DE4307475A1 - Betainised amino polyols - Google Patents

Abstract

Betainised amino polyols obtainable by subjecting epoxide compounds to a ring opening with aminosugars of the formula (I> Z-NH-R<1> in which Z is a reduced glycoside or oligoglycoside residue with 1 to 10 glycose units, R<1> is hydrogen, an alkyl and/or hydroxyalkyl radical with 1 to 18 carbon atoms, to form an amino polyol, and subsequently betainising the amino polyol in a manner known per se, a process for the preparation thereof in which aminosugars are betainised, aqueous detergent mixtures which contain betainised amino polyols, and the use of these substances for producing surface-active compositions.

Description

Subject of the invention

The invention relates to betainized aminopolyols, a Ver drive to their manufacture, where you betaini aminosugar based, aqueous detergent mixtures, the betainized aminopo contain lyols and the use of these substances for the manufacture provision of surfactants.

State of the art

Amphoteric or zwitterionic surfactants represent an important one Class of surface-active substances, which due to their Foaming power and their high skin cosmetic compatibility Can be used in a variety of cleaning agents the. An overview of this connection class is z. B. in HAPPI, 70, (1986) or Soap, Cosm. Chem. Spec. 46 (1990) given. However, there is a disadvantage of the surfactants mentioned in that they often have insufficient cold water disposition and are therefore difficult to solve or let disperse. Corresponding dispersions or solutions are therefore not always stable in storage and tend to separate tion.

The object of the invention was therefore to create new amphoteric or to develop zwitterionic surfactants that are characterized by characterized by improved cold water solubility.

Description of the invention

The invention relates to betaine aminopolyols which is obtained by using epoxy compounds with Amino sugars of formula (I)

Z-NH-R ¹ (I)

in the
Z for a reduced glycoside or oligoglycoside residue with 1 to 10 glycose units,
R ^{1 represents} hydrogen, an alkyl and / or hydroxyalkyl radical having 1 to 18 carbon atoms,
undergoes ring opening to form an aminopolyol and then betainized the aminopolyol in a manner known per se.

Surprisingly, it was found that the invention betainized aminopolyols are highly soluble in cold water have speed or dispersibility and become easy highly concentrated, low-viscosity solutions or dispersion have it processed. The compounds of the invention are also characterized by excellent detergent properties and a satisfactory biodegradability out.  

Another object of the invention relates to a method for the production of betainized aminopolyols in which one Epoxy compounds with amino sugars with the formula

Z-NH-R ¹ (I)

in the
Z for a reduced glycoside or oligoglycoside residue with 1 to 10 glycose units,
R ^{1 represents} hydrogen, an alkyl and / or hydroxyalkyl radical having 1 to 18 carbon atoms,
undergoes ring opening to form an aminopolyol and then betainized the aminopolyol in a manner known per se.

For example, add-ons come as epoxy compounds products from oxygen to terminal (alpha) or internal (i-) olefins into consideration which follow the formula (II),

R ² -CH = CH-R ³ (II)

in which R ^{2 represents} a linear or branched alkyl radical having 1 to 22 carbon atoms and R ^{3 represents} hydrogen or R ² .

Typical examples are epoxides of 1-octene, 2-octene, 1-de cen, 2-decene, 3-decene, 4-decene, 1-dodecene, 2-dodecene, 3-dode cen, 4-dodecene, 5-dodecene, 6-dodecene, 1-tetradecene, 2-tetra decene, 3-tetradecene, 4-tetradecene, 5-tetradecene, 6-tetrade cene, 7-tetradecene, 1-octadecene, 2-octadecene, 3-octadecene, 4- Octadecen, 5-Octadecen, 6-Octadecen, 7-Octadecen and 8-Octa decen and their technical mixtures. Preferably be  alpha or i-olefins used, the total of 8 to 18 Have carbon atoms.

Epoxies come easily or more as further input materials polyunsaturated fatty acid lower alkyl ester of the formula (III) into consideration

R ⁴ CO-OR ⁵ (III)

in which R ⁴ CO is an unsaturated acyl radical having 16 to 22 carbon atoms and R ^{5 is} a linear or branched alkyl radical having 1 to 4 carbon atoms.

