DE2339888A1 - BIODEGRADABLE SEQUESTRANT COMPOUND - Google Patents

Description

Dr. Hans-Heinrich Willrath

Dr. Dieter Weber Diploma in Phys. Klaus Seiffert

PATENT LAWYERS

D - 62 WIESBADEN "ft PO Box 1327

Gustav-Freytag-Strasse 25 «■ (04121) 372720 Telegram address: WILLPATENT

2030/2055 series

Les Produits du Santerre-Orsan 16-18, Rue Ballu, 75009 Paris / France

L'Air Liquide Societe Anonyme pour I ¹ Etude et 1'Exploitation des Procedes Georges Claude 75, Quai d'Orsay, 75007 Paris / France

Biodegradable sequestering compound

Priority i August 9, 1972,

No., E.N. 7 228 746, France

Nov 28, 1972, No. E.N, 7 242 210, France

The invention relates to a non-toxic, non-polluting, biodegradable sequestrant composition which contains an L- or DL- Ν, Ν-dicarboxymethylamino acid. The invention also relates to a method for dex ^ n Manufacturing. Numerous sequestrant connections are known

/ »09800/1174

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Postal check: Frankfurt / Main 6763-602 Bank: Dresdner Bank AG. Wiesbaden, Konio no. 276807

ORiGiNAL INSPECTED

fertilize, such as Tri-Polyp & Qsphate, ethylenediaminetetraacetic acid etc.; however, the majority of these compounds are not biodegradable and pollute the aquatic environment, In addition, as a result of them, phosphorus compounds fix very much

Oxygen with the pronounced reducing properties / known

harmful consequences for biological life "

As for chemical compounds of similar and neighboring structures of the main component of the new sequestrant composition concerns, we already know N-substituted derivatives of C (-dicarboxyamino acids, which are used in cleaning agents, Sequestrant compositions, dispersants and surfactants can be used, wherein the N-substituents from lower or higher carboxy alkyl groups, lower or higher acyl or lower or higher alkyl groups.

U.S. Patent 2,500,019, filed October 8, 1946, entitled "Method of producing polycarboxylic amino acids "describes a cumbersome one Process that involves several expensive and dangerous reaction stages such as sodium cyanide. Take place in the procedure a condensation reaction to form cyanohydrin, a hydrolysis reaction and a substitution reaction, It is necessary to carefully compare the rate of condensation with the rate of formation of the poly-

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to control carboxyanino acid. Another method for the production of Glutamic acid derivatives described, which in the hand " treatment of glutamic acid with magnesium bromoacetate or iodine acetate. In the presence of magnesium oxide and water, stands. The crystallized compound obtained is very hvgroscopic. The reaction components used make this process expensive and unsuitable for an industrial application,

According to the invention, a non-toxic and non-polluting biodegradable sequestrant was composed " Settlement of high efficiency found which has the advantage of being 85 to 90% biological includes degradable derivative of natural product. Every" if this sequestrant composition interferes, that only Contains carbon, oxygen and nitrogen but does not contain phosphorus, not the biological living water. Finally, due to its natural origin, the sequestrant according to the invention has no toxicity whatsoever,

The sequestrant of the invention becomes simpler Way by means of an immediate conversion in a single economical step with high yield of low »confessional prelude, which makes him a great deal

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Opens up the field of new uses.

According to the invention, the biodegradable sequestrant composition contains a derivative of an N, N-dicarboxymethylamino acid, by reacting monochloroacetic acid with the disodium salt of dicarboxyamino acid is obtained in an aqueous alkaline medium, around two carboxymethyl groups on the nitrogen atom to fix the amino group of this amino acid. For the Glutamic acid is particularly suitable for carrying out the invention and aspartic acid.

It has been found that monoacetic acid can advantageously be used without the Ν, Ν-dicarboxymethylamino acid to carboxymethylate on the nitrogen atom of the amino group, while so far only bromoacetic acid or a Bromoacetate and iodoacetic acid or an iodoacetate the practical Allowed extraction of the product.

