EP0731161A2 - Utilisation de carbohydrates comme activateurs de blanchiment ou agents complexants dans les formulations de nettoyage - Google Patents

Utilisation de carbohydrates comme activateurs de blanchiment ou agents complexants dans les formulations de nettoyage Download PDF

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Publication number
EP0731161A2
EP0731161A2 EP96102954A EP96102954A EP0731161A2 EP 0731161 A2 EP0731161 A2 EP 0731161A2 EP 96102954 A EP96102954 A EP 96102954A EP 96102954 A EP96102954 A EP 96102954A EP 0731161 A2 EP0731161 A2 EP 0731161A2
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EP
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Prior art keywords
acetate
carbohydrate
sucrose
sodium
acid
Prior art date
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Granted
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EP96102954A
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German (de)
English (en)
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EP0731161A3 (fr
EP0731161B1 (fr
Inventor
Markwart Dr. Kunz
Jörg Dr. Kowalczyk
Sonja Dr. Ehrhardt
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Suedzucker AG
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Suedzucker AG
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    • 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
    • C11D3/391—Oxygen-containing compounds
    • C11D3/3912—Oxygen-containing compounds derived from saccharides
    • 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
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof

Definitions

  • the invention relates to the use of peracetylated carbohydrates and in particular those from the group of sucrose, maltose, lactose, palatinose, trehalulose, glucose and fructose or their mixtures as bleach activators or complexing agents in detergent formulations.
  • detergents also contain per compounds as bleaching agents, e.g. Sodium perborate or bleach activators such as tetraacetylethylenediamine (TAED). Since TAED has only two acetyl groups for the formation of active species and the biodegradability of the residual molecule is inadequate and since the bleach-active components are also inactivated by the presence of metal cations, so that further complexing agents such as acrylates and ethylenediaminotetraacetate (EDTA) must be used, they all contain them Detergent components that are difficult to biodegrade.
  • bleaching agents e.g. Sodium perborate or bleach activators such as tetraacetylethylenediamine (TAED). Since TAED has only two acetyl groups for the formation of active species and the biodegradability of the residual molecule is inadequate and since the bleach-active components are also inactivated by the presence of metal cations, so that further complexing agents such as acrylates and ethylenediaminotetraacetate (ED
  • EP 0 325 184 acetylated sugar ethers are used for coarse detergents because of their action as bleach activators, as foam boosters and because of their softening properties.
  • EP 0 540 279 discloses 1-acyl-substituted acetylated sugars which, together with peroxides in detergents, produce the bleaching action and give other properties which are suitable for detergents.
  • DE 43 08 123 A1 discloses acylated aminosaccharides as bleach activators, some of which are present as a yellowish oil and for this reason alone are not very suitable.
  • bleach activators based on acetylated sucrose were described by Mentech et al in "Carbohydrates as organic raw materials” (G. Descotes, 1993, pp. 185-201).
  • the production of partially acetylated sucrose leads to product mixtures, it being shown that especially the hexa- or hepta-acetyl-sucrose derivatives as bleach activators correspond in their effectiveness only to the TAED.
  • the preparation of these products is difficult since the selectivity of the reaction in the direction of these derivatives can hardly be influenced.
  • the invention is based on the object of proposing very specific carbohydrate compounds for use as bleach activators or complexing agents in detergent formulations which no longer show the disadvantages of the products known hitherto.
  • peracetylated carbohydrate compounds from the group of sucrose, maltose, lactose, palatinose, trehalulose, glucose and fructose or mixtures thereof are proposed for use as bleach activators or complexing agents in detergent formulations which have one or two carboxyl functions and as mono- or diacid or as their alkali salt.
  • carbohydrate compounds are not only suitable from a technical and economic point of view in terms of their preparation, but that, in addition to their excellent action as a bleach activator, they also act as complexing agents and thus make the addition of conventional complexing agents unnecessary or reduce their proportion as detergent components.
  • the peracetylated carbohydrate compounds with one or two carboxyl functions to be used according to the invention can be produced by chemical oxidation, for example with NaOCl according to EP 0 278 107 or by electrochemical oxidation or by catalytic oxidation with noble metal catalysts. The latter is described in DE OS 43 07 388. By appropriate choice of the catalyst, it is also possible to obtain the dicarboxylic acids.
  • acetylated dicarboxylic acid derivatives are prepared analogously to the synthesis of the monooxidized compounds.
  • Acetylation is known per se; reference is made to E. Reinefeld, Zucker, 21 , 12 (1968).
  • sucrose is used as the carbohydrate
  • oxidation of one of the primary OH groups potentially capable of reaction gives a mixture of 2- [ ⁇ -D-glucopyranosyl] - ⁇ -D-fructofuranuronic acid (C-6 acid), 2 - ( ⁇ -D-glucopyranuronyl) - ⁇ -D-fructofuranoside (C-6'-acid) and 2-keto- [2- ( ⁇ -D-glucopyronosyl) - ⁇ -D-glucofuranonic acid (C-1-acid) with a purity of over 95%.