Typical examples are epoxidized methyl, ethyl, propyl, or butyl esters of palmoleic acid, oleic acid, elaidic acid, Petroselinic acid, linoleic acid, linolenic acid, gadoleic acid and Erucic acid and its technical mixtures. The used Epoxies can be completely epoxidized, they can however also contain double bonds; preferably is the degree of epoxidation - based on the available standing double bonds - at 50 to 100 and in particular 70 to 95%. As for the production of the epoxidized fatty acid ester usually technical cuts of unsaturated fat acid lower alkyl esters are still sown the use oxides can consequently contain also low proportions of saturated fatty acids lower have alkyl esters. The preferred feed is oil acid remethyl ester epoxide with an epoxy oxygen content of 4.5 up to 5.1% by weight.

Finally, epoxides are sown as further feedstocks saturated fatty acid glycerol esters of the formula (IV),  

in which R ⁵ CO, R ⁶ CO and R ⁷ CO independently represent unsaturated acyl radicals having 16 to 24 carbon atoms.

Typical examples are epoxides of unsaturated triglyce rides of vegetable or animal origin, such as soybean oil, Rape oil, olive oil, sunflower oil, cottonseed oil, peanut oil, Linseed oil, beef tallow or fish oil. These feedstocks too can contain saturated parts; usually ever but used epoxides of such fatty acid glycerol esters that an iodine number in the range of 50 to 150, preferably 85 to 115. As described earlier, come as an Substitutes both completely and partially epoxidized Esters into consideration. Preferred feed is epoxidized Soybean oil with an epoxy oxygen content of 4.5 to 6.5% by weight.

As amino sugar, which are used as raw materials for production the betainized aminopolyols according to the invention are suitable compounds with the above formula (I) come in Consideration. These amino sugars are known Substances according to the relevant procedures of the preparative organic chemistry can be obtained. A procedure too their production consists, for example, of mono-, di- or oligosaccharides in the presence of ammonia or a primary amine or alkanolamine to a reductive amination subject, such as in the international Patent application WO 92/06984 (Procter & Gamble) becomes.  

Aminosugars which differ from the Maltose, lactose, pallatinose or in particular from the glu derive cose. The preferred amino sugars are therefore amino pentaole ("glucamine") of formula (I), in which Z for a right induced glucose residue (sorbityl residue). About the Her The position and use of glucamines is described by H. Kelkenberg detailed in Tens. Surf. Det. 25, 1 (1988) reports.

The aminosugars can differ from a variety of amines conduct. Typical examples are aminosugar, which one goes through reductive amination of mono- or disaccharides, preferred wise glucose, with primary or secondary amines or alka nolamines, such as B. methylamine, ethylamine, propylamine, Octylamine, decylamine, dodecylamine, tetradecylamine, hexa decylamine, octadecylamine, octadecenylamine, N, N-dimethylamine, N, N-diethylamine, N-methyl-N-ethylamine, N-methyl-N-propylamine, N-methyl-N-octylamine, N-methyl-N-decylamine, ethanolamine, Pro panolamine, diethanolamine or their technical mixtures holds.

Aminosugars of the formula (I) in which R ^{1 is} a methyl radical are preferably used. The preferred aminosugars are glucamine, N-methylglucamine, N-ethylglucamine and N-hydroxyethylglucamine.

The epoxides and the aminosugars can usually be found in the mola ren ratio of 1: 0.5 to 1: 1.5, preferably 1: 0.9 up to 1: 1.1 - based on the epoxy content - used the.

In view of the shortest possible response time, it is recommended it, the ring opening reaction at temperatures from 80 to 150, preferably 110 to 130 ° C. The ring opening can be carried out in the absence of solvents  the. In the context of a special embodiment of the invention however, are organic solvents and in particular short chain alcohols, such as isopropyl alcohol used.

The betainization of the aminopolyols can be carried out in a manner known per se Way with the help of sodium salts of halocarboxylic acids 1 to 4 carbon atoms, the halogen being chlorine or bromine can be, or acrylic acid. Esters of Halogen carboxylic acids are used, the Acids with primary alcohols with 1 to 18 carbon atoms, especially fatty alcohols with 12 to 18 carbon atoms, were esterified. Chloroacetic acid esters, Na triumchloroacetate or acrylic acid used. The betainisia tion can be in a closed stirring apparatus or in a Pressure reactor are carried out. Typically aminopolyol and betainizing agent in molar ver ratio of 1: 0.5 to 1: 1, preferably 1: 0.9 to 1: 0.95 set and at a temperature in the range of 30 to 100, preferably brought to 50 to 90 ° C to react.

