DE2360868A1 - (DICARBOXY) -ALKYL ETHER, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS BUILDER-SALT (BUILDER.) - Google Patents

Description

(Dicarboxy) alkyl ethers, process for their preparation and
their use as building salts (builders)

The invention relates to new organic compounds, viz
(Dicarboxy) alkyl ethers, which are used in particular as building salts
(Builder) in detergent, dishwashing and cleaning agent compositions are advantageous.

Such compositions are also referred to as detergents, and these can be both soap-free and soap-containing. The building salts used in such compositions are often used as builders, structural substances or
Detergent booster called.

Recently, attention has been drawn to the potential contribution of the commonly used tripolyphosphate builder salts in cleansing compositions pointed to the eutrophication of lake and river waters, and studies have already been made to

409824 / 1U7

■ »~ 5if; ~ r-- · ■ <- '· ■ * - ■ ·»; .-? r. ·,. .tr_ ■ ·, · -. ■ _ ■ % «1 * ι w>."->; ■ £ ■; ■ - .if- \ ir-i \ i. ^ A "'J ^

to replace such tripolyphosphate builder salts. So was z. B. in the Dutch patent application 72 01 313 special, polybasic ether carboxylic acids proposed as builders or building salts for detergent compositions. Examples of such polybasic ether carboxylic acids are bis- (C-carboxymethyl) -ethylene glycol, tris- (C-carboxymethyl) -glycerol, O-carboxyniethyltartronic acid, bis-CC-carboxymethyl) -tartaric acid and the like. According to Dutch patent application 72 01 ^ ΛΛ, these compounds can be prepared by reacting glycol, glycerol, esters of tartronic acid and esters of tartaric acid with diazoacetic ester in the presence of a Lewis acid and saponifying the resulting product.

There have now been special, new (dicarboxy) alkyl ethers and salts thereof as useful and advantageous builders or synthesis salts found whose enhancing effect is comparable to that of a tripolyphosphate builder salt. The ability for complexing calcium from various of these (dicarboxy) alkyl ethers is better than that of various of the polybasic Ether carboxylic acids according to the earlier proposal mentioned above.

The particular (dicarboxy) alkyl ethers according to the invention are Di-ü-malonyl derivatives of tartaric acid, propylene glycol and triethylene glycol, "the Kono-O-malonyl-mono-C-acetyl derivative of ethylene glycol and the mono- and di-O-succinyl derivatives of ethylene glycol, Propylene glycol and diethylene glycol.

The (cicarboxy) alkyl ethers according to the invention can be obtained by the following general formula can be reproduced:

COOK

ti j r Tl

E _Λ -CO-CH

¹ I '

CCCIi

₂₂ ) _m

GE, ^3rd

8 2 4/11 ul

₀ -C

² H

in which formula R ^ -E, -CE ^ or -COOM

E ₂ -E or -CO ₁ OH E- «E, -CE ₂ COOM or COOM

-CE COOM

η β 0 or 1

m «0, i or 2

M «E, -CE-. -C ₂ E ₅ or an alkali metal,

provided that Ep may only be COGiI if R ,. -COOM is; furthermore, if η ■ 0, R ^ either COOM

-CE

COOM

or -CE ₂ COOK must be ₉ where H, only -CE ₂ CCOM may be, if E. β Ep «= H and m = 0, and that if m» is 1, η may only be Λ .

The inventive compounds may be prepared by reacting the appropriate starting material with a Diazomalonsäureester or Diazobernsteinsäureester in the presence of copper powder at a temperature of about 100 ⁰ C in itself. is implemented in a known manner, followed by a hydrolysis. Depending on the structure of the compound, this hydrolysis is carried out in an acidic and / or in an alkaline medium. The compounds can be used in the acid form as well as in the form of suitable alkali metal salts such as sodium and potassium salts. Compounds with a pK value of 4.8 and higher

v / S

are preferred, especially those with a pK _ß value of 6.1 and higher such as z. B. Tartaric acid dimalonyl ether (TDM).

The following table I lists compounds according to the invention and their calcium complex constants, P ^ _Ca ^.

