DE2364440A1 - Novel surface active betaines - for use in low phosphate or phosphate-free detergent compsns - Google Patents

Abstract

Novel surface active betaines are of formula- R(CH2-CHOH-CH2OH)2-N+-A-Z (I), (where R is a (un)satd. 8-20C, pref. 12-18C aliphatic gp., A is 1-4C alkylene, opt. substd. by OH, and X is sulph(on)ate or carboxylate). (I) are used in low phosphate or phosphate-free washing compsns. and have excellent surface active props.

Description

Henkel & Cie GmbH

Dr.HH / sch « _ΛΛ ~ / #" Γ «

4000 Düsseldorf, the 21st I2.iS7J 2364440

Henkelstrasse 6?

Patent application

D 4814
"Surface active betaines"

The invention relates to surface-active compounds with Betaine structure, the valuable surfactants for detergents and cleaning agents, represent in particular for low-phosphate and phosphate-free detergent formulations, as well as processes for the production of the new fabrics.

Surface-active compounds with a betaine structure are known. It is understood to mean compounds that have both positive and negative charges in the molecule, which are intramolecular are balanced. In particular, betaines are understood to mean zwitterionic quaternary ammonium compounds. They are usually given by the formula

R.
r — N®— A - X ^Θ .

reproduced, where one of Reste.R is a fatty alkyl radical with 12-18 carbon atoms and the other two radicals R Alkyl radicals with 1-5 carbon atoms or hydroxyalkyl radicals with 2 - 5 carbon atoms, A an aliphatic, optionally hydroxy-substituted radical and X © the sulfonate, Are sulfate or carboxyl group.

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50982 7/100 3 original inspected

Henkel & Cie GmbH

X 9-5R /. /. /.Π

■ > v ^ \ - / "™ f —5 * —r κ **

The invention relates to new antagonist ammonium compounds with betaine structure different from the known Compounds differ essentially in that they have the quaternary nitrogen atom instead of the two lower ones Alkyl or hydroxyalkyl radicals two 2, j5-dihydroxypropyl radicals own. It has surprisingly been found that this Both residues help determine the surface-active properties of the new active ingredients.

The new surface-active betaines are characterized by the formula I.

CH ₂ -CHOH-CH ₂ OH

RN @ —Α — Χ ^Θ - (I)

CH ₂ -CHOH-CH ₂ OH

in the R-- an unsaturated or saturated aliphatic A radical with 8-20 carbon atoms, preferably a saturated radical with 12-18 carbon atoms, A optionally one alkylene radical substituted with a hydroxyl group with 1-4 carbon atoms, preferably a radical from the group consisting of methylene, methylene and 2-hydroxypropane-1,3-diyl, and X® is a sulfonate, sulfate or carboxylate group mean. .

The new betaines have excellent surfactant properties. They are particularly suitable for use in low-phosphate and phosphate-free detergent formulations.

5038 ^ 7/1003

Hang! & Cie GmbH

η O R / /. /. C \ Patent department

Under low-phosphate detergent formulations such Preparations are understood that have at most half the phosphate content of commercially available detergents, i.e. the highest ^ g $ Giw .- # contain sodium tripolyphosphate. The phosphate-free detergents contain the usual detergent phosphates replaced by other water-soluble inorganic or organic builders. These builders contain either no inorganically or organically bound phosphorus, such as those known as washing alkalis Alkali carbonates, bicarbonates, silicates or borates, or the aminopolycarboxylic acids known as calcium ion complexing agents, Ether carboxylic acids, hydroxycarboxylic acids, polyacrylic acids, etc. or they contain organically bound phosphorus in an amount far below that of detergent phosphates, such as those known as calcium complexing agents organic phosphonic acids of the Phosphonoalkanpolyearböns-uren type and the amino- and hydroxy-substituted alkane polyphosphonic acids.

For example, the following substances belong to the new class of surface-active betaines?

