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WO1996018575A1 - Complexes pulverulents de polyaspartimide-peroxyde d'hydrogene, leur procede de fabrication et leur utilisation - Google Patents

Complexes pulverulents de polyaspartimide-peroxyde d'hydrogene, leur procede de fabrication et leur utilisation Download PDF

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Publication number
WO1996018575A1
WO1996018575A1 PCT/EP1995/004789 EP9504789W WO9618575A1 WO 1996018575 A1 WO1996018575 A1 WO 1996018575A1 EP 9504789 W EP9504789 W EP 9504789W WO 9618575 A1 WO9618575 A1 WO 9618575A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen peroxide
complexes
powdered
polyaspartimide
aspartimide
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
PCT/EP1995/004789
Other languages
German (de)
English (en)
Inventor
Matthias Kroner
Jörg Breitenbach
Dieter Boeckh
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.)
BASF SE
Original Assignee
BASF SE
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
Application filed by BASF SE filed Critical BASF SE
Publication of WO1996018575A1 publication Critical patent/WO1996018575A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/22—Peroxides; Oxygen; Ozone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88—Polyamides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/08—Preparations for bleaching the hair
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides

Definitions

  • Powdery polyaspartimide-hydrogen peroxide complexes process for their preparation and their use
  • the invention relates to powdery complexes of aspartimide units containing polycondensates and hydrogen peroxide, processes for their preparation and their use as additives for washing and cleaning agents, as preservatives and disinfectants, as bleaches in hair cosmetics and as poly ⁇ merization initiator.
  • polyvinylpyrrolidone-hydrogen peroxide complexes The production of polyvinylpyrrolidone-hydrogen peroxide complexes is known, cf. US-A-3 376 110 and US-A-3 480 557.
  • polyvinylpyrrolidone is mixed with an excess of hydrogen peroxide in aqueous solution and enough water is evaporated to leave a dry residue.
  • Powdered polyvinylpyrrolidone-hydrogen peroxide complexes with a hydrogen peroxide content of 2 to 70% by weight are obtained.
  • the hydrogen oxide content of the complexes mentioned depends very much on the drying conditions and is difficult to reproduce.
  • the object is achieved according to the invention with powdery complexes of polycondensates containing aspartimide units and hydrogen peroxide with an average particle diameter of 10 ⁇ m to 5 mm and a hydrogen peroxide content of 1 to 45% by weight.
  • the invention also relates to a process for the preparation of the above-mentioned powdery complexes, in which polycondensates containing powdery aspartimide units with an average particle diameter of 10 ⁇ m to 5 mm are brought into contact with hydrogen peroxide and the mixture is dried.
  • the powdered aspartimide units containing polycondensation products are preferably brought into contact with hydrogen peroxide in a fluidized bed through which an inert gas is passed at temperatures in the fluidized bed of 20 to 80 ° C.
  • the mixture is dried, for example, to a water content of less than 5% by weight.
  • Hydrogen peroxide in the form of concentrated or dilute solutions can be used to prepare the polyaspartimide-hydrogen peroxide complexes according to the invention.
  • solvents which can be used are water, polyalkylene glycols, nonionic surfactants and common solvents which are miscible with hydrogen peroxide, such as diethyl ether, phosphoric acid or sulfuric acid.
  • Mixtures of solvents which can be used as diluents for hydrogen peroxide can also be used, e.g. Mixtures of water and phosphoric acid with a content of, for example, 0.01 to 5% by weight of phosphoric acid.
  • the preferred solvent for hydrogen peroxide is water.
  • concentration of the hydrogen peroxide in the solutions is, for example, 1 to 90, preferably 3 to 70% by weight. Commercial 30 or 50% by weight aqueous solutions of hydrogen peroxide are particularly preferred.
  • hydrogen peroxide is stabilized with polycondensates containing aspartimide units.
  • Suitable as polycondensates containing aspartimide units are condensation products which contain at least 30 mol% of aspartimide units. These can be homocondensates of aspartic acid and cocondensates of aspartic acid with compounds which can be co-condensed with aspartic acid.
  • Polyaspartimide is preferably used to stabilize hydrogen peroxide.
  • Polycondensates containing aspartimide units are prepared, for example, by known processes by thermal polycondensation of L- or D, L-aspartic acid. In the thermal polycondensation of aspartic acid, the reaction temperatures are, for example, at least 190 ° C.
  • Acids suitable for the production of polyaspartimides are, for example, phosphoric acid, phosphorous acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, amidosulfonic acid, ammonium bisulfate, trimethylammonium bisulfate, triethylammonium bisulfate or hydrochloric acid.
  • Polycondensates containing apartimide units are also known from the reaction of maleic acid or maleic anhydride and ammonia and polymerization of the resulting maleic acid monoamide. See US-A-4 839 461, WO-A-94/06843 and WO-A-94/06845.