409824/1 147

Table I.

link

Abbreviation pK. *) Starting material reactants

O
CD
OO

Veinsic acid dimalonyl ether TDH 7.1

Propylene glycol dimalonyl ether PGDM 6.1

Triethylene glycol dimalonyl ether TEGDM 4.8

Ethylene glycol disuccinyl ether EGDS 4.9

Propylene glycol disuccinyl ether PGDS 5.3

Propylene glycol monosuccinyl ether PGHoS 3.8

Diethylene glycol disuccinyl ether DEGDS 5.2

Diethylene glycol monosuccinyl ether DEGMoS 3 _? ß

Ethylene glycol monosuccinyl ether EGMoS 5.0

Ethylene glycol monoacetyl monomalonyl EGAM 4.8 ether

Dimethyl tartrate
Propylene glycol
Triethylene glycol
Ethylene glycol
Propylene glycol
Propylene glycol
Diethylene glycol
Diethylene glycol
Ethylene glycol
Ethylene glycol

Dimethyl diazomalonate, dimethyl diazomalonate, dimethyl diazomalonate Diethyl diazosuccinate diethyl diazosuccinate diethyl diazosuccinate diethyl diazosuccinate Diethyl diazosuccinate diethyl diazosuccinate

Dimethyl diazomalonate / diazoacetate

*) determined accordingly:

J. Schubert in "Methods of Biochemical Analysis", Vol. Ill, editor D. Glick, Interscience Publishers Inc., New York (1956)

Conditions; pH - 10,

Temperature = 25 ⁰ C, yu ■ 0.02

These new compounds are advantageous building salts or builders for detergent compositions. You can in Detergent compositions are used which an anionic, a non-ionic, a cationic, synthetic detergent or a soap or mixtures thereof contain, and which, in addition, the normal additives or have auxiliaries for cleaning agents.

The detergent compositions essentially comprise one or more, anionic, nonionic, amphoteric or zwitterionic detergent active compounds, or mixtures thereof, in addition to detergency builders.

The synthetic detergent active compounds which can be used in the compositions of the present invention are preferably anionic detergent active compounds which are readily available and relatively inexpensive, and mixtures thereof. These compounds are usually water-soluble alkali metal salts of organic sulfates and sulfonates, which have alkyl radicals having from about 8 to about 22 carbon atoms. Examples of such synthetic, anionic, detergent-active compounds are sodium and potassium alkyl sulfates, especially those which are obtained by sulfating the "higher (Cg-C ^ g) alkoxides, which were obtained by reducing the glycerides of tallow or coconut oil, or that of Synthetic alcohols derived from petroleum were obtained; sodium and potassium alkyl CCg-CpQ ^ benzenesulfonates, in particular liatrium-linear-sec.-alkyl- (C _/ . ₀ -C ^ c) -benzenesulfonates; sodium alkyl glyceryl ether sulfates, especially ethers of the higher alcohols derived from tallow or coconut oil and the synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium and potassium salts of sulfuric acid esters of higher (CQ-C _< .g) alcohol-alkylene oxide reaction products, in particular with ethylene oxide, the reaction products of fatty acids like

4 O 9 8 TU I 1 U 7

Coconut fatty acids, esterified with isethionic acid and neutralized with sodium hydroxide; Sodium and potassium salts of fatty acid amides of diethyltaurine; Alkane monosulfonates such as those produced by reacting alpha-olefins (Co-Cp ₀ ) with sodium bisulfite and by reacting paraffins with SOp and CIp or 0 ~ and subsequent hydrolysis with a base to form a mixed sulfonate; and Glefinsulfonate, whereby this term is intended to include the material which was obtained by reacting olefins, in particular alpha-olefins, with SO, and subsequent neutralization and hydrolysis of the reaction product.

If necessary, non-ionic detergent-active detergents can also be used Connections are used. Examples include the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C £ -Cp) phenols, generally 5 to 25 EO (EO ■ Ethylene oxide unit), d. H. in which there are 5 to 25 ethylene oxide units per molecule; the condensation products of aliphatic (C -C, .o) alcohols with ethylene oxide, in general 6 to 30 EC units, as well as by condensation of ethylene oxide Products made with the reaction products of propylene oxide and ethylene diamine. Other so-called non-ionic, Detergent active compounds include long chain, tertiary amine oxides, long chain, tertiary phosphine oxides and Dialkyl sulfoxides.