The implementation according to the invention is a substitution reaction in an aqueous alkaline medium

COONa COONa

^CH 2 * 2 (NaOH) i ^(CH 2 ⁾ 2 ^ CH ₀ COONa

11) ^ H-NH ₂ + 2 CH ₂ Cl - COOH

: 00Na

409808/1174 + 2ciNa

The two hydrogen atoms of the ot-amino group of glutamic acid are replaced by two carboxymethyl groups derived from monochloroacetic acid. One of the essential Difficulties in obtaining the substituted derivative in good yield arise from the hydrolysis of monochloroacetic acid. This side reaction leads to the formation of sodium glycolate (see reaction 2). To remedy this deficiency, the conversion must therefore be carried out in the presence of free monochloroacetic acid and the alkaline one must be allowed Add agents only gradually in order to favor reaction (1) at the expense of reaction (2). The reaction rates namely, these two reactions are influenced by the concentration of free hydroxyl groups.

(2) CH ₂ Cl - COOH + NaOH ► NaCl + CH ₃ OH - COOH

(irreversible reaction) glycolic acid

The possibility of this hydrolysis reaction was established (2) minimize under the condition of carrying out the reaction at a weak point alkaline pH. As a result, one works advantageously during the reaction at pH between 8 and 10, preferably between 9 and 9.7. The yield obtained under these conditions is higher than 75% of theory, based on based on the monochloroacetic acid used and almost 100% based on glutamate. In contrast to previous methods, the

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It is advisable not to adjust the pH by means of an alkaline earth but rather an alkali, in particular sodium hydroxide in the form of concentrated lye. The reactants are allowed to react in an aqueous environment and for this purpose a softened or demineralized water or even distilled water is used. One works at a temperature between 70 and 100 ⁰ C, preferably between 80 and 90 ⁰ C;

If the speed of reaction (1) / is more favored by the rise in temperature than the speed of reaction (2), monosodium glutamate is advantageously used as the starting material, which is cheap and abundant on the market, although the acid itself can also be used. It is advantageous to work with an excess of monochloroacetic acid in order to compensate for any hydrolysis (reaction 2). The reaction proceeds with 2 _f 4 to 2.7 mol »preferably with 2.7 mol of monochloroacetic acid per one mol of glutamic acid (instead of the theoretical ratio of 2: 1)

The substitution reaction of the carboxymethyl groups expediently proceeds by pouring a monochloroacetic acid solution together and caustic soda in the sodium glutamate solution. The end of the reaction is preferred determined by the following tests:

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1. Dosing of the inorganic chlorine,

2. Potentiometric determination of the complex formation force,

3. Dosage of the NH or NHR groups by ninhydrin,

/ can isolate the crude product, which is immediately in liquid Form or by spraying the resulting solution is usable. The latter, which is close to a dry matter content 50% can be sprayed in a stream of warm air to obtain a white powder.

The process according to the invention is advantageously continuous carried out, which means a very great industrial advantage, namely a limitation of the plant and lowering of the cost cycle as a result of a production output to a greater extent. The powder obtained by spraying can be cleaned in the following two ways will:

1. Acidification with concentrated hydrochloric acid to pH 3r then spraying, extraction of the dry product with acetone, concentration of the extract for Dry. The oil obtained is treated with methanol and the final product crystallizes with a purity according to Seguestrantkraft of 95%.

2, adsorption on a strongly acidic cationic resin,

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then elution with sodium hydroxide solution and subsequent concentration.

The oil obtained is treated with methanol, from which the end product crystallizes. The purity of the Final product is 96 to 98% according to the sequestrant strength.

The composition according to the invention offers remarkable sequestrant properties not only with respect to alkaline earths, but also towards heavy metal ions, so that the agent is superior to what has been received so far, resulting in indisputable industrial advantages and usefulness result from the following areas:

Separation of metals via ion exchange columns.

Treatment of metals and degreasing of metallic surfaces,

Cleaning of radioactive surfaces, treatment of textiles,

Preparation of detergents and detergent products how they are used for washing dishes, use in perfumery and cosmetics and in the dairy.

The composition of matter of the invention satisfies smoothly its sequestering task, it forms soluble cation complexes with Ca, Mg, Li, Fe etc. in the presence of chemical Agents normally in aqueous solution, in particular

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Buffered alkaline environment can provide precipitation would. The composition is also used to mask or modify the chemical activity of cations used in reactions other than precipitation reactions in hard water, it especially binds them Detergent action-diminishing calcium in a complex. The sequestrant composition "potentializes", So the cleaning effect of the soap besides the inactivation of the cations «It also has an interesting one "Threshold effect" as opposed to previous compositions the use of minimal amounts is permitted. The composition according to the invention can be used with great advantage in detergent Mixtures of oils for household or industrial use.

