WO1995011251A1

WO1995011251A1 - Oligomeric alkyl- and/or alkenyloligoglycoside glycerine ethers

Info

Publication number: WO1995011251A1
Application number: PCT/EP1994/003378
Authority: WO
Inventors: Manfred Weuthen
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1993-10-21
Filing date: 1994-10-13
Publication date: 1995-04-27
Also published as: DE4335956A1

Abstract

In the method proposed, oligomeric alkyl- and/or alkenyloligoglycoside glycerin ethers are obtained by reacting with glycerin and/or technical-grade oligoglycerin mixtures alkyl- and/or alkenyloligoglycosides of the formula (I) R1-O-[G]¿p? in which R?1¿ is an alkyl and/or alkenyl group with 1 to 22 carbon atoms or a glycerin, ethylene glycol, propylene glycol or sorbitol group, G is a sugar with 5 or 6 carbon atoms and p is a number from 1 to 10. The products have excellent detergent properties.

Description

Oligαmere alkyl and / or alkenyl oligoglycoside glycerol ether

Field of Invention

The invention relates to a new oligomeric alkyl and / or alkenyl oligoglycoside glycerol ether, a process for their preparation in which alkyl and / or alkenyl oligoglycosides are reacted with glycerol and / or technical oligoglycerol mixtures, and their use for the production of surface coatings tive means.

State of the art

Alkyl oligoglycosides and in particular alkyl oligoglucosides are nonionic surfactants that are becoming increasingly important due to their natural raw material base - fatty alcohol and sugar - and are used, for example, in manual dishwashing detergents or cosmetic products [cf. Tens. Surf.Det. .28, 413 (1991)]. Nevertheless, alkyl oligoglycosides show in some applications that their foaming power is not completely satisfactory. The solubility in cold water and the crystallization behavior are also in need of improvement. In the past, there has been no lack of attempts to chemically derivatize alkyl oligoglycosides and in this way to bring about an improvement in the properties mentioned by hydrophilizing the molecule.

An example of this is the sulfation of alkyl oligoglucosides, which, however, leads to anionic surfactants, which in turn are undesirable for a number of applications [EP-A 0 186 242 (Procter & Gamble), US Pat. No. 4,609,478 ( Olin)].

Another possibility of hydrophilization consists in the addition of alkylene oxide to the free OH groups of the glycosides. However, the alkoxylates obtainable here surprisingly show unsatisfactory biodegradability [EP-A 0 077 167 (Rohm & Haas)].

The object of the invention was therefore to provide new nonionic derivatives of the alkyl and / or alkenyl oligoglycosides which are free from the disadvantages described.

Description of the invention

The invention relates to oligomeric alkyl and / or alkenyl oligoglycoside glycerol ethers which are obtained by adding alkyl and / or alkenyl oligoglycosides of the formula (I)

_R l_0- [G] _p (I) in which R ^{1 is} an alkyl and / or alkenyl radical having 1 to 22 carbon atoms or a glycerol, ethylene glycol, propylene glycol or sorbitol radical, G is a sugar having 5 or 6 carbon atoms and p is a number from 1 to 10 , with glycerol and / or technical oligoglycerol mixtures.

Surprisingly, it was found that the new ethers have greater foaming power, better solubility in cold water and a reduced tendency to crystallize compared to alkyl oligoglycosides. In addition, they are well tolerated by the skin and are completely biodegradable. The invention includes the knowledge that under the specified process conditions, self-condensation of the glycerol and etherification with the glycosides take place simultaneously.

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

Rl-0- [G] _p (I)

in which R ^{1 is} an alkyl and / or alkenyl radical having 1 to 22 carbon atoms or a glycerol, ethylene glycol, propylene glycol or sorbitol radical, G is a sugar having 5 or 6 carbon atoms and p is a number from 1 to 10 , with glycerol and / or technical oligoglycerol mixtures. Feedstocks

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 oligoglucosides.

The index number p in the general formula (I) gives the degree of oligomerization (DP degree), ie. H. the distribution of mono- and oligoglycosides is present and stands for a number between 1 and 10. While p must always be an integer in a given compound and can in particular assume the values p = 1 to 6, the value p is for a specific alkyl oligoglycoside an analytically calculated quantity, 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 point of view, preference is given to 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 ¹ can be derived from primary alcohols having 1 to 11, preferably 8 to 10, carbon atoms. Typical examples are methanol, butanol, capron alcohol, caprylic alcohol, capric alcohol and undecyl alcohol as well as 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 oxosynthesis. Alkyl oligoglucosides are preferred

Chain length

3), which are obtained as a forerunner in the separation of technical Cg-Cig-coconut fat alcohol by distillation and may be contaminated with a proportion of less than 6% by weight of Ci2- ^A - ¹ 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 their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated Ci2 / i4 coconut alcohol with a DP of 1 to 3 are preferred.

