WO1994009018A1

WO1994009018A1 - Alkyl- and/or alkenyloligoglycoside ester sulphate salts

Info

Publication number: WO1994009018A1
Application number: PCT/EP1993/002672
Authority: WO
Inventors: Manfred Weuthen
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1992-10-09
Filing date: 1993-09-30
Publication date: 1994-04-28
Also published as: EP0663920A1; DE4234019A1; JPH08502267A

Abstract

The alkyl- and/or alkenyloligoglycoside ester sulphate salts described can be prepared by transesterifying, in the presence of alkaline catalysts, alkyl- and/or alkenyloligoglycosides of the formula (I): R1-O-[G]¿p?, in which R?1¿ is a straight-chain or branched-chain alkyl and/or alkenyl group with 4 to 22 carbon, G is a saccharide group with 5 or 6 carbon atoms and p is a number from 1 to 10, with α-sulphocarboxylic acid lower-alkyl ester salts of formula (II), in which R2 is hydrogen or an alkyl group with 1 to 20 carbon atoms, R3 is a straight-chain or branched-chain alkyl group with 1 to 4 carbon atoms and X is an alkali metal. The products are suitable for use in the production of a wide variety of surface-active agents.

Description

Alkyl and / or alkenyl oligoglycoside estersulfonate salts

Field of the Invention

The invention relates to alkyl and / or alkenyl oligoglycoside ester sulfonate salts, a process for their preparation in which alkyl and / or alkenyl oligoglycosides are transesterified in the presence of alkaline catalysts with alpha-sulfocarboxylic acid lower alkyl ester salts and the use of these products for Manufacture of surfactants.

State of the art

Alkyl oligoglycosides and especially alkyl oligoglucosides are nonionic surfactants, which have become increasingly important due to their excellent detergent properties and high ecotoxicological compatibility.

There has been no shortage of attempts in the past to also produce anionic surfactants based on alkyl oligoglycosides. For example, EP-A1 0 186 242 (Procter & Gamble) describes the sulfation of alkyl oligoglucosides in dimethylformamide with sulfur trioxide and EP-A1-0 363 601 (Hoechst) describes sulfation with a sulfur trioxide. Amine complex known. Gas sulfonation of alkenyl glycosides in inert solvents is described in DE-Al 39 18 135 (Henkel). DE-Al 40 06 841 (Henkel) finally proposes to sulfate mixtures of alkyl oligoglycosides and fatty alcohols together. However, all of these methods have disadvantages: sulfation in solvents is complex and places high demands on occupational safety. Since the solvents have to be separated off again after the reaction, these processes are also not very profitable. If, instead of inert solvents, those are used which are also converted into anionic surfactants in the course of the sulfation, the anionic modified, ie sulfated, alkyloligo glucosides are obtained only in a mixture.

The object of the invention was to develop new anionically modified alkyl and / or alkenyl oligoglucosides, the production of which is free from the disadvantages described.

Describe bnnσ of the invention

The invention relates to alkyl and / or alkenyl oligoglycoside estersulfonate salts which are obtained by alkyl and / or alkenyl oligoglycosides of the formula (I),

R ^l _0- [G] _p (I)

in the R ~ for a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G for one Sugar residue with 5 or 6 carbon atoms and p represents numbers from 1 to 10, in the presence of alkaline catalysts with alpha-sulfocarboxylic acid lower alkyl ester salts of the formula

(II),

R ² -CH-COOR ³ (II)

I S0 ₃ X

in which R2 represents hydrogen or an alkyl radical having 1 to 20 carbon atoms, R ^{3 represents} a linear or branched alkyl radical having 1 to 4 carbon atoms and X represents an alkali metal.

Surprisingly, it was found that anionically modified alkyl and / or alkenyl oligoglycosides can be obtained in high yields without the use of solvents if the alcohol component in alpha-sulfocarboxylic acid ester salts is exchanged for the alkyl and / or alkenyl oligoglucoside.

The invention further relates to a process for the preparation of alkyl and / or alkenyl oligoglycoside ester sulfonate salts, in which alkyl and / or alkenyl oligoglycosides of the formula (I),

Rl_0- [G] _p (I)

in R ¹ for a linear or branched alkyl and / or alkenyl radical with 4 to 22 carbon atoms, G for a sugar radical with 5 or 6 carbon atoms and p for numbers of 1 to 10, in the presence of alkaline catalysts with alpha-sulfocarboxylic acid lower alkyl ester salts of the formula (II),

R ² -CH-COOR ³ (II)

I S0 ₃ X

in which R ^{2 represents} hydrogen or an alkyl radical having 1 to 20 carbon atoms, R ^{3 represents} a linear or branched alkyl radical having 1 to 4 carbon atoms and X represents an alkali metal.