  • this product composition is briefly referred to as "sucrose acids”.
  • the sucrose acids obtained are isolated by drying as the sodium salt.
  • composition of the mono-oxidized product mixtures depends on the catalyst used.
  • the peracetylation of the sucrose monooxidation products sometimes leads to new compounds which are excellent as bleach activators own.
  • the acetylation can also be controlled so that all OH functions on the molecule are esterified.
  • the products completely acetylated on the OH functions are designated with the abbreviation of the oxidation products and the note acetate (eg sac acetate).
  • the carboxyl function is obtained under the reaction conditions, so that compounds can be isolated which are excellent bleach activators with 7 acetyl groups and at the same time show sufficient water solubility for the washing process.
  • the acetylation can be carried out in various ways. Alkyl anhydrides or alkyl acid chlorides and various catalysts can be used as acylating agents. Table 2 shows various methods for the preparation of peracetylated sucrose monocarboxylic acids. Tab.
  • lactobionic acid maltobionic acid
  • oxidized isomaltulose gluconic acid
  • gluconic acid were acetylated using process (c) with acetic anhydride / zinc chloride.
  • the peracetylated products based on disaccharide are obtained as water-soluble solids, while the glucose product can only be isolated as an oil.
  • TAED and peracetylated glucose were used as reference substances.
  • Their hydrogen peroxide and their peracetic acid formation as a function of time, pH and bleaching agent (sodium perborate, sodium percarbonate) were recorded titrimetrically.
  • the hydrogen peroxide content was determined cerimetrically in acidic solution (5% sulfuric acid) at 0 ° C., the formation of peracetate was determined indirectly by titration of the iodine released by the peracid with sodium thiosulfate solution (FP Greenspan, DG Mackellar, Anal. Chem., 20 , 1061-1062 , 1948).
  • Figure 1 shows the formation of hydrogen peroxide for the bleach system TAED / perborate compared to acetylated sucrose monocarboxylic acids / perborate at 30 ° C. Except for the initial concentration, the hydrogen peroxide concentration in the carbohydrate-based bleach activator lies above the TAED curve. This was also observed when using sodium percarbonate as a bleach. With regard to the formation of peracetate, the curve of the carbohydrate bleach activator is also above that of TAED.
  • Acetylated sucrose acids or other carbohydrate-based peracetylated products show an excellent bleaching effect with the usual bleaching agents such as sodium perborate and sodium percarbonate.
  • the effectiveness is initially lower, but the formation of hydrogen peroxide and peracetate is higher than with the TAED.
  • the calcium binding capacity of the reaction solution was checked by titrimetry.
  • the calcium binding capacity of the free carbohydrate acids was determined.
  • the free acids (1 g each) were neutralized with 0.1 N NaOH and then mixed with 10 ml of 2% sodium carbonate solution.
  • the solution was made up to 100 ml (pH adjusted to 11) and titrated with 0.25 M Ca acetate solution. In both cases it could be shown that the carbohydrate-based bleaching components show corresponding complexing behavior towards calcium.
  • Example 1 Preparation of acetylated sucrose acids by esterification with acetyl chloride and pyridine
  • the product obtained was obtained as a white solid and could be used directly for the application tests.
  • Example 2 Preparation of acetylated lactobionic acids by esterification with sodium acetate and acetic anhydride
  • the product obtained was yellowish and was obtained as a white solid after recrystallization.
  • Example 3 Preparation of acetylated sucrose acids by esterification with zinc chloride and acetic anhydride
  • the product obtained is obtained as a white solid, which can be used directly in detergent formulations.
  • gluconic acid was acetylated with acetic anhydride / zinc chloride for comparison, the product being able to be isolated only as an oil.
  • EDTA ethylenediaminetetraacetic acid
  • 28.7 ml of a 0.1 N sodium hydroxide solution at 30 ° C. the corresponding amount of the activator (0.08 molar solution) and 6.6 ⁇ 10 -3 mol sodium percarbonate (1,036 g) are added.
  • 3 ml samples are taken every 15 minutes, dripped into 3.5 ml of 5% sulfuric acid while cooling with ice and titrated rapidly with 0.1 N cerammonium sulfate solution (1 NH 2 SO 4 ) (indicator ferroin). Then the solution with 1 ml of 10% Potassium iodide solution added. The resulting iodine is titrated with 0.1 N sodium thiosulfate solution.
  • a borax / NaOH buffer solution (at 20 ° C., pH 10) is used instead of 0.1 N sodium hydroxide solution.
  • the calcium binding capacity of the reaction solution was checked by titration according to Hampshire. For this purpose, 10 ml of a 2% sodium carbonate solution were added to the reaction solution and made up to 100 ml. The mixture was then titrated with 0.25 M calcium acetate solution until it became cloudy.
  • the calcium binding capacity was determined in the presence of sodium percarbonate, the values listed in Table 7 below being determined.
  • Tab. 7 Hampshire test of peracetylated carbohydrates in the presence of sodium percarbonate substance Ca carbonate amount (mg) Sac acetate 33 Lac acetate 31 Glu acetate 28 Mal acetate 30th
  • the solution After 30 minutes of activating at 30 ° C., the solution, cooled to room temperature, is mixed with 10 ml of aqueous 2% sodium carbonate solution, the pH is adjusted to 11 with 1N sodium hydroxide solution and the volume is increased to 100 ml with distilled water. The solution is titrated with 0.25 M calcium acetate solution until it becomes cloudy.