5- (N-dodecyl-N, N-bis (2, j5-dihydroxypropyl) ammonio) propane sulfonate;

5- (N-dodecyl-N, N-bis (2,5-dihydroxypropyl) ammonio) -2-hydroxypropanesulfonate;

4- (N-Docecyl-N, N-bis (2,3-dihydroxypropyl) -ammonio) -butanesulfonate j ^ - (N-Tetradecyl-NiN-bis (2,5-dihydroxypropyl) -ammonio) -propane sulfonate j.

> - (N-Tetradecyl-N, N-bis (2,5-dihydroxypsropyl) -ammonio) -2-hydroxypropanesulfonatej -

2- (N-hexadecyl-N, N-bis (2, ^ -dihydroxyppopyl) -ammonio) -.

ethanesulfonate; \. -

5- CN-Octadecyl-N, N-bis (2,> - dihydr oxypropyl) -ammonio) - < ^: -

pröpansulfonatj t

5- (N-Oc: tadecyl-N, N-bis (2,5-dihydr oxypropyl) -ammonio) -. » 2-hydroxypropanesulfonatej 5

5- (N-hexadecyl-N, N-bis (2,5-dlhydroxypropyl) -ammonio) -

2-hydroxypropyl sulfate j. -> '- ·

N-Te tradecyl-N, N-bis (2, jj-dihydroxypropyl) -ammonloacetat j ^'f N-hexadecyl-N, N-Msi2,3-äihvdrqxypropyl) -ammonioacetat. ^v > - - ^ ~.

** 236 A 440 Henkel & Cie GmbH

(j Patent department

In practice, those compounds according to the invention are particularly useful which are derived from the fatty amines which can be prepared from natural sources and which are corresponding mixtures of substances with alkyl or alkenyl radicals of different lengths. Typical representatives of such betaines are, for example, the products derived from coconut amine and tallow amine 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) ammonio) propanesulfonate and 3- (N-tallow alkyl-N, N-bis (2, j3 ~ dihydroxypropyl) ammonio) -2-hydroxypropanesulfonate, the radicals "coconut alkyl" or "tallow alkyl" essentially referring to the C ^ / ^ lA "* ^or * C, g / C, g-alkyl or alkenyl fractions of the corresponding fats.

The new betaines are obtained by having a tertiary amine of formula II.

"- · RN (CH ₂ -CHOH-CH ₂ OH) ₂ (il)

has in the H angegebeme in formula I, is reacted with a group -AX "introductory Cuaternierungsmittel of formula III '■ ■

ZAX ¹ (III),

where Z is a halogen atom, in particular chlorine, or one to X ^! leading bond- ,. A is the radical given in formula I and X ^! denote the alkali salt radical of the sulfonate, sulfate or carboxylate or the sulphonyloxy radical connected to A via a free bond Z. ^;

Accordingly, the alkali salts of haloalkanesulfonic acids, or the half esters of haloalkylsulfuric acids, or haloalkanecarboxylic acids with carbon chains of C ^ -C ^ are suitable as puring agents of the formula III; for the. If Z is a free bond and X ^{1 is} the radical -SO ₂ -O-, the quaternizing agents are sultones. <.

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^ Henke! & Cie GmbH

Patent department

Fuaternating agents which can be used according to the invention are for example the compounds ^ -Chlor ^ -hydroxypropansodiumulfonat, j5-chloro-2 ~ hydroxypropyl sodium sulfate, Sodium chloroacetate, propane sultone and butane sultone.

According to a variant of the manufacturing process can also introduce the 2-hydroxypropyl sulfate residue in that man the tertiary amine of the formula II initially with ös-glycerol chlorohydrin to the N-alkyl-N, NiN-tris (2,3-dihydroxypropyl) ammonium chloride cmaternated and then with a Sulphating agents such as chlorosulphonic acid or sulfur trioxide j sulphated.