  • the polycondensation of maleic acid monoamide, the ammonium salt of maleic acid amide, of mono- and diammonium maleate or of mono- and diammonium fumarate is usually carried out at temperatures above 130 ° C.
  • the polyaspartimides can be the reaction temperature and the duration of the polycondensation and, if appropriate, the concomitant use of the catalysts contain up to 70 mol% of polyaspartic acid units.
  • the polycondensation of D- or D, L-aspartic acid is preferably carried out under reduced pressure. This gives polycondensates containing aspartimide units which contain at least 30 moles of aspartimide units in condensed form.
  • the molecular weight (weight average) of the polycondensates containing aspartimide units is, for example, 500 to 200,000 and is preferably in the range from 1,000 to 100,000.
  • the polyaspartimides have an average particle diameter of 10 ⁇ m to 5 mm, preferably 50 ⁇ m to 1 mm.
  • the powdery complexes according to the invention of polycondensates containing aspartimide units and hydrogen peroxide are obtained by contacting solid powdered aspartimide with an average particle diameter of 10 ⁇ m to 5 mm with hydrogen peroxide and drying the mixture.
  • the polyaspartimides and hydrogen peroxide are brought into contact with one another, for example, at temperatures of 10 to 80, preferably 20 to 60 ° C.
  • a method of operation is particularly preferred in which powdered polyaspartimide with a particle size of 50 ⁇ m to 2 mm is placed in a fluidized bed at temperatures from 30 to 50 ° C. and in the specified temperature range with a 30 to 50% strength aqueous solution of hydrogen peroxide sprayed under vortex.
  • air or preferably an inert gas such as nitrogen, carbon dioxide or mixtures of nitrogen and carbon dioxide can be used as the fluidizing gas.
  • the water introduced together with the hydrogen peroxide solution is removed from the fluidized bed by the gas stream.
  • Hydrogen peroxide is preferably metered in such an amount that the polyaspartimide is present as a free-flowing powder during the entire contact time.
  • the water content of the solid, free-flowing complex of polycondensates containing aspartimide units and hydrogen peroxide can be reduced to values of less than 5% by weight by further swirling the reaction mass.
  • you can increase the temperature up to 80 ° C. Powdery complexes of polyaspartimide and hydrogen peroxide are then obtained which are free-flowing and which do not stick together.
  • the complexes of the invention can also be prepared, for example, by slurrying polycondensates containing powdered aspartimide units in hydrogen peroxide or in a solution of hydrogen peroxide in an organic solvent and isolating them from the slurry by known methods after, for example, 10 minutes to 2 hours.
  • the complexes of polymers containing aspartimide units and hydrogen peroxide are advantageously dried in vacuo, e.g. at pressures from 0.1 to 200 mbar.
  • the complexes of polycondensation containing aspartimide units and hydrogen peroxide contain, for example, 1 to 45, preferably 5 to 20,% by weight of hydrogen peroxide.
  • the determination of the hydrogen peroxide content can be carried out, for example, using Cer IV ions according to D. Swern, Organic Peroxides, Vol. I, Wiley Interscience, New York, 1970, pages 500-510.
  • the hydrogen peroxide in the complexes can be physically associated with polyaspartimide or via a hydrogen bond.
  • hydrogen peroxide can also be added with ring opening of the polyaspartimide and with the formation of ⁇ - and / or ⁇ -polyperoxyaspartic acid.
  • Polyperoxyaspartic acid decomposes at higher temperatures to form oxygen and polyaspartic acid.
  • the complexes out Polycondensates containing aspartimide units and hydrogen peroxide are stable at temperatures up to 65 ° C. and can be stored safely.
  • the decomposition temperature of the complexes according to the invention can be determined with the aid of thermoanalytical methods. Two exothermic conversions are obtained with a maximum at 90 ° C and a second exothermic conversion at 125 ° C.
  • the powdery complexes of aspartimide units containing polycondensates and hydrogen peroxide can optionally be coated with at least one layer of a water-soluble compound.
  • Suitable water-soluble compounds are, for example, carboxyl-containing homopolymers and copolymers which are soluble in water at least in the form of the sodium salts.
  • Compounds of this type are, for example, polyaspartic acid in the form of the free acid or in the form of the alkali metal or alkaline earth metal salts, polyacrylic acids, copolymers of acrylic acid and maleic acid, homopolymers of maleic acid and copolymers of acrylic acid and acrylamidopropanesulfonic acid.
  • the complexes can also be coated with polyvinylpyrrolidone or with urea.
  • the coating of the complexes according to the invention with water-soluble compounds contributes to an increase in the stability of the complexes.
  • the average particle size of the release agents is e.g. 1 to 100 ⁇ m and is preferably below 10 ⁇ m.
  • the amounts of finely divided release agents are, for example, 0.1 to 5% by weight, based on the complexes.