Finally, the starting materials can also be polyoligoglycosides, preferably glycerol, ethylene glycol, propylene glycol or sorbitol oligoglucosides.

Large-scale production of glycerin occurs in the pressure splitting of fats and oils. Technical oligoglycerol mixtures, preferably those which have a high diglycerol content, become more basic through self-condensation of glycerol in the presence Catalysts obtained by methods of the prior art. Oligoglycerol mixtures which have an average degree of condensation of 1.5 to 10 are preferably used.

The alkyl and / or alkenyl oligoglycosides and the glycerol or the oligoglycerols can usually be used in a molar ratio of 3: 1 to 1:30. This means that the stoichiometric conversion of the reactants is not always sought. In particular, there is an interest in mixtures in which only a certain proportion of the alkyl and / or alkenyl oligoglycosides are etherified. Conversely, an excess of glycerol or oligoglycerin is required if the reaction is to be carried out as completely as possible. Usually, however, an application ratio of 3: 1 to 1:10 and in particular 1 × 3 to 1: 5 is recommended.

Veretherunσ

Although the etherification can also be carried out purely thermally, the use of catalysts is recommended. In principle, both acidic and basic compounds come into consideration; in view of the acetal bond present in the alkyl and / or alkenyl oligoglycosides, the use of basic catalysts, for example alkali and / or alkaline earth oxides, hydroxides, is of course not recommended. carbonates or Cτ.-C4 alcoholates. Typical examples are sodium hydroxide, sodium hydrogen carbonate, sodium methoxide, potassium hydroxide and potassium carbonate. The operational The amount of the alkaline catalysts can be 0.5 to 5, preferably 1 to 2, mol%, based on the glycoside.

The mixing of the reactants is not critical per se. In a preferred embodiment of the process, glycoside and glycerol or oligoglycerol are introduced, heated, mixed with an optionally aqueous or alcoholic solution of the catalyst at the reaction temperature and the solvent introduced is optionally removed in vacuo.

However, it is also possible to introduce glycoside and catalyst, if appropriate to separate off the solvent and to meter in the glycerol or oligoglycerol when the reaction temperature has been reached. Under the conditions of the process according to the invention, a parallel reaction by self-condensation of glycerol leads to the formation of oligoglycerols which can react with the glucosides in the same form as the glycerol. Portions of such higher oligomers are even expressly desired since they further improve the hydrophilicity and therefore water solubility of the products. The oligomers according to the invention are in any case complex mixtures of etherification products between the glycosides and oligoglycerols, regardless of whether the oligoglycerols are used directly or are prepared in situ.

The reaction is preferably carried out at temperatures in the range from 180 to 230, preferably 180 to 200 ° C; the reaction time can be between 1 and 35 hours. The reaction is preferably carried out in an inert gas atmosphere and the water of reaction is continuously removed from the equilibrium. After etherification, the products can be dissolved in water or pasted with water and in themselves known manner, e.g. B. be bleached by adding hydrogen peroxide.

Industrial applicability

The oligomeric alkyl and / or alkenyl oligoglycoside glycerol ethers according to the invention have surface-active properties. They promote the wetting of hard surfaces and the emulsification of otherwise immiscible phases.

Another object of the invention therefore relates to the use of the oligomeric alkyl and / or alkenyl oligoglycoside glycerol ethers according to the invention for the production of surface-active agents, in particular detergents, dishwashing detergents and cleaning agents and products for hair and body care, are used in which they can contain in amounts of 1 to 50, preferably 5 to 30% by weight, based on the composition.

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

Examples

Example 1;

Implementation of dodecylglucosxd and glycerin (1: 2). In a three-necked flask with stirrer, gas inlet tube and gas outlet tube with attached cold trap, 348 g (1 mol) of dodecyl glucoside (DP grade: 1.1) were dissolved in 184 g (2 mol) glycerol at 120 ° C. in a nitrogen atmosphere with stirring. Then 10.6 g of potassium hydroxide (corresponding to approximately 1 mol% based on the starting materials) were added and the mixture was further heated to 150.degree. A gentle stream of nitrogen was then passed through the solution and the reaction temperature was raised to 180.degree. The water of reaction expelled with the nitrogen stream was collected in a trap cooled with liquid nitrogen. The temperature was raised further to 210 ° C. within 4 h. The heat source was then removed, the gas discharge pipe was replaced by a distillation attachment and unconverted glycerol was distilled off under reduced pressure (approx. 1 mbar); in order to avoid excessive foaming, the stirrer speed was also increased.