The invention also relates to solid form, as pastes, Detergents and cleaning agents present in dispersions or solutions with a content of a surface-active betaine and at least one other usual cleaning agent active substance from the group of anionic and nonionic; n Surfactants and the organic and inorganic builder substances, these agents being surface-active Betaines, the compounds of formula I in amounts of 1.5 - ^ O Wt .- ^ included.

Of particular interest is the use of the new ones Betaine surfactants in low-phosphate detergents which contain not more than 20% by weight of sodium tripolyphosphate and for which a loss of detergency due to the reduction in the amount of phosphate is compensated again by a content of the betaine surfactants according to the invention.

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The low-phosphate detergents contain, accordingly, in addition to other conventional ingredients 10 - 20 wt .- ^ Natriumtr phosphate and are characterized in that they betaine the invention of formula I in an amount of 10 - contain% - 30 wt..

Phosphate-free preparations in which the new surfactants according to the invention can be used contain, instead of the usual detergent phosphates, the aforementioned inorganic and organic water-soluble builders in one Amount, which is generally in the range of 5- ^ 0 wt .- ^, based on the entire preparation.

Inorganic water-soluble builders are primarily the salts known as washing alkalis from the group of the carbonates, bicarbonates, borates and silicates of the alkalis. Of the alkali silicates, the sodium silicates with a Na ₂ O: SiOp ratio such as. 1 ί 1 to 1: 5.5.

Suitable organic builders are the water-soluble ones. Salts of aminopolycarboxylic acids, such as, for example. Nitrilotriacetic acid, ethylenediaminetetraacetic acid; the hydroxycarboxylic acids, such as citric acid, gluconic acid; of the carboxymethyl ether carboxylic acids, such as, for example, carboxymethyloxysuccinic acid, carboxymethyltartronic acid, ethylenedioxydiacetic acid, oxydiethylenedioxydiacetic acid; the water-soluble salts of polymeric carboxylic acids, such as polyacrylic acid, poly-OC-hydroxyacrylic acid, polycarboxylic acids from copolymers of maleic anhydride with ethylene, propylene, vinyl methyl ether, etc., as well as those obtainable from acrolein and acrylic acid with EUO ₀ and subsequent Cannizzarp reaction, hydroxycarboxylic acids. - "

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ORIGINAL INSPECTED

2364A40 Henkel & Cie GmbH

Patent department

The water-soluble salts of the compounds from the group of the phosphonoalkanepolycarboxylic acids are suitable as organic phosphonic acids and the amino and hydroxy substituted alkane polyphosphonic acids, such as the salts of Aminotrimethylene tr! Phosphonic acids dimethylaminomethanediphosphonic acid, 1-Hydroxy-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tr! Carboxylic acid.

In order to obtain free-flowing powder preparations, recommends usually an addition of sodium sulfate as a carrier substance. Further structural substances because of their hydrotropic properties mostly used in liquid agents are the salts of the non-capillary-active 2-9 carbon atoms Sulfonic acids, carboxylic acids and sulfocarboxylic acids, wJe e.g. the alkali salts of benzene, toluene, xylene or cumene sulphonic acids, sulphoboic acids, sulphophthalic acid, SuIf © succinic acid and the salts of acetic acid or Lactic acid.

The detergents and cleaning agents according to the invention can in addition to the new betaine surfactants of the formula I, the usual änionic and non-ionischeη surfactants as well as usual Supplements included. ■

The anionic surfactants include the washing-active compounds which, in aqueous solution, form an anion that contains the hydrophobic part of the molecule. In addition to soaps of natural or synthetic, preferably saturated fatty acids, belong to this class of compounds, especially the alkali metal salts of organic sulfonates or sulfates, such as the Alkylary! Sulfonates * tnd the sulfates of Fett-- · ¹ alcohols and Fettalkoholäthoxylierungsprodukten. The sodium salts of dodecylbenzenesulfonate and of laurylstilfonate are typical examples of these ionic surfactants. Other useful surfactants of the sulfonate type are the ester salts of saturated α-sulfofatty acids, for example the sodium salts of OC sulfo acids. from the methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. '·

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The nonionic surfactants owe their hydrophilic properties to the presence of a polyethylene glycol ether chain from 3-20 ethylene glycol units, or one Amine oxide or sulfoxide function. Really important are the ethoxylation products - natural or synthetic Fatty alcohols.