  • the amounts of water-soluble compounds applied as a coating on the complexes are, for example, 2 to 20% by weight, based on the complexes.
  • the pulverulent complexes of polycondensates containing aspartimide units and hydrogen peroxide are used as additives for detergents and cleaning agents, as preservatives and disinfectants, as bleaches in hair cosmetics and as polymerisation initiators.
  • preservatives and disinfectants the complexes according to the invention are contained, for example, in toothpastes or are used as germicides in the treatment of skin diseases.
  • the complexes act as bleaching agents, the condensate containing aspartimide units with the complex-bound hydrogen peroxide acting as an activated bleaching system under the washing conditions. This manifests itself in a higher bleaching action of the complex according to the invention compared to pure hydrogen peroxide when using the same molar amounts. For example, when using a washing machine formulation which contains no further bleach activator or bleach, in the washing test a higher effect of the complex according to the invention compared to the same amount of hydrogen peroxide, perborate or percarbonate (calculated on the same molar amounts of hydrogen peroxide).
  • the polyaspartic acid that forms in the alkaline wash liquor which can also partly be present as peracid, has a dispersing effect on pigment dirt and incrustation formers such as calcium and magnesium carbonate, lime soaps, silicates etc.
  • the complexes according to the invention are added to the washing and cleaning agents in an amount of 0.1 to 30% by weight. They can be contained as the sole bleaching components or can be used in combination with the known bleaching systems.
  • composition of the detergent and cleaning agent formulations can be very different.
  • Detergent and cleaning agent formulations usually contain 2 to 50% by weight of surfactants and, if appropriate, builders. This information applies to both liquid and powder detergents.
  • Detergent and cleaning agent formulations which are common in Europe, the U.S.A. and Japan can be found, for example, in Chemical and Engn. News, Vol. 67, 35 (1989) tabulated.
  • the detergents can additionally contain bleaching systems.
  • this is a bleaching agent such as Hydrogen peroxide, sodium perborate, sodium percarbonate or sodium hypochlorite.
  • a bleaching agent such as Hydrogen peroxide, sodium perborate, sodium percarbonate or sodium hypochlorite.
  • An overview of the usual bleaching agents for detergents and cleaning agents can be found in P. Kerzel and Th. Lieser, Tenside Surf. Det. ___, 13-28 (1990) and in J. Hofmann, G. Just, W. Pritzkow and H. Schmidt, Prakt. Chem. 334, 293-297 (1992). given.
  • the bleaching agents are often also used in combination with bleach activators, e.g.
  • Tetraacetylethylenediamine or Pentaacetylglucose used, which increase the effectiveness of the bleaching system at lower temperatures.
  • the usual bleach activators are mentioned in the above literature.
  • the reactor consists of a granulating cylinder, the underside of which is sealed with a sieve with a mesh size of 10 to 500 ⁇ m and the top of which is sealed with 4 filter bags, which are periodically cleaned with the aid of compressed air.
  • 150 g of polyaspartimide which has a molar mass M w of 6,000 and was prepared by thermal polycondensation of aspartic acid at 240 ° C., are placed in this reactor.
  • the polyaspartimide is whirled up by blowing in air (120 m 3 / h) and heated to a temperature of 50 ° C.
  • the average particle diameter of the polyasparimide is 100 ⁇ m.
  • Example 1 is repeated with the exception that 100 g of 30% hydrogen peroxide solution are sprayed onto 100 g of polyaspartimide within one hour. After drying, a powdery polyaspartimide-hydrogen peroxide complex with an average particle size of 100 ⁇ m and a hydrogen peroxide content of 15% by weight is obtained.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Veterinary Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Detergent Compositions (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne des complexes pulvérulents constitués de polymères de condensation contenant des motifs aspartimide et de peroxyde d'hydrogène, présentant un diamètre particulaire moyen de 10 νm à 5 mm et une teneur en peroxyde d'hydrogène de 1 à 45 % en poids; un procédé pour produire ces complexes pulvérulents par réaction de peroxyde d'hydrogène avec des polymères de condensation pulvérulents contenant des motifs aspartimide et présentant un diamètre particulaire moyen de 10 νm à 5 mm, et séchage du mélange; ainsi que l'utilisation des complexes de polyaspartimide-peroxyde d'hydrogène comme additif à des détergents et à des nettoyants, comme conservateur et désinfectant, comme décolorant en cosmétologie capillaire et comme initiateur de polymérisation.
PCT/EP1995/004789 1994-12-16 1995-12-06 Complexes pulverulents de polyaspartimide-peroxyde d'hydrogene, leur procede de fabrication et leur utilisation Ceased WO1996018575A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19944444975 DE4444975A1 (de) 1994-12-16 1994-12-16 Pulverförmige Polyaspartimid-Wasserstoffperoxid-Komplexe, Verfahren zu ihrer Herstellung und ihre Verwendung
DEP4444975.5 1994-12-16

