15 Sieving Paul F Polychelants containing macrocyclic chelant moieties
WO1994004485A1 (fr) * 1992-08-19 1994-03-03 Mallinckrodt Medical, Inc. LIGANDS UTILISES DANS LA TOMOGRAPHIE CARDIAQUE A POSITONS REALISEE AVEC DU Ga-68
JPH06256512A (ja) * 1993-03-05 1994-09-13 Rikagaku Kenkyusho 積層大環状ポリアミン誘導体及びその製造方法
US5554749A (en) * 1994-01-14 1996-09-10 Mallinckrodt Medical, Inc. Functionalized macrocyclic ligands for imaging applications
WO1997048787A1 (fr) * 1996-06-19 1997-12-24 Unilever N.V. Activation d'un agent de blanchiment
JPH10279411A (ja) * 1997-03-31 1998-10-20 Lion Corp カビ取り剤組成物
DE19756361A1 (de) * 1997-12-18 1999-06-24 Philips Patentverwaltung Organische lichtemittierende Diode mit Terbiumkomplex

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Title
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TR200201278T2 (tr) 2002-08-21
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CN1384837A (zh) 2002-12-11
AU7903300A (en) 2001-03-26
WO2001016272A3 (fr) 2001-08-30

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