The usual detergent and cleaning agent additives are dirt carriers, optical brighteners, textile softeners, Active oxygen and active chlorine bleaching agents, antimicrobials, foam regulators, enzymes, dyes and fragrances.

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Patent department Examples

Example 1: 3- (N-Hexadecyl-N, N-bis (2,3-dihydroxypropyl) -ammonio) -propanesulfonate

To a solution of 120.5 g (0.5 mol) of hexadecylamine in 400 ml of ethanol, 74 g (1 mol) of glycide are added dropwise under reflux. The mixture is allowed to stir for a few hours under reflux and then 60 - 70 ⁰ C. 61 g (0.5 mol) are added dropwise propane sultone molten. After a further 4 hours under reflux, the alcohol is distilled off in vacuo and the product is obtained as a residue in the form of a colorless, soft paste. Decomposition point 190-195 ° C (Kofler heating bench).
Elemental analysis;

Nitrogen: found 3.1 % over 2.7 % \ sulfur: found. 6.2 % i . 6, 3.

Example 2: -3- (N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonio) -2-hydroxypropanesulfonate

To 194.5 g (0.5 mol) of N-hexaecyl-N, .N-bis (2,3-dihydroxypropyl) amine (See example 1 for representation) in 500 ml of ethanol one leaves at reflux temperature the solution of 100 g (approx. 0.5 mol) I-chloro-S-hydroxypropyl-1-Na sulfonate in 150 ml of water is added dropwise and the mixture is stirred under reflux for a further 8 hours, then concentrated the solution is taken up, the residue is taken up in ethanol and filtered the excreted table salt from, constricts again and the product is thus obtained as a colorless, solid mass.

Infrared spectrum (information in cm "")

3350 s, 2950 sh, 29IO s, 2840 s, 1465 m, 1215 s, Il4o m, 1055 s, 720 m;

(s = »strong; m = medium; sh = shoulder).

~ 10 -

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Patent department

' JO.

Example ^: N-Hexadecyl-N, N-bis (2,5-dihydroxypropyl) ~ ammonio acetate

To the solution of 0.5 mol of the amine prepared as in Example 1 in 400 ml of ethanol is added at reflux temperature 47.5 g (0.5 mol) of chloroacetic acid, which had previously been carefully neutralized with dilute sodium hydroxide solution while cooling was and stirs for 8 hours. Then the precipitated common salt is filtered off and the solvent is evaporated off. The The residue is taken up in ethanol and a further 1J g of NaCl is sucked in and narrow the solution. The product is thus obtained as a yellowish mass which solidifies amorphously.

Infrared spectrum (information in cm ")

5500s, £ 950s, 29IOs, 2840s, I6OOs, 1465m, 1410m, 1520m, 1110 m, 1075 m> 1045 m, 720 ra.

Elemental analysis:

Carbon: found 64.0 #} calc. 64.4 %; ·

Hydrogen: f. 11.6 % over 11.0 #j nitrogen: found 5.5 % '> cal. 5.1 ^.