Publications (1)

Publication Number Publication Date
WO1996018575A1 true WO1996018575A1 (fr) 1996-06-20

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PCT/EP1995/004789 Ceased WO1996018575A1 (fr) 1994-12-16 1995-12-06 Complexes pulverulents de polyaspartimide-peroxyde d'hydrogene, leur procede de fabrication et leur utilisation

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DE (1) DE4444975A1 (fr)
WO (1) WO1996018575A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3480557A (en) * 1967-01-30 1969-11-25 Gaf Corp Solid stabilized hydrogen peroxide compositions
WO1992017158A1 (fr) * 1991-04-08 1992-10-15 Isp Investments Inc. Procede de production de produits en pvp-h2o¿2?
WO1994003526A1 (fr) * 1992-08-07 1994-02-17 Bayer Aktiengesellschaft Decoloration de polyaspartate et de copolymeres de polyaspartate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3480557A (en) * 1967-01-30 1969-11-25 Gaf Corp Solid stabilized hydrogen peroxide compositions
WO1992017158A1 (fr) * 1991-04-08 1992-10-15 Isp Investments Inc. Procede de production de produits en pvp-h2o¿2?
WO1994003526A1 (fr) * 1992-08-07 1994-02-17 Bayer Aktiengesellschaft Decoloration de polyaspartate et de copolymeres de polyaspartate

Also Published As

Publication number Publication date
DE4444975A1 (de) 1996-06-20

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