DE2265058A1 - DETERGENT PREPARATIONS - Google Patents

Description

DR. BERG DIFL.-INfG. STAPF DIPL.-ING. SCHWABE DR DR. SANDMAiR

PATENT LAWYERS

8 MUNICH 86, POST BOX 86 02 45

Dr. Berg Dipl.-Ing. Stapf and Partner, 8 Munich 86, PO. Box 860245

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Lawyer file no .: 26 "29

MONSANTO COMPANY St. L o u i s, Missouri / USA

"Detergent preparations"

This invention relates to detergent compositions with a content of at least 8 wt -.% Of surface-active agents (surfactants), namely one or more anionic, nonionic, zwitterionic, ampholitischer and / or amphoteric surfactants.

X / dr

609816/0995

* (089) 988272 987043 983310

Telegrams: BERGSTAPFPATENT Munich TELEX: 0524560 BERGd

Benches: Bayerische Vereinsbank Munich 453100
Hypo-Bank Munich 3892623
Post check Munich 65343-808

Numerous materials are known which, as a result of their ability to increase the detergency of detergent formulations in combination with various surface-active substances (surfactants) to increase, as adjuvants, enhancers, supplements, Raising agents, potentiators and / or conditioning agents in detergent formulations wherein such materials are usually used as detergent builders (detergent boosters) are designated, are suitable. It should be noted that although many detergent builders also use as Sequestrants are useful in determining the materials that are inherently effective as detergent builders is a complex empirical process and not with certainty from the known properties of these materials is predictable.

Many materials of the aforementioned type are characterized by a high phosphorus content, such as the alkali metal tripolyphosphates, which have found extensive use as detergent builders. It is recently believed that such compounds can contribute to the acceleration of eutrophication processes. One makes a special effort accordingly in the detergent builder art to find other functional compounds that are free of phosphorus.

609818/0995

It was therefore an object of the present application to provide detergent preparations with improved properties.

According to the invention, this object has now been achieved by a detergent preparation with a content of at least 8% by weight of surface-active agents (surfactants), namely one or more anionic, nonionic, zwitterionic, ampholitic and / or amphoteric surface-active agents, ranging from 1 to 75 contains% of a detergency builder compound of the following general formula: - wt.

Ü ■ * ■ / "I _B / * \ ΓΊ" R

COOM COOM

COOM R- *

wherein the radical M are alkali metals and / or ammonium, the

1 2
R and R are independently hydrogen, methyl and / or ethyl and R is hydrogen, methyl and / or COOM.

The detergent builder compounds (except those where R

2 3

and R is hydrogen and R is COOM) by using the appropriate halomalonate

COO (methyl or ethyl) ι I

R- ¹ CX

COO (methyl or ethyl)

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(where X is chlorine when R is hydrogen and is chlorine or bromine when R is methyl) with the sodium salt of the appropriate α-hydroxy ester

COO (methyl or ethyl) NaO CR ²

in an inert solvent such as 1,2-dimethoxyethane or Tetrahydrofuran.

This reaction provides the ester forms of the detergent builder compounds, which can be saponified by conventional methods, whereby the desired ammonium or Receives alkali metal salts. The acidic forms of the compounds of this invention are obtained by acidifying the salts. The acids can be recrystallized according to conventional methods, whereby valuable precursors for salts are obtained of high purity. It should be noted that if R is hydrogen, the acid because of its tendency to be a to suffer rapid decarboxylation is relatively unstable.

Compounds wherein R is COOM, including those wherein R and R are hydrogen, can be prepared by a solution (preferably about 1 molar) of compounds the general formula

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COO (methyl or ethyl) COO (methyl or ethyl) 1 I '2

"D" ^ Λ * Ο ι ι ι. ι Ii ^ R

J I

H H

in tetrahydrofuran is added two equivalents of lithium diisopropylamide in tetrahydrofuran (about 1 molar preferably) adding at a temperature of about -78 ⁰ C.

It is believed that this process results in the formation of a lithium salt of the following general formula:

COO (methyl or ethyl) COO (methyl or ethyl) -il I ρ

• ρ- » ρ r \ ρ p * -

I I

Li Li

It then becomes gaseous C0 _? forming a product of the general formula:

COO (methyl or ethyl) COO (methyl or ethyl)

1 'Ip

R ^x C 0 CR

COOLi COOLi

introduced.

The dilithium salt becomes a half-ester-half acid compound COO (methyl or ethyl) COO (methyl or ethyl)

1 I I?

TJ O f \ / Ί ■ "D * ~

COOH COOH

by treating with an organic strongly acidic cation exchange resin, for example a sulfonated polystyrene

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resin as it is available from Fischer Scietific Co. under the trademark Rexyn 101 (H) is launched. the Salt forms are obtained by saponification of the half-ester half-acid product.

