EP0373546B1 - Utilisation d'éthanolamines triacylées comme activateurs liquides et miscibles à l'eau, de composés peroxydes - Google Patents

Utilisation d'éthanolamines triacylées comme activateurs liquides et miscibles à l'eau, de composés peroxydes Download PDF

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Publication number
EP0373546B1
EP0373546B1 EP89122759A EP89122759A EP0373546B1 EP 0373546 B1 EP0373546 B1 EP 0373546B1 EP 89122759 A EP89122759 A EP 89122759A EP 89122759 A EP89122759 A EP 89122759A EP 0373546 B1 EP0373546 B1 EP 0373546B1
Authority
EP
European Patent Office
Prior art keywords
activators
water
triacylated
ethanolamines
liquid
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.)
Expired - Lifetime
Application number
EP89122759A
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German (de)
English (en)
Other versions
EP0373546A3 (fr
EP0373546A2 (fr
Inventor
Hajime Dr. Endo
Hanspeter Dr. Gethöffer
Fritz-Feo Dr. Grabley
Gerd Dr. Reinhardt
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.)
Hoechst AG
Original Assignee
Hoechst AG
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Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0373546A2 publication Critical patent/EP0373546A2/fr
Publication of EP0373546A3 publication Critical patent/EP0373546A3/fr
Application granted granted Critical
Publication of EP0373546B1 publication Critical patent/EP0373546B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds