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  • Chemical & Material Sciences (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)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP96102954A 1995-03-04 1996-02-28 Formulations de nettoyage contenant des hydrates de carbone peracétylés ou acylés comme activateurs de blanchiment ou agents complexants. Expired - Lifetime EP0731161B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19507668 1995-03-04
DE19507668A DE19507668C2 (de) 1995-03-04 1995-03-04 Waschmittelformulierungen, enthaltend eine acylierte Disaccharidcarbonsäure

Publications (3)

Publication Number Publication Date
EP0731161A2 true EP0731161A2 (fr) 1996-09-11
EP0731161A3 EP0731161A3 (fr) 1997-07-02
EP0731161B1 EP0731161B1 (fr) 2002-09-04

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EP96102954A Expired - Lifetime EP0731161B1 (fr) 1995-03-04 1996-02-28 Formulations de nettoyage contenant des hydrates de carbone peracétylés ou acylés comme activateurs de blanchiment ou agents complexants.

Country Status (5)

Country Link
US (1) US5968886A (fr)
EP (1) EP0731161B1 (fr)
AT (1) ATE223474T1 (fr)
DE (2) DE19507668C2 (fr)
DK (1) DK0731161T3 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19624345A1 (de) * 1996-06-19 1998-01-08 Suedzucker Ag Acylierte Carboxyalkylsaccharide, Verfahren zu deren Herstellung und deren Verwendung in Waschmitteln
US6316606B1 (en) * 1996-06-19 2001-11-13 Canon Kabusiki Kaisha Polymeric compound comprising glycopolymer and a method for decomposing the same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5448142B2 (ja) * 2005-03-09 2014-03-19 エクソンモービル・ケミカル・パテンツ・インク オレフィンのオリゴマー化
US7414006B2 (en) * 2005-03-09 2008-08-19 Exxonmobil Chemical Patents Inc. Methods for oligomerizing olefins