Example 4: 5- (N-hexadecyl-N, N-bis (2,5-dihydroxypropyl) ammonio) -2-hydroxypropyl sulfate

56 g (0.5 mol) of Otz glycerol chlorohydrin are first mixed with 200 ml Chloroform and then, with vigorous stirring, 58 g (0.5 mol) of chlorosulfonic acid were added dropwise. Then 5 hours stirred at room temperature and then the majority of the remaining hydrogen chloride by introducing nitrogen removed. 100 ml of water are added, the aqueous solution is separated off and concentrated in vacuo. The residue will taken up in ethanol and neutralized. This solution wire * at Reflux temperature with 204 g (0.5 mol) of N-hexadecyl-NjN-bis (2,5-dihydroxypropyl) amine, dissolved in 400 ml of ethanol, ver; sets and stirred under reflux for 8 hours. After narrowing in The precipitated common salt is filtered off in vacuo and taken up again in ethanol. The Filtrafe is concentrated and so is the product obtained as a colorless, pasty mass.

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Henkel & Cie GmbH

Patent department

ti

Elemental analysis:.

Nitrogen: found 2.25 f> \ her. $ 2.58;
Sulfur: found 5.67 % '> calc. 5 * 90 ^.

Example 5: ^ - (N-Dodecyl-NiN- bis ^^ - dihydroxypropyl) -ammonio) -2-hydroxypropyl sulfate

85 g (0.25 mol) of N-dodecyl-N, N-bis (2,5-dihydroxypropyl) amine, prepared analogously to Example 1, are added to 300 ml of dimethylformamide
27.7 g (0.25 mol) of oc-glycerol chlorohydrin were added and the mixture was stirred under reflux for 10 hours. After the solvent has been stripped off, the intermediate product obtained is N-dodecyl-N, N, N-tris (2,5- <Äihydroxypropyl) -ammoniumchloride. This substance is mixed with 200 ml of chloroform and distributed as finely as possible by stirring vigorously.
At 10-15 ° C., 2 "g of chlorosulfonic acid are slowly added, the mixture is stirred for 5 hours and then concentrated in vacuo. The product is thus obtained as a yellowish, pasty mass.

Elemental analysis:

Nitrogen: found 2.6 % ', calc. 2.7 % -,
Sulfur: found 6.2 % over 6.5 #.

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Henkel & Cie GmbH

Patent department

The following examples illustrate the invention Use of the new surface-active betaines in detergents and cleaning agents *. The salty components of the Unless otherwise stated, preparations are in the form of the sodium salts.

Example 6: Low-phosphate heavy-duty detergent

20.0 wt .- ^ 3- (N-Cocosalkyl-N, N-bis (2,3-dihydroxypropyl) -

ammonio) propane sulfonate. 3.0 wt .- ^ soap (proportion of C ₂₀ ZCg ₂ fatty acids: 48 % _t

Iodine number 5)
20.0 wt% triphosphate

5.0 wt -% Sodium Silicate (1: 3.3). 24.0 wt -% perborate.
2.5 wt. $ Magnesium silicate
1.5 g (3W .- ^ carboxymethyl cellulose 0.2 Giiw .- ^ Kthylenediamine tetraacetate remainder "sodium sulfate and water *

Example 7: Phosphate-free heavy duty detergent

50.0 wt .- ^ 3- (N-tetradecyl-N, N-bis (2,3-dihydroxypropyl) ammonio) -2-hydroxy propanesulfonate

2.5 wt .- ^ oleyl-ZCetylalkohoi-Äthoxylat (10 mol ethylene oxide, Iodine number of alcohol = 45)

15.0 Gaw .- $ Citrate ■

10.0 wt -.% * Sodium silicate (1 J 3.3) 20.0 wt -.% Perboratte.trahydrat

2.0 wt -.% Magnesium silicate

1.5 wt% carboxymethyl cellulose 0.3 wt% optical brightener

0.2 wt -.% Sschauminhibitor
Rest . Sodium sulfate and water. * ·.

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Patent department

Example 8: Phosphate-free pre-wash detergent

10.0 wt -.% _J5- (N-Dode © yl-N, N-bis (2,3-dihydroxypropyl) -ammonio) -2-hydroxypropylsulfat

3.0 wt % dodecylbenzenesulfonate 20.0 wt% soda

5.0 wt - $ Sodium Silicate (1: 3.3). 1.5 wt .- ^ carboxymethylcellulose 1.5 wt -% enzymes.