The majority of liquid or powder detergents of the trade contains namely a sequestrant agent, its Present use in calcareous, so-called hard

The water allowed without precipitation of lime soap salts notable disadvantages in terms of pollution problems or environmental protection. So this most often includes tripolyphosphate used phosphorus in considerable quantities and the runoff from washing water in rivers or lakes vd-t contributed to their nutrient depletion «The

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In contrast, the invention provides a composition of matter which allows the lifting position of 'detergents that are free of phosphorus or contain reduced amounts of phosphorus and can therefore overcome this problem.

As a substitute for tripolyphosphate in detergents are others organic compounds, especially tertiary amine derivatives, such as sodium salts of ethylenediaminetetraacetic acid or such of nitrile chloroacetic acid or those of diethylenetriaminepentaacetic acid have been proposed. The sequestrant force these compounds are analogous (equivalent of cation complex to mole sequestrant). However, these connections are difficult to biodegrade and often provide toxic products for flora and fauna during their decomposition of waters, this behavior therefore limits their use, or the amount that, in the cleaning streams of urban Wastewater can be introduced without endangering the bacterial flora can. On the other hand, it has been shown that this type of compound has all its properties in a wide pH range, especially preserved in a neutral or alkaline environment. In particular, its sequestering effect is on strongest between pH 8 and 11, which is the alkalinity of the corresponds to usual detergents. It also changes the presence of oxidizing agents such as persalts and especially nothing of sodium perborate in the detergent

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em the properties described, on the contrary, it it has been shown that this compound has the catalytic effects of certain metals such as iron and Copper on the decomposition of peroxide compounds like Perborate prevented. This results in a reduction in the chemical breakdown of cellulose during the Washing process.

All these advantages over the previously used sequestrant products in detergent compositions make the compositions of matter according to the invention very superior to them for the known applications and allow detergents to be obtained for the various purposes which, in particular, allow very effective washing,
without supplying waste water that, <Ue so far with the
various fixings of the trade encountered
Have flaws.

The sequestrant composition for washing purposes according to the Invention contains at least 40% sodium salt of the derivative of N, N-bis-dicarboxymethylamino acid obtained in the above manner, The total or partial replacement of the tripolyphosphate in a balanced approach, i. H. containing a soap, a surface active product, a bleach and a. Filler, given

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if odor, whitener and deposit inhibitor. particularly permitted due to standardized. Dirtiest to get identical or slightly better results than with them a detergent containing 40 wt .-% tripolyphosphate, detergent compositions with about 20% are sequestrant compositions according to the invention which are sequestrant agents instead of tripolyphosphate especially interesting. Finally, measurements carried out have shown that the composition described is much more effective than tripolyphosphate, because it is an amount between one and a half and two times its weight can replace this phosphorus derivative depending on the conditions of use. One can provide detergent compositions, the sequestrant agent for calcium is a mixture of equal parts of tripolyphosphate and the sequestrant composition included according to the invention. The compositions with one part sequestrant composition, called "OS.j" and two parts tripolyphosphate are also from Interest, It has also been found that it is possible to sequester heavy metals by degrading cellulose caused by successive washes carried out in an oxidizing environment when one Detergent! Compositions used in which the sequestrant agent approximately 5% combined from the composition "OS-j" with about 1% magnesium silicate. This finding

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-. 13 -

further increases the value of the composition for washing purposes, because it allows the amount of substance contained in the wastewater to be determined according to urban household applications to be reduced in proportions that should not be neglected. Also allows the use of a Detergent with a seguestrant of the type described above for washing cotton fabrics a reduction in fabric wear as a result of the considerable reduction in chemical degradation of CeTlulose,

All detergent compositions which contain N, N-dicarboxymethylamino acid derivatives as sequestering agents, are due to the possibly complete reduction of the phosphate content, their biodegradability

β
and their nontoxicity to the flora and fauna of lakes and rivers. The following examples demonstrate the advantages resulting from the use of the composition described in the washing of soiled fabrics. In all tests carried out, a composition of matter was used that results from the reaction of monochloroacetic acid with the. Sodium salt of glutamic acid in an alkaline environment under the conditions given above. The composition obtained, designated as OS- in the tables, contains:

Sodium-N, N-bis-carboxymethylgluta »at 60% Sodium glycolate 12%

Salt rest z «10Q%

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It is in the form of a white powder with a bulk density of 0.56. The biodegradable sequestrant composition is non-toxic and has no harmful effects Irritant effects on the eyes or skin.