Another object of the invention relates to aqueous Detergent mixtures containing betainized aminopolyols is obtained by using epoxy compounds with Amino sugars of formula (I)

Z-NH-R ¹ (I)

in the
Z for a reduced glycoside or oligoglycoside residue with 1 to 10 glycose units,
R ^{1 represents} hydrogen, an alkyl and / or hydroxyalkyl radical having 1 to 18 carbon atoms,
is subjected to a ring opening to form an aminopolyol and the aminopolyol is then betainized in a manner known per se, as well as further anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants.

Typical examples of anionic surfactants are alkylbenzene sulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfate fonates, glycerol ether sulfonates, alpha-methyl ester sulfonates, Sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, Gly cerine ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, sulfosuccinates, Sulfosuccinamates, sulfotriglycerides, ether carboxylic acids, isse thionates, taurides, sarcosinates, alkyl oligoglycoside sulfates and Alkyl (ether) phosphates. If the anionic surfactants poly contain glycol ether chains, they can be a conventional, but preferably a narrow homolog distribution point.

Typical examples of nonionic surfactants are fatty alcohols holpolyglycol ether, alkylphenol polyglycol ether, fatty acid po lyglycol esters, fatty acid amide polyglycol ethers, fatty amine polygly kolether, alkoxylated triglycerides, alk (en) yloligoglycosides, Fatty acid glucamides, polyol fatty acid esters, sugar esters, Sorbi tanesters and polysorbates. Unless the nonionic surfactants Containing polyglycol ether chains, they can be a conventional nelle, but preferably a narrow homolog distribution have lung.

Typical examples of cationic surfactants are quaternary Am monium compounds and quaternized difatty acid trialkano laminester.  

Typical examples of amphoteric or zwitterionic surfactants are aminobetaines, alkylamidobetaines, aminopropionates, amino glycinates, imidazolinium betaines and sulfobetaines.

The surfactants mentioned are exclusively known connections. Regarding the structure and manufacture These substances are based on relevant reviews referenced such. B. by J. Falbe (ed.), "Surfactants in Con sumer Prcducts ", Springer Verlag, Berlin, 1987, pp. 54-124 or J. Falbe (ed.), "Catalysts, Surfactants and Mineral oil additives ", Thieme Verlag, Stuttgart, 1978, pp. 123-217 ver grasslands.

The aqueous detergent mixtures can be those according to the invention betainized aminopolyols in amounts of 1 to 99, preferably as 2 to 50 and in particular 5 to 25 wt .-% - based on the solids content of the mixtures - included.

Industrial applicability

The betainized aminopolyols according to the invention are light soluble or dispersible in cold water and good organic biodegradable. You can easily to aqueous Kon Process low viscosity concentrates. A wide one The subject matter of the invention therefore relates to their use for the production of surface-active agents, as in the following are described as examples:

• - Powdered universal detergents containing 10 to 30 % By weight - based on the average - of the invention betainized aminopolyols of the formula (I) and given if necessary, further anionic, nonionic, cationic,  amphoteric or zwitterionic surfactants as well as usual Auxiliaries and additives.
• - liquid universal detergents containing 10 to 70% by weight - Based on the agent - be the invention tainized aminopolyols of formula (I) and given if necessary, further anionic, nonionic, cationic, amphoteric or zwitterionic surfactants as well as usual Auxiliaries and additives.
• - liquid mild detergent containing 10 to 50% by weight - based on the agent - the betaini according to the invention based aminopolyols of the formula (I) and, if appropriate further anionic, nonionic, cationic, ampho tere or zwitterionic surfactants and usual auxiliary and additives.
• - Hand dishwashing detergent containing 10 to 50 wt .-% - be moved to the agent - the betaini according to the invention based aminopolyols of the formula (I) and, if appropriate further anionic, nonionic, cationic, ampho tere or zwitterionic surfactants and usual auxiliary and additives.
• - Rinse aid containing 10 to 50 wt .-% - based on the Agent - the betainized aminopoly according to the invention Oles of the formula (I) and optionally further anioni cal, non-ionic, cationic, amphoteric or zwit terionic surfactants as well as usual auxiliary agents and additives fabrics.
• - Containing liquid cleaning agents and disinfectants 10 to 30 wt .-% - based on the average - invented betainized aminopolyols of the formula (I) according to the invention  and optionally further anionic, nonionic, cationic, amphoteric or zwitterionic surfactants as usual auxiliaries and additives.
• - Hair shampoos containing 10 to 30 wt .-% - based on the agent - the betainized amino according to the invention polyols of the formula (I) and optionally further ones anionic, nonionic, cationic, amphoteric or zwitterionic surfactants as well as usual auxiliary agents and additives fabrics.
• - Hair rinses containing 10 to 30 wt .-% - based on the agent - the betainized amino according to the invention polyols of the formula (I) and optionally further ones anionic, nonionic, cationic, amphoteric or zwitterionic surfactants as well as usual auxiliary agents and additives fabrics.
• - Bubble baths containing 10 to 30 wt .-% - based on the agent - the betainized amino according to the invention polyols of the formula (I) and optionally further ones anionic, nonionic, cationic, amphoteric or zwitterionic surfactants as well as usual auxiliary agents and additives fabrics.