The crude oligomeric dodecylglucoside glycerol ether was mixed with 450 g of water at a temperature of 60 ° C. at 120 ° C., the solution cooling to a mixing temperature of 80 ° C. The product was then bleached by adding 40 g of hydrogen peroxide (30% by weight aqueous solution). Product characteristics;

Water of reaction 16 g distillate 45 g glycerin (purity: 95%) yield 53% of theory color 4 to 5 (Gardner, 2 cm cuvette)

Example 2t

Implementation of dodecyl glucoside and glycerin (1:10). Analogously to Example 1, 348 g (1 mol) of dodecyl glucoside, 920 g (10 mol) of glycerol and 19 g of potassium hydroxide were reacted in a 2-1 three-necked flask. The reaction was stopped after 80% of the theoretical amount of water had been separated off. Pasting with water and bleaching were avoided.

Characteristics of the product:

Water of reaction 137 g distillate 129 g glycerol (purity: 95%) yield 94% of theory color 15 (Gardner, 2 cm cuvette)

Example 3:

Conversion of hexadecyl glucoside and glycerin (1: 4). Analogously to Example 1, 348 g (1 mol) of hexadecyl glucoside (DP grade: 1.4), 460 g (5 mol) of glycerol and 18 g of potassium hydroxide were reacted.

Characteristics of the product:

Water of reaction 66 g distillate 104 g glycerol (purity: 95%) yield 88% of theory color 5 (Gardner, 2 cm cuvette)

Example 4:

Implementation of glycerol glucoside and glycerin (1:25). Analogously to Example 2, 270 g (1 mol) glycerol glucoside (DP grade: 1.1), 2300 g (25 mol) glycerol and 18 g potassium hydroxide were reacted in a 5-1 three-necked flask.

Characteristics of the product:

Water of reaction 400 g distillate 237 g glycerol (purity: 95%) yield 97% of theory color 14 (Gardner, 2 cm cuvette) Example 5:

Conversion of dodecyl glucoside and oligoglycerin (1:10). Analogously to Example 2, 348 g (1 mol) of dodecyl glucoside, 1260 g (10 mol) of technical oligoglycerol with an average degree of condensation of 1.7 and a diglycerol content of 42% by weight and 19% were in a 2-1 three-necked flask g of potassium hydroxide reacted.

Characteristics of the product:

Water of reaction 140 g

Yield 91% of theory

Color 15 (Gardner, 2 cm cell)

Claims

claims

1. oligomeric alkyl and / or alkenyl oligoglycoside glycerol ethers, obtainable by reacting alkyl and / or alkenyl oligoglycosides of the formula (I),

^ O-EGJp (I)

in which R represents an alkyl and / or alkenyl radical having 1 to 22 carbon atoms or a glycerol, ethylene glycol, propylene glycol or sorbitol radical, G represents a sugar having 5 or 6 carbon atoms and p represents numbers from 1 to 10, reacted with glycerol and / or technical oligoglycerol mixtures.

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

Rl-0- [G] _p (I)

in which R ^{1 is} an alkyl and / or alkenyl radical having 1 to 22 carbon atoms or a glycerol, ethylene glycol, propylene glycol or sorbitol radical, G is a sugar having 5 or 6 carbon atoms and p is a number from 1 to 10 , with glycerol and / or technical oligoglycerol mixtures.

3. The method according to claim 2, characterized in that alkyl and / or alkenyl oligoglucosides of the formula (I) are used in which R * is alkyl and / or alkenyl radicals having 1 to 11 carbon atoms.

4. The method according to claim ", characterized in that one uses alkyl and / or Alker._loligoglucoside of formula (I) in which R ^{1 is} alkyl and / or alkenyl radicals having 12 to 22 carbon atoms.

5. The method according to claims 2 to 4, characterized gekenn¬ characterized in that the alkyl and / or alkenyl oligoglyglycosides and the glycerol or oligoglycerol are used in a molar ratio of 3: 1 to 1:30.

6. The method according to claims 2 to 5, characterized gekenn¬ characterized in that one carries out the reaction in the presence of basic catalysts.

7. The method according to claim 6, characterized in that one uses the alkaline catalysts in amounts of 0.5 to 5 mol% - based on the glycoside.

8. Process according to Claims 2 to 7, characterized in that the reaction is carried out at temperatures in the range from 180 to 230 ° C.

9. Use of the oligomeric alkyl and / or alkenyl oligoglycoside glycerol ether according to claim 1 for the preparation of surface-active agents.