Mixtures of detergent-active compounds, e.g. B. mixed anionic and mixed anionic and nonionic compounds can be used in the detergent compositions be used, in particular to give them controlled, low-foaming properties. This is particularly the case Compositions beneficial to be used in foam-non-foaming automatic washing machines. Mixtures of amine oxides and ethoxylated, non-ionic compounds can also be beneficial.

409824/1 1 47

Many suitable detergent active compounds are commercially available and described in the literature, e.g. B. in "Surface Active Agents and Detergents" by Schwartz, Perry and Berch.

Amounts of amphoteric or zwitterionic detergent active compounds can also be used in the compositions of the invention, but this is normally undesirable because of their relatively high cost. If any amphoteric or zwitterionic detergent-active compounds are used, this is generally done in small amounts in compositions which are based on the more commonly used, anionic or non-ionic, detergent-active compounds _a

The amount of synthetic detergent active used Compound or these compounds is generally in the range of, depending on the properties desired about 10 to. 50 wt .- τύ, preferably about 15 to 30 wt .- ^, based on the compositions »

The weight ratio of the builder compounds to the detergency The invention relating to the detergent-active compounds is for use in laundry detergents and dishwashing detergents for hand rinsing generally in the range of about 1: to about 20: 1, preferably about 1: 3 to 10: 1, especially preferably about 1: 1 to about 5 * 1. If the builders for the Cleaner, however, in gowns for mechanical dishwashing (Machine wash), the ratio of detergency builder to detergent compound is im generally about 10: 1 to about 50: 1, since then much smaller amounts of the detergent-active compound than usual are used will.

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The builder compounds according to the invention for cleaning power can be used either as the only builder for cleaning power or optionally in conjunction with other builders for cleaning power, examples of these other builders being tetrasodium and tetrapotassium pyrophosphate, pentasodium and pentapotassium tripolypnosphate, trisodium and tripotassium nitrilotriacetate, ether polycarboxylates, Citrates, oxidized starch and cellulose derivatives, especially those with dicarboxyl _{radicals, sodium alkenyl (C ^ 0} -Cp _O ) succinates, sodium sulfo fatty acids, alkali metal carbonates and orthophosphates and polyelectrolyte builders such as sodium polyacrylate and sodium copolyethylene maleate.

Other conventional materials can be used in the present invention Detergent compositions are present, e.g. B. Suspending agents for dirt, hydrotropes, corrosion inhibitors,! Dyes, Fragrances, fillers, abrasives, optical brighteners, Enzymes, foam boosters, foam suppressors, germicides, anti-tarnish agents, cationic detergents, fabric softeners, Chlorine-releasing agents, oxygen-releasing bleaching agents such as sodium perborate with or without peracid precursors, Buffers and the like. The rest of the detergent composition consists of water, e.g. B. in the range of about 5 to 15% in powder detergent compositions.

The detergent compositions of the invention can be in any of the conventional physical forms for compositions such as powders, pearls, curls, bars, tablets, noodles, liquids, pastes, and the like. The detergent compositions are prepared and applied in conventional manner, e.g. B. in the iall of Powdered detergent compositions can be prepared by spray drying aqueous slurries of the detergent ingredients or by dry blending processes.

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The invention is explained in more detail below with the aid of examples.

example 1

This example illustrates the preparation of hexasodium tartaric acid dimalonyl ether (TDIl).