The lethal dose was determined using the spray dried compositions in the form of a powder containing 67.6% active ingredient expressed as the trisodium salt. The test was carried out on Swiss mice, the product being administered by the oral route and, in a single case, by tube insertion into the stomach. A volume of 0.5 ml was administered to each 20 g of the animal. The results obtained allow the conclusion that a dose as high as 2.845 g / kg body weight is without acute toxicity for a solution at a concentration of 11.3%. The lethal dose 50 (DL ₅₀ ) = 10.6 g / kg «This value was obtained by interpreting the results obtained after treating mice with solutions of 56% according to the formula of Karber and Behrens.

The eye irritation number was determined on the rabbit eye carried out in accordance with the provisions laid down in Appendix II of the Ordinance of April 5, 1971 and by the French General Commission for the Association of

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Analysis methods (Commission XX) have been established. This investigation has shown that no ocular reaction whatsoever was observed in any of the animals during the entire duration of the investigation occurred with the 56% solution of the spray-dried composition of 67.6% active substance, expressed treated as trisodium salt.

The primary stimulation number was determined after

in the

the measures taken / journal Officiel of April 21, 1971 are defined. For these experiments, the solution concentrated to 56% was dried by spraying Composition used containing 67.6% active substance expressed as trisodium salt. Despite their high With its active substance content, this solution was found to be only slightly irritating.

The biodegradability of the solution according to the invention was determined by testing on the bacterial bed. The tests carried out allow the conclusion that the composition is non-toxic for the microorganisms living in the formulation environment or in the cleaning stations appears and is able to be biodegraded by this microflora.

example 1

Preparation of N, N-BIs- (carboxymethyl) -glutamic acid Dissolve 1870 g (10 mol) of monosodium glutamate monohydrate in 2.5 l of water and 0.53 l of sodium hydroxide solution (10 mol) of solution A.

k 0 9.8 0 8/11 7 4

2339838

A solution of 2570 g (27 mol) of monochloroacetic acid in 2.5 liters of water and a 19 η sodium hydroxide solution (57 mol) are simultaneously poured into this solution in order to maintain the pH between 8 and 9 while at the same time the temperature of the reaction mixture is kept between 80 and 90 ^° C. for 1 hour 30 minutes.

The yield is 97 to 100% of N, N-bis (carboxymethyl) -Glutamic acid. When the monochloroacetic acid over "shot is decreased, a decrease in the yield occurs.

Monochloroacetic acid excess 0 5% 10% 35% Yield 76% 92% 95.5% 97% to 100%

On the other hand, a pH minimum of 8 is due to the second Substitution necessary.

Spraying this solution gives a white powder with 60% by weight of the sodium salt of N, N-BIs- (carboxymethyl) -glutamic acid, 47% of which is acid form) and 6.9% segregation by the method of G. Schwärzenbach and H Flaxhka (Complexometry Titrations, page 174) Methuen and Co, Ltd. 1969 from GB. The mass contains au3 _n 14% by weight sodium chloride and 12% by weight sodium glycolate. The other 14% sodium chloride had been salted out, for example by centrifugation.

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68 kg (364 mol) of sodium monoglutamate and 74 liters of water are placed in a vat with a hard rubber lining. By means of the double lac imantELs the temperature is brought to 50 ⁰ C and then adjusted to pH 9.12 by the addition of four 1 50.2% sodium hydroxide solution. Then the simultaneous additions of monochloroacetic acid solution and 50.2% of the starting sodium hydroxide solution taking into account the fiLgenden two parameters: pH 9.2 to 9.5 and temperature between 70 and 75 ⁰ C. After 14h operation and introduction of 78 1 of monochloroacetic acid and 93 l of sodium hydroxide solution, the solution obtained is left to stand for 30 minutes with stirring and then analyzed. Analysis reveals the presence of 16% L- or DL-N-carboxymethylglutamic acid, i. h «58 mol. A solution of 5 kg of monochloroacetic acid in 4 l of water is prepared by adding to the reaction mixture

around
Introduces 55 to 60 °; and / to maintain the pH value, 7 1 of 50.2% sodium hydroxide solution are added at the same time. The solution obtained is left with stirring at 60 ° for 2 1/2 hours and then brought to the final concentration.