Alkyl and alkenyl oligoglycosides are known substances which can be obtained by the relevant processes in preparative organic chemistry. Representative of the extensive literature, reference is made here to the publications EP-Al-0 301 298 and WO 90/3977.

The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucos de.

The index number p in the general formula (I) indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer and here can assume the values p = 1 to 6, the value p is for a particular alkyl oligoglycoside an analytically determined arithmetic size, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application-technical point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.

The alkyl or alkenyl radical R- can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxo synthesis. Alkyl oligoglucosides of chain length are preferred

( ^{DP =} - -> - ^{s 3} ) 'which are obtained as a preliminary step in the separation of technical Cg-Cig coconut fatty alcohol by distillation and can be contaminated with a proportion of less than 6% by weight of Ci ^ alcohol and alkyl ¬ oligoglucosides based on technical Cg / n-oxo alcohols (DP = 1 to 3).

The alkyl or alkenyl radical R ¹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and the technical mixtures obtained as described above can. Alkyl oligoglucosides based on hardened Ci2 / 14 ^co- alcohol with a DP of 1 to 3 are preferred.

Also known are alpha-sulfocarboxylic acid n-edrigalkyl ester salts, which are also referred to as "alkyl ester sulfonates". They are usually prepared by sulfonating fatty acid lower alkyl esters, in particular fatty acid methyl esters with sulfur trioxide and subsequent neutralization.

Typical examples are sulfonates of esters of acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachic acid, behenic acid and their technical mixtures with ethanol, propanol, butanol and especially methanol in the form of their sodium or potassium salts. Alpha-sulfocarboxylic acid lower alkyl ester salts of the formula (II) are preferably used, in which R ^{2 represents} hydrogen or alkyl radicals having 10 to 16 carbon atoms, R ^{3 represents} a methyl group and X represents sodium. Alpha-sulfococonut or alpha-sulfotallow fatty acid estersulfonate sodium salts are particularly preferred.

The alkyl and / or alkenyl oligoglycosides and the alpha-sulfocarboxylic acid lower alkyl ester salts can be used in a molar ratio of 1: 2 to 2: 1. Since the transesterification usually takes place only via the primary hydroxyl group of the alkyl and / or alkenyl oligoglycosides, it is advisable to use the reactants in approximately stoichiometric amounts of from 1: 1.2 to 1.2: 1. Suitable alkaline catalysts are substances which are selected from the group formed by alkali and alkaline earth oxides, hydroxides, carbonates and bicarbonates. Typical examples are sodium hydroxide, sodium carbonate, potassium carbonate and potassium hydrogen carbonate. The catalysts are preferably used as anhydrous salts in amounts of 0.1 to 5, in particular 1 to 3,% by weight, based on the glycoside.

The transesterification can be carried out at temperatures from 100 to 200, preferably 140 to 190 ° C. in a manner known per se. It is advisable to continuously remove the alcohol released during the reaction from the reaction equilibrium and to neutralize the alkaline catalyst after the reaction has ended.

Industrial applicability

The alkyl and / or alkenyl oligoglycoside ester sulfonate salts reduce the surface tension of the water, wet hard surfaces and promote the emulsification of otherwise immiscible phases. In addition, they are characterized by a high ecotoxicological and skin cosmetic compatibility.

Another object of the invention therefore relates to the use of alkyl and / or alkenyl oligoglycoside ester sulfonate salts for the production of surface-active agents, in particular washing, rinsing and cleaning agents and agents for hair and body care, in which the salts in Amounts of 1 to 50, preferably 10 to 35 wt .-% - based on the agent - may be included.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

Examples

Example 1:

In a 400 ml three-necked flask equipped with a stirrer, reflux condenser and gas inlet tube, 150 g (0.6 mol) of butyl glucoside (DP grade = 1.1) and 189 g (0.5 mol) of methyl palmitic acid sulfonate sodium salt were added submitted, mixed with 3.4 g - corresponding to 2.3 wt .-% based on the glucoside - anhydrous potassium carbonate and heated to 140 ° C. with stirring. The methanol (16 g) released during the transesterification was continuously removed from the reaction mixture by passing a constant stream of nitrogen. After a reaction time of 5 h, the product was neutralized by adding phosphoric acid and processed at 70 ° C. with the addition of 485 g of water to give a paste with a solids concentration of approx. 40% by weight.