0.2 wt .- # foam inhibitor Remainder sodium sulfate and water.

Example 9 * Main detergent

10.0 wt .- ^ N-hexadecyl-N, N-bs (2,3-dihydroxypropyl) ammonium acetate

5.0 wt .- ^ Cocosfettalkoholätho.cylat (10 mol ethylene oxide)

j5,0 wt -% Cocosfettalkoholäthoxylat (J} moles of ethylene oxide 10.0 wt .- ^ triphosphate 15.0 wt .- ^ sodium silicate (1:.?. I, 4) 2.0 wt -% Carboxymethylcellulose 0.3 wt. - ^ ethylenediaminetetraacetate 0.2 wt -.% optical brightener

0.2 wt -.% Foam inhibitor moiety sodium sulfate and water.

Example 10: Liquid detergent and cleaning agent

10.0 wt .- ^ 3- (N-dodecyl-N, N-blsi2,3-dihydroxypropyl) -ammonio) -2-hydroxypropanesulfonate

3.0 percent -.% Cocosfettalkoholsulfat 6.0 Ge \ j .-%> Kaliumtoluölsulfonat 8, .O wt .- ^ potassium citrate

0.3 wt% perfume oil;

Remainder isopropyl alcohol and water.

Washing experiments with phosphate-free and low-phosphate detergent formulations using the new surface-active betaines have shown that the detergency of these preparations is assessed as equally good and in some cases better than the detergents . effect, known detergent containing phosphates.

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Claims (1)

Sheet 12j. To patent application D 4814 Pateritabteilung Claims 1. Surface-active betaines, characterized by the formula I. CH ₂ -CHOH-CH ₂ OH
R_M @ -A-XÖ (I) -CHOH-CHoCH " in which R is an unsaturated or saturated aliphatic radical with 8-20 carbon atoms, preferably a saturated one A radical with 12-18 carbon atoms, A is an optionally substituted with a hydroxyl group Alkylene radical with 1-4 carbon atoms, preferably one Radical from the group trimethylert, methylene and 2-hydroxy-propane-l, 3-diyl, and X® denotes a sulfonate, sulfate or carboxylate group. 2. Process for the preparation of the compounds of the formula] I according to claim 1, characterized in that a tertiary amine of the formula II RN (CH ₂ -CHOH-CH ₂ OH) ₂ (H) in which R has the meaning given in formula I, with a quaternizing agent introducing the group -A-X ® of formula III ZAX ¹ (III) converts, where Z is a halogen atom, in particular chlorine, "or · a bond leading to X ', A denotes the one given in formula I. Radical and X 'is the alkali metal salt radical of the sulfonate, sulfate or carbocxylate or the one above; free bond Z connected to A Mean suIfonyloxy radical. : - 15 - 509827 / 1QO3 Hang! & Cie GmbH Patent department J5. Process for the preparation of the compounds of formula I. according to claim 1, in which the group -A-X "is the 2-hydroxypropyl sulfate radical means, characterized in that a tertiary amine of the formula II RN (CH ₂ -CHOH-CH ₂ OH) ₂ (il) in which R has the meaning given in formula I, initially quaternized with 06-glycerol chlorohydrin and then with converts a sulfating agent. 4. Detergents and cleaning agents with a content of one surface-active betaine and at least one other customary cleaning substance from the group of anioniscs and nonionic η surfactants and the organic and inorganic Grjüstsubs dance, characterized in that they are as surface-active betaines the compounds of formula I according to Claims 1 - 5 contained in amounts of 1.5 - 40 wt .- ^. 5. Low-phosphate detergent according to claim 4 with a content of 10-20 wt. % Sodium triphosphate, characterized in that it contains the surface-active betaines of the formula I according to claim 1 - J> in an amount of 10-50 wt .- ^. 509827/1003