WO1996018575A1

WO1996018575A1 - Powdered polyaspartimide-hydrogen peroxide complexes, method for producing them and their use

Info

Publication number: WO1996018575A1
Application number: PCT/EP1995/004789
Authority: WO
Inventors: Matthias Kroner; Jörg Breitenbach; Dieter Boeckh
Original assignee: Basf Aktiengesellschaft
Priority date: 1994-12-16
Filing date: 1995-12-06
Publication date: 1996-06-20
Also published as: DE4444975A1

Abstract

Disclosed are powdered complexes of condensation polymers that contain aspartimide units and of hydrogen peroxide, with a mean paricle diameter of 10 νm to 5 mm and a hydrogen peroxide content of 1 to 45 wt.%; a method for producing the powdered complexes by reacting hydrogen peroxide with powdered condensation polymers containing aspartimide units with a mean particle diameter of 10 νm to 5 mm and drying the mixture, as well as use of the polyaspartimide-hydrogen peroxide complexes as admixture to detergents and cleaners, as preservative and disinfectant, as bleach in hair-care products and as polymerization initiator.

Description

Powdery polyaspartimide-hydrogen peroxide complexes, process for their preparation and their use

description

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.

The production of polyvinylpyrrolidone-hydrogen peroxide complexes is known, cf. US-A-3 376 110 and US-A-3 480 557. As is apparent from the above-mentioned prior art, 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 production of powdery complexes from polyvinyl pyrrolidone and hydrogen peroxide in a molar ratio of 1: 1 by reaction of polyvinyl pyrrolidone and solutions of hydrogen peroxide is known from US Pat. No. 5,008,106 and US Pat. No. 5,066,481 known. According to the process of US Pat. No. 5,077,047, powdered polyvinylpyrrolidone is brought into contact with an aqueous solution of hydrogen peroxide in a fluidized bed. This gives free-flowing powders of polyvinylpyrrolidone-hydrogen peroxide complexes which, according to the teaching of US Pat. No. 5,159,033, are used as polymerization initiators.

From DE-A-3 820 726 it is known to coat particulate hydrogen peroxide addition compounds such as sodium perborate with water-soluble homopolymers or copolymers containing free carboxyl groups in the acid form. This increases the storage stability of the hydrogen peroxide addition compounds without causing problems in the development of hydrogen peroxide when water enters. The aqueous solution of the polymer is preferably sprayed onto the particulate addition compounds of the hydrogen peroxide in a fluidized bed and the water is removed by drying. The invention has for its object to provide new complexes of hydrogen peroxide.

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 μm 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 μm 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. Examples of 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. The 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.

According to the invention, 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. and are preferably in the range from 200 to 270 ° C. The polycondensation of aspartic acid can be carried out under the catalytic influence of acids in the temperature range specified above or even at lower temperatures, for example in the range from 140 to 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. The production of polycondensates containing aspartimide units is known, for example, from US Pat. No. 3,052,655, J. Org. Chem. Volume 26, 1084 (1961), DE-A-4 023 463, US Pat. No. 5,116,513 and US-A-5 219 986. The production of cocondensates of polyaspartic acid is known, for example, from WO-A-94/01486.

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. Depending on the manufacturing conditions, 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 μm to 5 mm, preferably 50 μm 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 μm 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 μm 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. For example, 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. Here 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.

Depending on the reaction conditions, the hydrogen peroxide in the complexes can be physically associated with polyaspartimide or via a hydrogen bond. However, hydrogen peroxide can also be added with ring opening of the polyaspartimide and with the formation of α- and / or β-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. In order to keep them free-flowing, it may be necessary to powder them with finely divided release agents, e.g. with finely divided silica, alumina or bentonite. The average particle size of the release agents is e.g. 1 to 100 μm and is preferably below 10 μm. 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. As 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.

In detergents and cleaning agents, 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).

In addition, 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.

The 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.

Further information on the composition of detergents and cleaners can be found in Ulimann's Encyclopedia of Industrial Chemistry, Verlag Chemie, Weinheim, 4th edition, pages 63-160.

In addition to the complex according to the invention, the detergents can additionally contain bleaching systems. In the simplest case, this is 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 percentages in the examples mean percent by weight. example 1

The reactor consists of a granulating cylinder, the underside of which is sealed with a sieve with a mesh size of 10 to 500 μm 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 μm. 100 g of a 30% strength aqueous hydrogen peroxide solution are sprayed onto the polyaspartimide within 0.5 hours. After the hydrogen peroxide addition has ended, the reaction mixture is whirled at 25 ° C. for a further hour. The water content of the powdery polyaspartimide-hydrogen peroxide complex is then 4.2% by weight. The reaction mixture is cooled and removed from the reactor. A titration with Cer IV ions determines a hydrogen peroxide content of 10.5% by weight in the polyaspartimide-hydrogen peroxide complex. The average particle size of the complex corresponds to the average particle size of the polyaspartimide used.

Example 2

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 μm and a hydrogen peroxide content of 15% by weight is obtained.

Claims

claims

1. Powdery complexes of aspartimide units containing polycondensates and hydrogen peroxide with a medium

Particle diameter of 10 μm to 5 mm and a hydrogen peroxide content of 1 to 45% by weight.

2. A process for the preparation of powdered complexes according to claim 1, characterized in that powdered

Polycondensates containing aspartimide units with an average particle diameter of 10 μm to 5 mm are brought into contact with hydrogen peroxide and the mixture dries.

3. The method according to claim 2, characterized in that the powdered aspartimide-containing polycondensates in a fluidized bed through which an inert gas is passed, brought into contact with hydrogen peroxide at temperatures in the fluidized bed of 20 to 80 ° C. .

4. The method according to any one of claims 2 and 3, characterized gekenn¬ characterized in that the mixture is dried to a water content of less than 5 wt .-%.

5. The method according to any one of claims 1 to 4, characterized gekenn¬ characterized in that the powdery complexes are coated with at least one layer of a water-soluble compound.

6. Use of the powdered complexes according to claim 1 as an additive to detergents and cleaning agents, as a preservative and disinfectant, as a bleaching agent in hair cosmetics and as a polymerization initiator.