Example 2;

Analogously to Example 1, 190 g (0.5 mol) of dodecyl glucoside (DP grade = 1.2) in the presence of 4.1 g of potassium carbonate were reacted with 223 g (0.6 mol) of methyl palmitate sulfonate sodium salt. The temperature was increased from 140 to 180 ° C. in accordance with the reaction rate (methanol discharge). After a reaction time of 10 h, the product was cooled, neutralized and ground. Example 3;

In an apparatus according to Example 1, which was additionally equipped with a dropping funnel, 190 g (0.5 mol) of dodecylglucoside (DP degree = 1.2) were heated to 140 ° C. and 2.7 g of anhydrous potassium carbonate were added . 180 g of a methanolic suspension of 0.5 mol of methyl acetate sulfonate sodium salt were added dropwise to the mixture at a rate so that the stirrability of the mixture was ensured and the methanol could be discharged continuously. The temperature was increased from 140 to 180 ° C. in accordance with the reaction rate (methanol discharge). After a reaction time of 10 h, the product was cooled and processed by adding 270 g of water at 70 ° C. to a paste with a solids content of approx. 50% by weight.

Example 4:

Analogously to Example 3, 453 g (1.0 mol) of hexadecyl glucoside (DP grade 1.3) in the presence of 6.3 g of potassium carbonate with 720 g of a 25% by weight suspension of 1.0 mol of methyl acetate-sulfonate-Na- Transesterified salt in methanol. After working up, the crude product was dissolved in 1500 ml of methanol under reflux. After cooling to 0 ° C. and crystallization, 470 g of the product could be obtained by filtration. Example 5:

Analogously to the example, 453 g (1.0 mol) of hexadecyl glucoside (DP grade 1.3) were present in the presence of 8.1 g of potassium carbonate with 1440 g of a 25% by weight suspension of 2.0 mol of methyl acetate / estersulfonate Na salt transesterified in methanol. After working up, the raw product was allowed to solidify and ground.

Claims

1. alkyl and / or alkenyl oligoglycoside estersulfonate salts, obtainable by reacting alkyl and / or alkenyl oligoglycosides of the formula (I),

_R l_0- [G] _p (I)

in which R ^{1 stands} for a linear or branched alkyl and / or alkenyl radical with 4 to 22 carbon atoms, G for a sugar radical with 5 or 6 carbon atoms and p for numbers from 1 to 10, in the presence of alkaline catalysts with alpha-sulfocarboxylic acid lower alkyl ester salts of the formula (II),

R ² -CH-COOR ³ (II)

I S0 ₃ X

2. Process for the preparation of alkyl and / or alkenyl oligoglycoside estersulfonate salts, in which alkyl and / or alkenyl oligoglycosides of the formula (I),

_R l_0- [G] _p (I) in which R stands for a linear or branched alkyl and / or alkenyl radical with 4 to 22 carbon atoms, G for a sugar radical with 5 or 6 carbon atoms and p for numbers from 1 to 10, in the presence of alkaline catalysts with alpha-sulfocarboxylic acid lower alkyl ester salts of the formula (II),

R ² -CH-COOR ³ (II)

I S0 ₃ X

3. The method according to claim 2, characterized in that alkyl oligoglucosides of the formula (I) are used in which R ^{1 is} an alkyl radical having 4 to 9 carbon atoms, G is a glucose radical and p is a number from 1 to 3.

4. The method according to claim 2, characterized in that alkyl oligoglucosides of the formula (I) are used in which R is an alkyl radical having 10 to 22 carbon atoms, G is a glucose radical and p is a number from 1 to 3.

5. The method according to claim 2, characterized in that one uses alpha-sulfocarboxylic acid lower alkyl ester salts of the formula (II) in which R ^{2 is} hydrogen or Alkyl radicals with 10 to 16 carbon atoms, R3 is a methyl group and X is sodium.

6. The method according to claim 2, characterized in that one uses the alkyl and / or alkenyl oligoglycosides and the alpha-sulfocarboxylic acid lower alkyl ester salts in a molar ratio of 1: 2 to 2: 1.

7. The method according to claim 2, characterized in that one uses alkaline catalysts which are selected from the group consisting of alkali and alkaline earth metal, the hydroxides, carbonates and hydrogen carbonates.

8. The method according to claim 2, characterized in that one uses the alkaline catalysts in amounts of 0.1 to 5 wt .-% - based on the glycoside.

9. The method according to claim 2, characterized in that one carries out the transesterification at temperatures from 100 to 200 ° C.

10. The method according to claim 2, characterized in that the alcohol released during the transesterification is removed continuously from the reaction equilibrium.

11. Use of alkyl and / or alkenyl oligoglycoside estersulfonate salts according to claim 1 for the preparation of surface-active agents.