In a preferred embodiment of the invention, M is

12 3 sodium and the radicals R, R and R ^{J are} hydrogen. In a further preferred embodiment, M is sodium, R is methyl

2 3
and the radicals R and R are hydrogen. In another

preferred embodiment, M is sodium, the radicals R and

2 ~ Ί

R hydrogen and R COONa. These embodiments are because of the availability of raw materials for their manufacture and because of their excellent behavior as detergent builders preferred.

The detergent formulations comprising the compounds of this invention can use from 1 to 75 weight percent, preferably from 5 to 50 weight percent? of the salt, preferably the sodium salt forms of the compounds of this invention. Such compounds can be used as the only detergent builders in The formulations can be used or they can be combined with other known detergent builders, such as water-soluble ones inorganic builder salts, for example alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, silicates or organic builders, such as SaI-

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zen of phytic acid, sodium citrate and the water-soluble polymeric polycarboxylates such as those in US Pat 3 308 067 are described.

The detergent formulations can additionally at least

Contain 8% by weight of a surfactant. It can any of the numerous well known anionic, nonionic, zwitterionic, or ampholytic surfactants can be used. Examples of suitable anionic surfactants are alkyl ethyl sulfonates, Alkyl sulfates, acyl sarcosinates, acyl esters of Isocyanates, ayl-N-methyltaurides and alkylarylsulfonates. The aforementioned materials are in the form of their water-soluble sodium, potassium, ammonium and alkylammonium salts used. Specific examples include sodium lauryl sulfate, Sodium N-methylaluryl tauride, sodium dodecylbenzenesulfonate and triethanolamine undecanol benzene sulfate.

Examples of suitable nonionic detergents are alkylphenol and alcohol alkoxylates including the condensates of 1-decanol and 1-undecanol having from 3 to 5 molecular fractions Ethylene oxide, as described in US patent application Serial No, 707 480 are described, condensates of monohydroxy or Polyhydroxy alcohols such as oleyl alcohol or 1-tridecanol with

9 to 15 molecular fractions of ethylene oxides, internal alkyl

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Available dialkoxy or hydroxyalkoxy compounds, as described in U.S. patent application serial no. 852 898 and condensates of alkylene oxides with organic amines, such as for example ethylenediamine and amides such as N-octadecyl diethanolamide.

Suitable ampholitic surfactants include the amidoalkene sulfonates such as sodium C-pentadecyl, N-methylamidoethylsulfonate, Potassium C-octyl-N-naphthalenamidopropylsulfonate, Ammonium C-decyl, N-cyclopropylamidobutyl sulfonate and aliphatic amine derivatives wherein the aliphatic substituent is an anionic water-solubilizing agent Substituents such as a carboxy, sulfo, phosphato or Contains phosphino group, for example sodium 3-dodecylaminopropionate and sodium 3-dodecylaminopropionesulfonate.

Examples of zwitterionic surfactants are derivatives of quaternary ammonium, phosphonium and sulfonium compounds, such as 3- (N, N-dimethyl-N-hexadecylammonium) propane-1-sulfonate and 3- (N, N-dimethyl-N-hexadecylammonium) -2-hydroxypropane-1-sulfonate.

It should be noted that the above examples of additive surfactants are not are complete. There are numerous others to those skilled in the art

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known surfactants, in which context "Surface Active Agents" by A.M. Schwarz and James W. Perry is advised. It should also be noted that the use of such surfactants after conventional well known methods for detergent formulation. For example, cationic and anionic detergents are not normally used together, otherwise the known problems of precipitation insoluble products occur.

As is common practice, the ratio of the detergent builder components will be surfactants range from 1: 2 to about 12: 1 by weight.

In addition to the surfactant and detergent builder components, the detergent formulations can Fillers, such as sodium sulfate, and small amounts of bleach, Dyes, optical brighteners, soil release agents, perfumes and similar conventional detergent formulation additives contain.

It should also be noted that the connections of this invention is effective in machine wash formulations can replace all or part of the sodium tripolyphosphate.

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The invention is further illustrated by the following examples in which all parts and percentages are by weight unless otherwise stated.

example 1

A slurry of 34 g of sodium ethyl glycolate in 300 ml of 1,2-dimethoxyethane are added with stirring to a solution of 63 g of diethyl 2-bromo-2-methylmalonate in precooled to 5 ° C 100 ml of 1,2-dimethyloxyethane, the temperature on a Value is kept below 10 ° C. The reaction mixture is then kept at 25 ° C. for 16 hours with continued stirring and 2 hours at 65 ° C. The contaminants are collected by filtration and the solvent under reduced pressure removed. The residue is dissolved in chloroform and the solution is washed successively with 0.5N hydrochloric acid and saturated soda solution and water. The solution is then dried over anhydrous MgSOj. and removes the chloroform under reduced pressure Pressure. The residue is fractionally distilled, the product being collected at 95 to 97 ° C / 0.04 mm Hg.