3 »53 g ^β 19.9 mmol dimethyl tartrate and 190 mg powdered, active copper (see AI Vogel," A text-book of practical organic chemistry ", 3rd edition (1964), page 192) were in a 25 ml Two necked round bottom flask equipped with a reflux condenser and a serum cap was added. A plastic tube was attached to the top of the reflux condenser. The plastic tube leads via a drying tube to the lower part of an inverted measuring cylinder filled with water and submerged in a water bath. The mixture was stirred vigorously, and at about 105 ⁰ C were 7.05 g = 44.5 added mKol Dimethyldiazomalonat with the aid of an injection syringe, the needle was pierced through the serum cap. Nitrogen evolved, which was collected in the kettle cylinder. After the theoretical volume of nitrogen required for complete reaction of the dimethyldiazomalonate had been collected (25 Hin.), The reaction mixture was cooled. The copper powder was removed by filtration and washed twice with ethyl acetate (2 ml). The filtrate and washes were combined and then evaporated in vacuo to remove the ethyl acetate solvent. This gave 91.3 g of a colorless, liquid residue.

9.2 g of this residue were on top of a column with acidic, washed: em silica gel (trade name silica gel from Mallinckrodt cc-4, 450 g, 0.053-0.044 mm grain size), which with chloroform in a chromatographic column washed with chromic acid of 90 χ 4 cm was turned on, abandoned. Fractions of 15 ml were collected using a fraction collector (make LKB-Produkter AB, Stockholm, Sweden, LKB Ultrorac fraction collector "type 7000) using a gradient elution technique

4 09824/1147

collected, using ethanol-free chloroform as the eluent started and slowly the concentration of ethyl acetate therein was increased in the usual manner. The tractions, which pure C ^ * 95 £>, by KLB. checked) Hexamethyl-TDK contained, were combined C3 »1 g) ·

Analysis values of ^ p ^ -hexjmethjlester

IR spectrum (mm): 1755 cm "^ _t wide (^ CO); 1440 cm" ¹

in -OCH,); 1285, 1240, 1160 and 1025c (Jf-COC, ester); 1125 cm " ¹ (3T-COC, Ä

KKE voltage run

The proton magnetic Hesonanzspektruia was added at 40 ⁰ C using a Varian A-60 Spektroiaeters, which was operated at 60 IiIIz.

cm

" ¹

her).

The ci values are in ppc down from an internal and they are accurate to - 0.01 ppm.

-Default

_j ■ CO-CK ₃ Ca) Cb) HC-O-CECc)

CO-CK ₃ Ca)

CO-CH _x Ca)
Cb) HC-O-CHCc)
Ca) CH ₂ -OC CC
0 0

ppm multiplicity assignment

3.80 singlet 4.76 singlet 4.97 singlet

away

Solvent CDCl-

Mass spectrum

The react intensities are in the Table II indicated:

a) up to m / e 350, only peaks with intensities> 5 ° / ° are given, and

0 9 8 2 4/1 U 7

b) above m / e 350 there are also the small peaks, which are still characteristic are listed.

I. m / e I. Table II I. m / e I. m / e 5.5 104 12.2 m / e 5.3 263 10.7 18th 32.7 113 18.6 189 18.0 290 5.6 28 5.7 115 6.8 191 '14, 6 291 11.9 32 5Λ 131 6.5 201 7.9 319 17.7 45 20.4 132 18.0 203 5.0 347 9.5 59 7.4 133 5.9 217 92.8 351 6.1 69 10.4 145 15.6 219 8.5 379 13.1 73 54.0 146 6.1 220 9.5 394 0.4 75 8.2 159 8.5 231 11.6 406 0.1 85 8.1 161 13.7 233 8.9 4J8 Q ₉ I. 100 13.1 171 5.3 247 6.3 439 0.2 101 100 175 6 * 8 258 7 * 7 103. 259

5.3 g = 12.1 mmol of hexanethyl-ΪΒΗ were stirred at room temperature in 145 ml of aqueous 1N hydrochloric acid under an atmosphere of helium until the solid material had dissolved (4.5 h). The solution was neutralized with 15 ml of 1N aqueous sodium hydroxide solution, after which an excess of sodium hydroxide solution (15 ml in 10N) was added. The solution was then stirred under a helium atmosphere at room temperature for 20 hours.