In this procedure, the following amounts of starting materials are used used: Sodium monoglutamate 68 kg (364 mol) monochloroacetic acid 90 kg (953 mol), sodium hydroxide solution 97 1 and 4 1, 154 kg sodium hydroxide of 50.2%, i.e. 77.4 kg of pure sodium hydroxide (1930 moles), with the monosodium glutaraate and the monochloroacetic acid introduced water 175.6 1.

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It is concentrated in a vacuum and spun off on a turbine. This gives 204 kg of liquid mass according to the invention with a concentration of 46.2% by weight trisodium salt of N, N-bis (carboxymethyl) -glutamic acid. The liquid masses according to the invention with the designation "OS ₁ L" correspond to the following Norms «

Glutamic acid directly total nitrogen
Amraonia nitrogen dry extract
Density at 20 ^° C
sodium
iron
chlorine

pH (dilution to 10%) viscosity at 20 ⁰ C coloration (dilution to 10%) complex formation force ¹¹ OS ₁ (trisodium) "titer in%

ζ 0.2%

2% ± 0.2 <100 ppm 64 + 1 1.475-0.005

15% * 1 <100 ppm

2.5 ± 0.5

9.2 ± 0.3

8 poises -2p ^ lod N /

52 mg calcium / g ^ 45% solution

Example 3

The performance with respect Sequestrantkraft of the preparations of Examples 1 and 2 is determined by the method of water hardness test, 3e is the

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Creation of a broolution curve of the degree of water hardness as a function of the sequestering dose added. The softening effect of the water by the mass according to the invention in the liquid or solid state was compared with the various sequestrant agents ethylenediaminetetraacetic acid, nitrile triacetic acid and tripolyphosphate. Starting from a water of natural hardness of 26 ⁰ Th (French titer), they were measured by measuring the hardness as a function of the questrant dose in an ammoniacally buffered medium (25 ml / 1) at pH 10.

Fig. 1 of the drawing illustrates the results obtained with the liquid mass. The sequestrant dose in g / l is plotted on the abscissa and the hardness of lime in degrees Th (French titer) is plotted on the ordinate. Curve 1 corresponds to sodium ethylenediaminetetraacetate of 90% _f, curve 2 to sodium nitrilotriacetate, curve 3 to the composition according to the invention in the liquid state and curve 4 to tripolyphosphate.

Fig. 2 illustrates the results obtained with the mass obtained according to the invention in solid form. The dose of sequestrant in g / l is on the abscissa and that on the ordinate Lime hardness applied in degrees Th. As in Fig. 1, curve 1 corresponds to the sodium ethylenediamine tetraacetate of 90%,

2
the curve of the sodium nitrilotriacetate, the curve 3 of the

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Mass according to the invention in solid form and curve 4 the tripolyphosphate.

Beigiel 4

Washing tests are carried out in the TERG-0-TOMETER device. The water used had a hardness, expressed in French degrees <& of 22 ° Th. The water used for washing * The fabrics used are deliberately and in a standardized manner soiled laundry fabrics. Be treated in parallel the standard soiling according to the following reference values: EMPA 101, KREFELD, ACH, TNO cotton and TNO polyester. After washing, the detergent effect is measured and the percentage improvement is through the Treatment achieved white value derived from it. The formei / is used for this:

DBF "■ DBS% white value improvement DBI - DBS ^{x 10} ° ^{in which}

DBF means the white balance after the washing, DBS the white level of the soiled fabric before washing means,

DBI means the white value of the starting fabric before soiling.

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The white values are measured by determining the amount of reflected light. An ELREPHO reflectometer is used with a green filter, the values plotted in the daylight correspond to the mean value of several Individual experiments. The washes are carried out at 60 ° and 90 °, which are the working limit temperatures usually used are.