Definitions

  • Inorganic persalts have long been known as bleach additives in detergents. However, since they only develop their optimum bleaching power at temperatures above 60 ° C, a number of organic compounds have been described for their activation which react with hydrogen peroxide to release a peroxycarboxylic acid during the washing process. This already has a bleaching and disinfecting effect at 40-60 ° C.
  • activators such as N-acyl compounds (tetraacetylethylenediamine (TAED), tetraacetylmethylene diamine, tetraacetylglycoluril (TAGU)) or activated esters (pentaacetylglucose (PAG), acetoxybenzenesulfonate sodium, nonanoyloxibenzol sulfonate sodium (NOB) sulfonate sodium (NOB) sulfonate (S)
  • TAED tetraacetylethylenediamine
  • TAGU tetraacetylmethylene diamine
  • TAGU tetraacetylglycoluril
  • activated esters penentaacetylglucose (PAG), acetoxybenzenesulfonate sodium, nonanoyloxibenzol sulfonate sodium (NOB) sulfonate sodium (NOB) sulfon
  • Liquid textile detergents are being used more and more recently.
  • a disadvantage of the heavy duty liquids available so far, however, is the lack of a bleaching system for removing stubborn, oxidizable stains.
  • a number of patent applications therefore use aqueous bleaching systems based on hydrogen peroxide / activator Proposed, which are stored at pH values ⁇ 7 and are only combined with the surfactant mixture before washing begins, since this is the only way to ensure good storage stability.
  • DE-351151, EP-217454, EP-225654 describe anhydrous, liquid heavy-duty detergents which, in addition to a surfactant mixture, auxiliaries and builders, also contain a bleaching system of the activator / persalt type. Dispersions of finely ground perborate monohydrate and TAED are claimed.
  • the documents DE-3728256, DE-3,729,074 and EP 125,781 indicate the advantages of incorporating liquid, organic activators (e.g. acylals and diacetylmethylamine). However, the claimed activators (e.g.
  • ethylidene acetate benzoate have the disadvantage that they are only soluble in water to a limited extent, can only be used as a suspension in water-containing formulations and dissolve only slowly during the bleaching process.
  • Another disadvantage is that decomposition products form after perhydrolysis (low molecular weight aldehydes, N-methylacetamide), some of which must be regarded as environmentally problematic.
  • liquid activators e.g. DE-OS 27 33 849 also describes triacetylethanolamine, which is adsorbed on inorganic carrier materials, in powder detergents.
  • triacylated ethanolamines are very readily miscible with water and, in the presence of hydrogen peroxide or other per compounds, release one mole of a peracid at room temperature.
  • the invention therefore relates to the use of triacylated ethanolamine of the general formula (RCO) (R1CO) N- (CH2) 2-O-COR2 where R, R1, R2 are the same or different and are alkyl, alkenyl or aryl groups and the sum of all C atoms in the molecule is 8 to 14, as liquid, water-miscible peroxide activators in liquid detergents and cleaning agents.
  • RCO triacylated ethanolamine of the general formula (RCO) (R1CO) N- (CH2) 2-O-COR2
  • R, R1, R2 are the same or different and are alkyl, alkenyl or aryl groups and the sum of all C atoms in the molecule is 8 to 14, as liquid, water-miscible peroxide activators in liquid detergents and cleaning agents.
  • Triacylated ethanolamines are compounds known per se, the textile finishing effect of which is known (US Pat. No. 2,143,765). To produce them, ethanolamine is reacted with an excess of a carboxylic acid anhydride or carboxylic acid halide at elevated temperature. For economic and ecological reasons, however, they are preferably produced using the two-stage process described below.
  • ethanolamine is reacted with an acid at temperatures between 120 and 200 ° C with the release of water of reaction to carboxylic acid monoethanolamide or N, O-diacylethanolamine.
  • the product is reacted with a carboxylic anhydride at 130 to 170 ° C. in a second reaction step without further purification, the carboxylic acid formed being distilled off.
  • the reaction can optionally in the presence of an acidic or basic catalyst such as sulfuric acid, p-toluenesulfonic acid or Sodium acetate and be carried out under reduced pressure.
  • the carboxylic acid formed in the second reaction step can be introduced into the first reaction step, so that continuous production is possible.
  • the water solubility of the acylation products obtained in this way is strongly dependent on the number of carbon atoms contained.
  • Preferred compounds are triacetylethanolamine, diacetylpropionylethanolamine, tripropionylethanolamine, and benzoyldiacetylethanolamine, of which triacetylethanolamine has the best water solubility and is miscible with water in any ratio.
  • Compounds with more than 14 carbon atoms show no advantage over known solid activators, since they have to be emulsified or dispersed because of insufficient solubility.
  • Triacetylethanolamine (TAEA) in aqueous solution easily reacts with hydrogen peroxide or inorganic persalts to form peracetic acid, a highly bleaching and disinfecting substance.
  • Perborates, percarbonates, persulfates or perphosphates in the form of their sodium or potassium salts can be used as inorganic persalts.
  • the molar ratio of persalt: activator is 0.5-10 to 1, preferably 1-4 to 1.
  • a stable bleaching mixture is obtained which can be used directly or in combination with other additives as a washing, cleaning or disinfecting agent.
  • the mixture may contain anionic or cationic surfactants, enzymes, peroxide stabilizers, antigelling agents, perfume and dyes as further constituents.
  • a combination with others Peroxide activators or peroxy carboxylic acids such as dodecane diperoxy carboxylic acid are possible.
  • Another area of application of the compounds described is the use as a peroxide activator in a powdered detergent. For this purpose, the liquid activator on a solid such. B. zeolite or sodium perborate and possibly stabilized by additional granulation or coating.
  • the present invention is based on the property now found that the triacylated ethanolamines described are completely miscible with water. Due to this property, a completely homogeneous distribution of the peroxide activator in liquid detergents and in particular in the wash liquor is given and the disadvantages resulting from the inhomogeneous distribution of solid peroxide activators in such detergents, such as the formation of bleaching spots, are avoided.
  • the activators were pre-dissolved in a little water and added to the tempered wash liquor mentioned above. At the desired time intervals (1-5 min.), 50 ml samples were taken and the content of total active oxygen and peracid was determined by titration.
  • Tab. 1 pH dependence of the perhydrolysis of dissolved bleach activators at 22 ° C; required time [min] up to a 90 percent. Turnover at activator: pH 9 pH10 pH11 TAEA 12 min 7 min 1 min TAED 15 minutes 7 min 1 min Isonobs > 30 min 11 min 1.5 min
  • TAEA releases a mole of peracetic acid very quickly, analogous to pre-dissolved TAED. These perhydrolyses are faster than the formation of perisononanoic acid from isonobs.
  • the tests were carried out in the Launder-O-Meter at 60 ° C using the test fabric WFK 10 G cotton (tea soiling) and EMPA cotton No. 114 (red wine soiling) in 15dH water.
  • the bleaching systems activator / perborate
  • the bleaching systems were metered in such a way that in each case 25 mg of active oxygen per liter of wash liquor resulted.
  • 1.5 g of IEC basic washing powder per liter of washing liquor were used as detergents.
  • the washing time was 30 minutes.
  • the bleaching effect was determined as an increase in remission on the different test tissues.
  • the evaluation was carried out in a known manner.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Dental Preparations (AREA)

Claims (2)

  1. Produit de lavage et de nettoyage liquide ayant une teneur en activateurs de peroxydes liquides miscibles à l'eau, caractérisé en ce que les produits de lavage et de nettoyage liquides contiennent en tant qu'activateurs de peroxydes une éthanolamine triacylée de formule générale :