The excess sodium hydroxide was treated with an ion exchange resin in the acid form. (Trade name Lowex AG 5OW-X8) neutralized. After the ion exchange resin had been filtered off, the filtrate was evaporated to a concentrated solution in vacuo. A concentrated, aqueous solution of excess CaC4 was slowly added to this solution with stirring. The precipitated, white calcium salt TOn T ¹ DK was filtered off with water

409824 / 1U7

washed and then converted into the acid with the aid of an excess of ion exchange resin in the acid form (trade name Dowex AG 50W-X8). The ion exchanger was filtered off and the filtrate was neutralized with aqueous sodium hydroxide solution to zero against a pnenolphthalein indicator. Upon evaporation of the aqueous solution to dryness, a solid residue of hexasodium TDM was obtained. The compound was dried overnight at 70 ° C / 10 mm Kg. The yield was 6.3 g. According to the quantitative NI'iE analysis, the product consisted of 90.6% by weight of TDH and 9.3% by weight of 56 H ₃ O.

(TDM hexasodium salt)

NMR spectrum

The conditions were the same as for the NME spectrum of TDM hexamethyl ester (internal standard TSS). The coupling constants are accurate to within - 0.2 Hz.

O O ; -C-CH (b) c5ppm Multiplicity Assignment Na-O-C C-O-Na CO-Na
A. 4.13 Singlet a (Ah( V
CO-Na 4.28 Singlet b (a) HC-O-CH (b) Solution
medium D ₂ O Na-O ₁ J
O ; CO-Na
\

The melting point of the product could not be determined. The decomposition began at about 200 ^° C. both under nitrogen and in vacuo.

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Example 2

This example is the preparation of tetrasodium ethylene glycol disuccinyl ether (EGDS).

Letraethyl-EGDS was prepared by the method described in Example 1 from 11.6 g = 58 mmol of diethyl diazosuceinate and 0 * 89 g * 14.3 mol of ethylene glycol. The nitrogen evolved made up 99 % of the theoretical value. 9.7 g of liquid residue were obtained.

9.6 g of this liquid were chromatographed on a silica gel column (trade name silica gel from Ilallinckrodt cc-4, 450 g, 0.16-4 0.053 ram. Grain size, 90 χ 4 cm). Elution in 20 ml fractions was carried out as described in Example 1. The fractions which contained more than 90 % (detected by KT-IR) of tetraethylethylene glycol disuccinate were combined (4.4 g).

Analysis values (EGDS-Ietraethylester)

HME-Sgektrum

The conditions were as in Example 1 for the iiFiR spectrum indicated by TDIi-hexamethyl ester.

0.

OCH ₂ -CE.

* 2 ' Ce) (a!

(a) (e) HC-O-CH ₂ -CH 0-CH (g)

(d) (d)
i ₂ C

0.

(c) H _p C

C ^ ₂

₅₂ O ^ (f) (b]

(b) (f)

0 9 8 2 4/1147

Culturality JHz Assignment 2360868 <S ppm Triplet 7.0 a or B 1.23 Triplet 7.0 b or a 1.26 broadened doublet ea.6,3c / g C. 2.71 , 8 complex - d 3,4-3 quartet 7.0 e or f 4.09 quartet 7.0 f or e 4.15 Triplet, partially 4.28 overlaps e and i about 6.3g / c G Solution MiJ. χ / at
CDCl,
D.

Mass drink

The peak intensities are with the following restrictions

indicated in table III:

a) up to m / e 150 are all peaks with intensities> 5% stated, and

b) above m / e 150 all peaks are with intensities> 1% specified.

Table III

m / e Inten m / e Inten m / e Inten m / e Internal sity sity sity sity 18th 7.6 128 5.4 174 1.4 241 2.1 28 17.6 143 32.7 175 2.9 259 2.4 29 14.0 145 5.6 185 1.6 287 100.0 7.8 157 2.1 187 2.0 288 14.4 59 14.7 159 1.6 189 3.0 289 2.6 71 5.9 161 10.1 203 4.4 333 7.4 73 33.8 167 5.7 213 6.4 334 1.3 99 11.2 168 1.1 214 1.5 360 3.1 101 8.5 170 4.0 216 . 14.7 406 1.0 115 6.3 171 4.2 217 91.4 117 10.4 172 2.2 218 10.1 ■ ' 127 7.6 173 4.2 219 1.7