The washing liquids have the following compositions:

Sodium Carbonate Soap Chips Sodium Tripolyphosphate

Sequestrant composition according to the invention (denoted by "OS ₁ ")

hard water of 22 ⁰ th

3 g / 1-0.25 and 0.50 g / l 0 and 3 g / l 0, 1, 1.5 and 2 g / l filled up to 1 1

Table 1 A - wash at 60 ° C

sodium Tripolyphosphate soap 1 3 3g /] L. g / i 0 sodium 3 : 0 0 0
ψ ■ 0 0.5 2 0 ϊ g / i 1 1.5 , 2 "Composition
OS ₁ " 0 52 0 53 54 O | 25 g / 1 33 53 54 Weisswertverbes serunc 0 0 1r5 9808 / soap 35 1 44 36 U 0 0 31 174

Table II

B - washing at 90 °

Sodium carbonate sodium carbonate

3 g / l 3g / 1

Soap 0.5 g / l Soap 0.25 g / l

Tripolyphosphate 0300003000

"Composition.

OS ₁ "0 0 1 1.5 2 0 0 1 1.5 2

White level improvement

56 58 51 58 61 54 60 50 58 60

It can be seen that in the simple washing liquid containing sodium carbonate and soap, the washing with hard water is _{significantly improved by adding 1.5 g / l of the composition OS 1} , in order to obtain the same results, one has to double the amount by weight, namely 3 g / l add sodium tripolyphosphate.

Example 5

Various precise formulated detergent mixtures as

here
in the previous example are produced. In particular

do they all contain a soap, a non-ionic surface

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surface active compound, a "builder", a peroxide bleach and a filler. The approaches differ in the sequestrant agent or the sequestrant mixture used. Washing attempts are made at
60 ° with a TERG-0-TOMETER device in hard water
performed by 22 ° Th. The equivalent of 8 g / l of detergent, ie 6 g / l of the group designated as detergent and 2 g / l of sodium perborate, is used for each wash.

The structures used are pre-soiled
Fabrics such as EMPA 101, KREFELD, TNO cotton, TNQ polyester and ACH. After washing, the improvement in the cleaning value is measured according to the information in the above example.

The batches tested have the following composition, expressed in g / l detergent.

Table III

1 2 3 4 5

Sodium silicate 50/52 ° Be 11111 Copra soap 0.5 0.5 0.5 0.5 0.5

nonionic wetting agent

l ethoxylated alcohol) 0.5 0.5 0.5 0.5 0.5

Carboxymethyl cellulose 0.04 0.04 0.12 0.12 0.12 Sodium perborate 2 2 2 2 2 Tripolyphosphate 3.2 - - 0.8 1.6 Seque ^ rant Composition OS ^ - 1.6 1.6 o, 6. 0.8 Padding to 8 8 8 8 8

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The following results

White level improvement

in% 70.5 69 72 71.5 71

It can be seen that assuming a slight increase in the amount of carboxymethyl cellulose Except for 0.10 or 0.12 g / l detergent, the same bleaching improvement of the soiled one Tissue sample at 1.6 g / l of the composition described obtained, as measured in a detergent with 40 wt .-% tripolyphosphate. One can So do an equally good wash if you have one no tripolyphosphate containing approach used, wherein the seguestrantmittel from the composition on Based on the sodium salt of Ν, Ν-bis-dicarboxymethyl-glutamic acid consists. In this case you only need half the weight to achieve the same bleaching required to use tripolyphosphate.

Show the values contained in the table above also that the two sequestrant agents tripolyphosphate and composition OS ^ can be used in a mixture without their corresponding properties lose. You can also use half or three quarters of the usual content of tripolyphosphate in the detergent by half the amount by weight of the composition according to the Replace invention.

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Example 6

This example serves to demonstrate the sequestering properties of the OS mass with respect to heavy metals in alkaline Milieu.

It is known that the presence of certain catalyzed metals such as iron f copper, the decomposition of persalts and so causes a chemical degradation of the cellulose. In order to remedy this deficiency, a seguestrant agent in the hash liquid is generally used. Most of the batches used contain a magnesium silicate combined with the sodium salt of organic acids of the nitrilotriacetic acid or ethylenediaminetetraacetic acid type, which are to be regarded as poisonous for the fauna of the waters.