The product was determined by nuclear magnetic resonance and elemental analysis identified as triethyl-2-oxa-1,3 »3-butane tricarboxylate.

The ester is dissolved in an aqueous ethanol solution of sodium

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hydroxyd saponified at room temperature. By acidifying the solution with H-SO ₁ , the acid is obtained, which is extracted with ether and recrystallized therefrom.

The salt is precipitated by pouring the saponified solution into excess methanol.

Example 2

It has been found that detergent formulations having 12% linear alkyl benzene sulfonate with an average alkyl chain length of about 12 carbon atoms add from 5 to 75% trisodium 2 "-oxa-1,3» 3-butane tricarboxylate _s 12 % sodium silicate with an SiO ₂ Na ₂ O ratio of approximately 2.4 and an amount of sodium sulfate that is sufficient to make them up to 100 % , in normal washing processes soiled samples of cotton and polyester cotton cloths are much better cleaned than otherwise identical formulations that do not contain a trinatium -2-oxa-1,3,3-butane tricarboxylate These studies indicate that this material works effectively as a detergent builder.

Example 3

The tests of the previous example 2 are repeated, using a detergent formulation wherein Neodol 45-11 (a nonionic surfactant

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Agent that is an adduct of a modified CL ^ -C ^ alcohol with an average of 11 moles of ethylene oxide) is used instead of alkylbenzenesulfonate. It will be comparable Get results.

Example H

The studies of Example 2 are carried out with a detergent formulation repeated, in which sodium hydroxyalkyl-iC ^ -CLg-alkyl chain length) -N-methyl laurate, an ampholytic surfactant is used in place of the alkyl benzene sulfonate will. Comparable results are obtained.

Example 5

The studies of Example 2 are carried out with a detergent formulation repeats, wherein cocodimethylsulfopropylbetaine, a zwitterionic surfactant, is substituted of the alkylbenzenesulfonate is used. Comparable results are obtained.

Example 6

Detergent formulations containing 5 to 75 % trisodium 2-oxa-1,1,3-propane tricarboxylate are prepared and tested as in Examples 2 and 5. Comparable results are obtained.

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Example 7

A solution of 63 g of diethyl 2-bromo-2-ethyl malonate in 25 ml of tetrahydrofuran is added at 65 ° C. to a slurry of 59 g of sodium diethyl methyl tartronate in 300 ml of tetrahydrofuran. The mixture is refluxed for 18 hours, after which the tetrahydrofuran is removed in vacuo and the residue is diluted with ethyl ether. The ethereal solution is washed with water to remove NaBr _{, dried over anhydrous CaSO 1} and distilled to remove the ether.

The residue is subjected to fractional distillation, a product being collected at 130-135 ° C./0.06 mm Hg will. This product is identified as tetraethyl 3-oxa-2,2,4,4-hexatetracarboxylate by means of nuclear magnetic resonance and elemental analysis identified.

The sodium salt is obtained by saponification in a methanol solution of sodium hydroxide at room temperature and it is obtained by means of filtration.

Example 8

To a slurry of 34 g of sodium ethyl glycolate in 300 ml Tetrahydrofuran, which has been cooled to about 3 ° C., is added to a solution of 63 g of diethyl 2-bromo-2-ethylmalonate in 25 ml

609816/0995

Add tetrahydrofuran at about 3 ° C. Hold the mixture Two hours of stirring at 0 ° to 5 ° C, heat it up, keep it at about 25 ° C for 16 hours, then heat it up for two hours long at reflux.

The tetrahydrofuran is removed in vacuo and the residue treated as in Example 7 to give the ester product Triethyl-2-oxa-1,3,3-pentane tricarboxylate at 101 bis 107 ° C / 0.05 mm Hg collects and converted into the salt form as in Example 7.

Example 9

Sodium ethyl lactate, 38 g, and diethyl 2-bromo-2-ethyl malonate is reacted according to the method of Example 8, whereby an ester product, triethyl 3-oxa-2,4,4-hexane tricarboxylate, obtained that collected at 92 to 96 ° C / 0.04 mm Hg and how described in Example 8, is converted into the salt form.

Example 10

To a slurry of 98 g of sodium ethyl lactate in 400 ml of 1,3-dimethoxyethane 136 g of diethyl chloromalonate are added at the reflux temperature. The mixture is heated to 70 ° C. for 8 hours and then kept at 25 ° C. for 48 hours. The 1,2-dimethoxyethane is evaporated, the residue dissolved in carbon tetrachloride, treated with water to remove NaCl

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wash over MgSOj. dried and the CHCl, evaporated. Fractional distillation of the residue gives a product (boiling point 94 to 96 ° C./0.03 mm Hg) which is analytically identified as triethyl-2-oxa-l, l, 3-butane tricarboxylate. Obtained by saponifying the ester with NaOH one trisodium-2-oxa-l, 1,3-butane tricarboxylate.