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Hydrolyses

125 ml of ion exchange resin (trade name Dowex AG 5OW-X8) and 50 ml of water were added to 4.4 g of tetraethyl EGDS. The mixture was ^{stirred at 60 °} C. for 48 h. The ion exchanger was filtered off at room temperature and washed with water until it was free from acid. After the filtrate and washing liquids had been combined, the solution was neutralized against phenolphthalein indicator with aqueous sodium hydroxide solution. After the aqueous solution had been evaporated, the residue was dried in vacuo ^{at 70 ° C. overnight.} 3 »8 S of a light yellow, solid residue were obtained. The NMR analysis showed that the product consisted of tetrasodium EGDS and about 10% by weight HpO.

Examples 3 to 10

The following compounds according to the invention were prepared in a manner analogous to Examples 1 and 2 and their NKR spectra measured.

PGDM (tetrasodium salt)

, 0

/ ^x ONa (C) HC-O-CK (d)

^N 0Na

/ CNa

HpC-GCH (e)

ONa

ppm multiplicity JHz assignment

1.16 doublet 6.3 a

3 j 3-4,1 complex -. b + c

4.24 singlet **) - d 4.40 singlet - e

'4 09824/1147

* ♦) Assignment on a trial basis after comparison with the proton c of the spectrum of EGAIi.

TEGDH (tetrasodium salt

NaO J j ONa

Cb) HC-O-CE ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CHCb)

(a) (a) (a) (a) (a) (a)

ONa

NaO

Vl

flppm cultiplicity JHz

4.24

complex singlet

Assignment a
b

PGDS (tetrasodium salt) *)

(a)

, C

3i

HC

9 "CHa

(d) HC-O-CK-

8th

(λ ^ XI / "* ΓΛ /" ¹ TT / " ¹ TI

- I _A 0

ONa

0Na 0

0Na

ppm cultiplicity JKz

Assignment;

1.18
2.54
3.3-4.4

complex complex complex

a p c + d + e

409824/1 1 47

PGMoS ( disodium salt)

2360888

'PHI (a) CH ₃
(c) HC-OK 'Cultiplicity O Assignment Ί2 J (e) (b) Doublet a 56 (d) H ₀ CO-CH-CH ₀ -C ^ AB part of the ABX system ONa b 3-4, ^N 0Na 3 complex JHz c + d + e 6.5 - 2, * - 3,

DEGDS (tetrasodium saiz)

^c ;

j ONa (c) HC-O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-Ch (c)

I (b) (b) (b) (b)! -, (a) H ₂ C CH ₂ (a)

NaO

'ONa

Cultural Citizenship

JHz

Assignment;

2.56 AB part of the ABX system - a 3 »72 broadened singlet - b 4.13 X-2 part of the ABX system 8.5; 4.6 c

(Disodium saiz)

c;

ο.

GNa

HOCH ₂ -CH ₂ -O-Ch ₂ -CH ₂ -O-CH (c)

(b) (b) (b) (b) CH ₂ (a)

I yo

^: . ^: _ :> 0Na ■ '' 409824 / 1U7

iSppm

Multiplicity

JHz assignment

2.52 AB part of the ABX system - a

3 »5-3» 9 complex - b

4.13 X part of the ABX system 9.0; 4.5 c

EGKoS (Dina t r iutasal ζ)

ONa

HO-CH ₂ -CH ₂ -O-CE (c) CH ₀ (a)

, P

ONa

Multiplicity

JIIz assignment

2.56 AB part of the ABX system 3.70 broadened singlet 4.11 X part of the ABX system 8.0; 4.8 a b c

EGAK (trisodium salt)

^N 0Na Cb) H ₂ CO-CH ₂ -CK ₂ -G-CH (c)

ONa

ι ppm

multiplicity

JHz assignment

3.69 widened singlet 3.98 singlet

4.24 singlet

a b c

*) The compounds marked with *) are mixtures of the diastereoisomers. This complicates the Iu ^- IIi spectra.