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991010719A1 (fr) * 1990-01-22 1991-07-25 Novo Nordisk A/S Composition detergente de blanchissage
EP0517969A1 (fr) * 1991-06-10 1992-12-16 AUSIMONT S.p.A. Procédé pour améliorer l'efficacité de blanchiment d'un "persel" inorganique ou d'hydrogène peroxyde
EP0527039A2 (fr) * 1991-08-06 1993-02-10 Unilever Plc Composition détergente de blanchissage contenant des dérivés de sucre comme précurseurs de blanchiment
DE4402051A1 (de) * 1994-01-25 1995-07-27 Henkel Kgaa Gerüststoff für Wasch- oder Reinigungsmittel

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GB1385403A (en) * 1971-07-14 1975-02-26 Unilever Ltd Process for preparing oxidised carbohydrates
US3784475A (en) * 1971-11-17 1974-01-08 Procter & Gamble Detergent compositions containing oxidized polysaccharide builders
AT333781B (de) * 1972-11-06 1976-12-10 Krems Chemie Gmbh Verfahren zur herstellung neuer gemischter partialester
US3919107A (en) * 1973-03-23 1975-11-11 Procter & Gamble Built detergent compositions containing dextrin esters of poly carboxylic acids
JPS5039707A (fr) * 1973-08-15 1975-04-12
JPS5423364B2 (fr) * 1973-12-17 1979-08-13
JPS5313354B2 (fr) * 1974-03-06 1978-05-09
JPS60120800A (ja) * 1983-12-05 1985-06-28 旭電化工業株式会社 洗浄剤組成物
DE3704166A1 (de) * 1987-02-11 1988-08-25 Solvay Werke Gmbh Verfahren zur herstellung von aldonsaeuren oder deren salze
US4889651A (en) * 1988-01-21 1989-12-26 Colgate-Palmolive Company Acetylated sugar ethers as bleach activators and detergency boosters
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JPH051090A (ja) * 1991-06-26 1993-01-08 Shiseido Co Ltd シヨ糖脂肪酸エステルの分離・精製方法
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WO1991010719A1 (fr) * 1990-01-22 1991-07-25 Novo Nordisk A/S Composition detergente de blanchissage
EP0517969A1 (fr) * 1991-06-10 1992-12-16 AUSIMONT S.p.A. Procédé pour améliorer l'efficacité de blanchiment d'un "persel" inorganique ou d'hydrogène peroxyde
EP0527039A2 (fr) * 1991-08-06 1993-02-10 Unilever Plc Composition détergente de blanchissage contenant des dérivés de sucre comme précurseurs de blanchiment
DE4402051A1 (de) * 1994-01-25 1995-07-27 Henkel Kgaa Gerüststoff für Wasch- oder Reinigungsmittel

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19624345A1 (de) * 1996-06-19 1998-01-08 Suedzucker Ag Acylierte Carboxyalkylsaccharide, Verfahren zu deren Herstellung und deren Verwendung in Waschmitteln
US6316606B1 (en) * 1996-06-19 2001-11-13 Canon Kabusiki Kaisha Polymeric compound comprising glycopolymer and a method for decomposing the same
DE19624345B4 (de) * 1996-06-19 2004-12-23 Südzucker AG Mannheim/Ochsenfurt Acylierte Kohlenhydrate mit mindestens einer mit dem Kohlenhydrat veretherten Carboxyalkyl-Gruppe, Verfahren zu deren Herstellung und deren Verwendung in Waschmitteln
US6900295B2 (en) 1996-06-19 2005-05-31 Canon Kabushiki Kaisha Polymeric compound comprising glycopolymer and a method for decomposing the same

Also Published As

Publication number Publication date
EP0731161A3 (fr) 1997-07-02
DE59609612D1 (de) 2002-10-10
US5968886A (en) 1999-10-19
DK0731161T3 (da) 2003-01-13
DE19507668C2 (de) 2000-01-27
DE19507668A1 (de) 1996-09-12
ATE223474T1 (de) 2002-09-15
EP0731161B1 (fr) 2002-09-04

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