Example 11

To a slurry of 77 g of sodium ethyl lactate in 300 ml A solution of 127 g is added to 1,2-dimethoxyethane at 45 ° C Add diethyl 2-bromo-2-methylmalonate in 1,2-dimethoxyethane and lets the temperature rise to about 65 ° C. The mixture is refluxed until the p "value of an aqueous Solution of the mixture is about 7. The 1,2-dimethoxyethane is evaporated and the residue is washed to remove the NaBr with water. The dried residue is distilled and a product is obtained (collected at 82 ° C / 0.05 mm Hg) which is identified analytically as triethyl 3-oxa-2,2,4-pentane tricarboxylate. Trisodium 3-oxa-2,2,4-pentane tricarboxylate is obtained by saponifying the ester with NaOH.

Example 12

A 1 liter flask is flushed with nitrogen and charged with 400 ml of tetrahydrofuran, cools to -30 ° C. in a dry ice-acetone bath, then gives 115 ml of 2.3 molar solution of

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n-Butyllithium in tetrahydrofuran and cools the solution to -75 ° C. A solution of 21 g of diethyl glycolate in 100 ml of tetrahydrofuran is then added and the temperature is maintained below 70 ° C, CO- will then bubble into the mixture for about an hour and warms the mixture to room temperature and, after the tetrahydrofuran has evaporated, a yellow powder is obtained. The powder is dissolved in water and 100 ml of Rexyn 101 (H) ion exchange resin are used admitted. An insoluble gum separates out and is removed. The remaining solution is then passed through a column containing sufficient resin to cause conversion to the half-ester / half-acid product to effect.

The aqueous solution of the half-ester / half-acid product is dried to a syrup. This material is dissolved in 25 ml of ethanol, ¹ IO ml of benzene and 0.2 g of concentrated HpSO. ₁ The water is removed azeotropically and the residue is dissolved in benzene, washed with NaHCO 3 solution and then with water and dried over MgSO 2. The benzene is evaporated and the residue is distilled. The product collected at Uli at up to 112 ° C./0.05 to 0.1 mm Hg is identified as tetraethyl 2-oxa-l, l, 3,3-propane tetracarboxylate.

The saponification of the half-ester / half-acid product with sodium hydroxide provides tetrasodium-2-oxa-l, l, 3> 3-propane tetracarboxylate.

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Example 13

To a slurry of 56 g of sodium diethyl methyl tartronate
in 300 ml of refluxing tetrahydrofuran is added
a solution of 63 g of diethyl 2-bromo-2-methylmalonate in 25 ml of tetrahydrofuran is added and the mixture is kept for 16 hours
Reflux. The solvent is evaporated and the residue is diluted with ethyl ether. NaBr is removed by washing the ethereal solution with water, the washed solution is _{dried over CaSO 1} and MgSO ₁ , and the solvent is evaporated.

By distilling the residue, a fraction is obtained which is collected at 125 ° C./0.05 mm Hg and which is called
Tetraethyl 3-oxa-2,2,4,4-pentanetetracarboxylate identified.

The saponification with NaOH gives the tetrasodium salt.

Example 14

Detergent formulations containing 5 to 75 % of the salt forms of the compounds of Examples 7 to 13 are prepared and tested as in Examples 2 to 5. It
comparable results are obtained.

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Claims (1)

Claims ί l) detergent composition of surfactants containing at least 8 parts by weight Jt agents (surfactants), namely one or more anionic, nonionic, zwitterionic, ampholitischer and / or amphoteric surfactants, characterized in that they from 1 to 75 wt. - % of a detergent builder compound of the general formula below, COOM COOM R ¹ COOM wherein the radical M are alkali metals and / or ammonium, the 1 2 R and R independently of one another are hydrogen, methyl and / or ethyl, and R ^ is hydrogen, methyl and / or COOM is. 2. Preparation according to claim 1, characterized in that the detergent builder in one Quantity from 5 to 50 wt .->? the preparation is present. 3. Preparation according to claim 1, characterized that the remainder M is sodium. 1. Preparation according to claim 1, characterized in that - - 19 609816/0995 1 2 indicates that the radicals R and R are hydrogen and / or methyl groups and R is hydrogen. 5. Preparation according to claim 1, characterized in that the remainder R is COOM. 6. Preparation according to claim 5 » thereby ge - 1 2 indicates that the radicals R and R are methyl groups are. 7. Preparation according to claim 5 » thereby ge indicates that the radical R is a methyl group ο
and the remainder R are hydrogen. 609816/0995