409824 / 1U7

The (diearboxy) alkyl ethers are used as builders or structural substances or build-up salts in detergent compositions advantageous « This is proven by Uaschversuche in which the cleaning power the detergent compositions which either liatrium tripolyphosphate or various (diearboxy) alkyl ethers according to the invention contained in tergotometer examinations

/became
bestinmrt /, artificially soiled cotton textile test pieces were used, which are known under the names AS 8 and AS 12 and VCD. The detergent compositions used contained the following ingredients:

Wt%

Sodium dodecylbenzenesulfonate
Sodium soap of hardened tallow dinonylphenol condenses with 16 kol of ethylene oxide

Nonylphenol condenses with 10 moles of ethylene oxide

Sodium silicate

Sodium sulfate

Sodium carboxymethyl cellulose

Ethylenedianiine tetraacetic acid

Sodium perborate

as well as one of the following builders (building salts)

a) Sodium tripolyphosphate (STP) 30% by weight

b) liatrium TDh equivalent to STP, ratio col / mol

c) Sodium PGDK ""

d) Sodium TEGDH "" "

e) Sodium ZGDS ""

f) ITatriuni-rGDS ""

g) Katrium-DEGDS ""

h) Sodium LGATi 30% by weight

6th 5 3 2 1 7th 14th O, O, 22nd

AO982A / 1 1 Ul

The conditions of the examinations for cleaning power were: speed 75

Time / temperature from 25 "to 90 ⁰ C in 4-5 minutes;

5 minutes at 90 ° C

Test fabric · AS 8; AS 12 and VCD

Ratio fabric / lye 1: 50

Water hardness 10 ° DH (Ca ⁺⁺ : Kg ⁺⁺ - 4: 1)

Concentration 5 6 Detergent /!

The results of the cleaning power test are summarized in Table IV below:

40982W 1 1 47

Table IV

Washing effectiveness (%) *)

TDH STP PGDH STP TEGDHSTP 'EGDS STP. PGDS STP .. DEGDS STP V- EGAM STP

AS 8 65.2 65.1 67.9 71.3 63.3 67.8 65.7 67.8 * 61.9 65.1 63.0 65.1 6T, 7 67, ί

§ AS 12 77.6 '77.3 71.1 73.5 74.1 79.4 76 _V 4 79.4 75 _r 5 77.3 74.5 77 * 3 73 * 1 79V

§ ^ VCD 53.4 51.0 53.3 50.2 43.9 54,, O 50.0 54,> O 47.4 51.0 48 _V 6 51.0 '45 _{; 1;} 5 54 ^ j

to ■. ■■ ': OI

IiC-Rs ^X

Rw β V / ert of the reflectivity, the gewasclienea. Testgewe "esp

Rs' = V / ert the reflectivity of the non-normal test tissue

Rc ■ = value of the reflectivity of clean test fabric

The values given are the average values of two tests in each case.

Claims (2)

(JUUUUV Pat entan would speak '1. (Dicarboxy) alkyl ether of the general formula COOK R_C-O- CH j CGO RCOR, ■ -'Ε ⁵ in which mean: R. = H, -CH ₅ or -COCM K ₂ - K or -CCGH R-, = H, -CKpCOOK or COOH -CH cocri η = 0 or 1 m = 0, 1 or 2 Ti = H, -Cli ,, -C ₂ Hr- or an alkali metal, assuming it ₂ only. -CCCh may be if Ry. -CCCM is; furthermore, if η = 0, K ₇ . either CCCM -CII CCOH or -CHpCCGh, where Iw may only be -CHpCCCM, if liy. = rp = ix η may only be 1. if liy. = rp = ix and m = 0, and that when m = 1, 409824/1 1 BAD ORfGINAL 236 ^ 868 2. Tartaric acid diinalonyl ether and its hexasodium salt. 3 · Process for the preparation of (licarboxy) alkyl ethers of general formula according to claim 1, characterized in that the corresponding hydroxyl groups containing starting materials in a manner known per se with the corresponding, low molecular weight dialkyldiazomalonic acid or dialkyldiazosuccinic acid esters are reacted. ; 4-. Use of the (dicarboxy) alkyl ethers of claim 1 specified formula or their salts as building salts or builders in detergents, dishwashing detergents and cleaning agents. 40982W 1 1 47