            (RCO) (R₁CO)N- (CH₂)₂-O-COR₂

    dans laquelle R, R₁ et R₂ sont identiques ou différents et représentent des groupes alkyle, alcényle ou aryle et la somme de tous les atomes de carbone dans la molécule est de 8 à 14.
  2. Produit de lavage et de nettoyage liquide selon la revendication 1, caractérisé en ce qu'il contient la triacétyléthanolamine en tant qu'activateur de peroxydes.
EP89122759A 1988-12-14 1989-12-09 Utilisation d'éthanolamines triacylées comme activateurs liquides et miscibles à l'eau, de composés peroxydes Expired - Lifetime EP0373546B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3842008 1988-12-14
DE3842008A DE3842008A1 (de) 1988-12-14 1988-12-14 Verwendung von triacylierten ehtanolaminen als fluessige, wassermischbare peroxidaktivatoren

Publications (3)

Publication Number Publication Date
EP0373546A2 EP0373546A2 (fr) 1990-06-20
EP0373546A3 EP0373546A3 (fr) 1991-04-03
EP0373546B1 true EP0373546B1 (fr) 1996-04-10

Family

ID=6369102

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89122759A Expired - Lifetime EP0373546B1 (fr) 1988-12-14 1989-12-09 Utilisation d'éthanolamines triacylées comme activateurs liquides et miscibles à l'eau, de composés peroxydes

Country Status (7)

Country Link
US (1) US5045222A (fr)
EP (1) EP0373546B1 (fr)
JP (1) JPH02202600A (fr)
AT (1) ATE136580T1 (fr)
CA (1) CA2005331A1 (fr)
DE (2) DE3842008A1 (fr)
ES (1) ES2087070T3 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7390432B2 (en) * 1998-06-30 2008-06-24 Sandia Corporation Enhanced formulations for neutralization of chemical, biological and industrial toxants
US6210639B1 (en) 1998-10-26 2001-04-03 Novartis Ag Apparatus, method and composition for cleaning and disinfecting
US9371556B2 (en) 2004-03-05 2016-06-21 Gen-Probe Incorporated Solutions, methods and kits for deactivating nucleic acids
US20060019854A1 (en) * 2004-07-21 2006-01-26 Johnsondiversey. Inc. Paper mill cleaner with taed
US8940660B2 (en) * 2008-12-04 2015-01-27 Uop Llc Simultaneous warm gas desulfurization and complete CO-shift for improved syngas cleanup
US8017545B2 (en) * 2008-12-04 2011-09-13 Uop Llc Dynamic composition for the removal of sulfur from a gaseous stream
US7811474B2 (en) * 2008-12-04 2010-10-12 Uop Llc Simultaneous warm gas desulfurization and CO-shift for improved syngas cleanup
US7935324B2 (en) * 2008-12-04 2011-05-03 Uop Llc Integrated warm gas desulfurization and gas shift for cleanup of gaseous streams
US7759282B2 (en) * 2008-12-04 2010-07-20 Uop Llc Catalyst for removal of sulfer from a gaseous stream
US20120322873A1 (en) * 2010-12-28 2012-12-20 Nalco Company Use of a buffer with a biocide precursor
US9242880B2 (en) 2010-12-28 2016-01-26 Nalco Company Strategy for on-site in situ generation of oxidizing compounds and application of the oxidizing compound for microbial control

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL49392C (fr) * 1938-04-26
NL97449C (fr) * 1959-06-19
DE2733849A1 (de) * 1977-07-27 1979-02-15 Basf Ag Feste kaltbleichaktivatoren fuer aktivsauerstoff abgebende verbindungen enthaltende wasch- und reinigungsmittel
GB8310081D0 (en) * 1983-04-14 1983-05-18 Interox Chemicals Ltd Peroxygen compounds
US4786431A (en) * 1984-12-31 1988-11-22 Colgate-Palmolive Company Liquid laundry detergent-bleach composition and method of use
DE3519689A1 (de) * 1985-06-01 1986-12-04 Henkel KGaA, 4000 Düsseldorf Fluessiges waschmittelkonzentrat
EP0217454B1 (fr) * 1985-09-30 1992-03-11 Unilever N.V. Composition détergente liquide non aqueuse et perborate anhydre
US4772413A (en) * 1986-08-28 1988-09-20 Colgate-Palmolive Company Nonaqueous liquid nonbuilt laundry detergent bleach booster composition containing diacetyl methyl amine and method of use

Also Published As

Publication number Publication date
DE58909648D1 (de) 1996-05-15
ATE136580T1 (de) 1996-04-15
ES2087070T3 (es) 1996-07-16
US5045222A (en) 1991-09-03
JPH02202600A (ja) 1990-08-10
DE3842008A1 (de) 1990-06-21
CA2005331A1 (fr) 1990-06-14
EP0373546A3 (fr) 1991-04-03
EP0373546A2 (fr) 1990-06-20

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