These tests are TERG-O-tometer apparatus carried out by successive washings of bleached and unbleached cotton fabric (cretonne) in a at 90 ⁰ C. The cellulose degradation is measured according to the French standard AFNOR No. 12-005. The used basic detergent is a commercial detergent without perborate, the 2 g Natriumperbor attetrahydrat _e j percentage amount of 6 g of detergent added. A mixture of 1% (based on the complete detergent with perborate contained therein), magnesium silicate and either ethylenediaminetetraacetic acid or composition OS are also used for the tests. Finally sets

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you use the catalytic heavy wash bath at the start of work « metal amounts to, namely

Copper as Cu iron as Fe ⁺⁺

0.5 ppm 1.5 ppm

The results obtained are shown in the following Tabel:

Table IV

EMPA fabric Ethylene diamine tetra 1 230 Wet cretonne Stabilizer (Initially DP acetic acid 1 280 (Initially DP before before washing: 1600) Claimed: 1 280 Washing: 25ΟΟ) approach 1% Mg silicate 40 9 8 08/1174 • after 5 washes <- OS 5% after 5 washes without 980 κ os ^ 10% 1 085 known: 1% mg I- OS 15% silicate and 1 190 1 290 0.2% 1 455 1 455 1 455

~ ²⁷ ~ 233988a

DP =? Degree of polymerization

Ethylenediaminotetraacetic acid as sodium salt + OS - composition

It can be stated that 5% of the OS composition allows better cellulose protection to be achieved » than the known approaches with derivatives of the ethylenediaminotetraacetic acid type or with nitrilotriacetic acid allow. The invention therefore offers in addition to the resulting lower wear Advantage of the delivery of washing wastewater without any products harmful to the environment.

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Claims (18)

~ ²⁸ ~ 233988a Claims /. Process for making a non-toxic, non-polluting, biodegradable seguestrant composition with a derivative of L- or DL-N, N-dicarboxymethylamino acid, characterized in that one monochloroacetic acid with the disodium salt of the dicarboxyamino acid in an aqueous medium with fixation of 2 carboxymethylgxppen on the nitrogen atom the amino group converts the amino acid, 2. The method according to claim 1, characterized in that a monochloroacetic acid solution and a solution of an alkaline agent are introduced simultaneously into an aqueous solution of the disodium salt of dicarboxyamino acid using such an excess of the alkaline agent that the pH of the reaction mixture is between 8 and 10 and the temperature of the reaction mixture is between 50 and 100 ^° C. 3, method according to claim 1, characterized in that at one / the reaction approximately 2.4 to 2.7 moles of monochloroacetic acid is used per mole of dicarboxy amino acid. 4. The method according to claim 1, characterized in that the temperature of the reaction mixture between 70 and 40 9808/1 174 7339883 is held 5. The method according to claim 1, characterized in that that the pH of the reaction mixture is kept between 9 and 9.7. 6. The method according to claim l _f, characterized by the use of sodium hydroxide. 7. The method according to claim 1, characterized by the Use of glutaric acid, preferably in the form of Disodium salt. 8. The method according to claim 1, characterized by the Use of softened, demineralized or distilled water in the reaction mixture. 9. The method according to claim 1, characterized in that it is carried out continuously. 10, method according to claim 1, characterized in, that the crude product after completion of the fixation reaction of the carboxymethyl groups by spraying the reaction mixture is distilled. 4098 08/1174 733988a 11. The method according to claim 1, characterized in that that the crude product obtained is purified to a purity higher than 95% by known methods. 12, non-toxic, non-polluting biodegradable Sequestrant detergent, labeled by a content of at least 40% of a sodium salt of the Ν, Ν-Bisdicarboxymethylderivates a Amino acid. 13. Detergent according to claim 12, characterized by a content of soap, surface-active product, bleaching agent and filler _y optionally an odorous substance, a whitening agent and a deposit inhibitor. 14, detergent according to claim 12, characterized by a content of soaps, nonionic surface-active Agents, an active oxygen-containing compound such as sodium perborate, carboxymethyl cellulose, Sodium silicate and a filler, odorant, optical whitener and a scale inhibitor. 15. Detergent according to Anspxch 13, characterized by a level of about 20% of the composition 409808/1 174 '233988g according to claim 12 « 16. Detergent according to claim 15 _t characterized by a content of a mixture of equal parts of tripolyphosphate and the composition according to claim 12, 17. Detergent according to claim 13, characterized by the content of a mixture of the composition according to Claim 12 and two parts of tripolyphosphate 18. Detergents with sequestering power against heavy metals and limitation of successive ones Washing in an oxidizing environment causes cellulose degradation, characterized in that it is about 5% from the composition of claim 12 in association with about 1% magnesium silicate 409808/1174 Blank page