Detergents, dishwashing detergents and cleaning agents based on the invention According betainized aminopolyols can be used as auxiliaries and additives substitutes for example builders, salts, bleaches, Bleach activators, optical brighteners, graying inhibitors contain solubilizers and enzymes.

Common builders are sodium aluminum silicates (zeolites), Phosphates, phosphonates, ethylenediaminetetraacetic acid, nitri lotriacetate, citric acid and / or polycarboxylates.  

Sodium sulphides, for example, come as salts or adjusting agents fat, sodium bicarbonate or sodium silicate (water glass) in Consideration. As typical individual examples for further additions substances are sodium borate, starch, sucrose, polydextrose, TAED, stilbene compounds, methyl cellulose, toluenesulfonate, Cumene sulfonate, long-chain soaps, silicones, mixed ethers, Li pass and call proteases.

Hair shampoos, hair lotions or bubble baths based on the Betainized aminopolyols according to the invention can be used as auxiliary and additives, for example emulsifiers, oil components, Fats and waxes, greasing agents, superfatting agents, organic gene active ingredients, film formers, fragrances, dyes, pearl gloss agents, preservatives and pH regulators included ten.

Common oil components are substances such as paraffin oil, plant zen oils, fatty acid esters, squalane and 2-octyldodecanol, while as fats and waxes, for example walrus, beeswax, Montan wax, paraffin and cetylstearyl alcohol Use fin the. Substances such as as polyethoxylated lanolin derivatives, lecithin derivatives and Fatty acid alkanolamides are used, the latter also serve as foam stabilizers. Suitable Ver Thickeners are, for example, polysaccharides, in particular their xanthan gum, guar guar, agar agar, alginates and tyloses, Carboxymethyl cellulose and hydroxyethyl cellulose, further ho hermolecular polyethylene glycol monoesters and diesters of fat acids, polyacrylates, polyvinyl alcohol and polyvinyl pyrrole don and electrolytes such as table salt and ammonium chloride. Under biogenic active ingredients are, for example, plant extracts, Understand protein hydrolyzates and vitamin complexes. Custom Liche film formers are, for example, polyvinyl pyrrolidone,  Vinylpyrrolidone-vinyl acetate copolymers, polymers of Acrylic acid series, quaternary cellulose derivatives and the like Links. Suitable preservatives are, for example as formaldehyde solution, p-hydroxybenzoate or sorbic acid. Glycol distearic acid, for example, comes as a pearlescent agent esters such as ethylene glycol distearate, but also fatty acid mono glycolester into consideration. As dyes for cos Use suitable and approved substances for be detected, such as in publications "Cosmetic Colorants" of the Deuter Dye Commission research community, published by Che mie, Weinheim, 1984. These dyes are usually in concentrations of 0.001 to 0.1 % By weight, based on the mixture as a whole.

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

Examples Preparation of the starting compounds Preparation example 1a

Ring opening of 1-dodecane epoxide with N-methylglucamine. In egg 1-liter three-necked flask with stirrer, dropping funnel and back The flow cooler was a mixture of 66 g (0.33 mol) of 1-dodecane epoxy (epoxy oxygen content: 8.1% by weight) and 195 g (1 mol) N-methylglucamine submitted and heated to 130 ° C. Within After 30 minutes, a further 132 g (0.67 mol) of 1-dodecane epoxide added dropwise, the temperature rising to 135 to 140 ° C. After the end of the epoxy addition, the reaction mixture was started stirred at 130 ° C for a further 30 min. The aminopolyol was in practically quantitative yield as a light yellow colored solid receive fabric; the residual epoxy oxygen content was 0.1 % By weight.

Production example 1b

Synthesis of the chloroacetic acid ester. A mixture of 785 g (3 mol) of tallow alcohol (Hydrenol D, Henkel KGaA, Duesseldorf / FRG), 283.5 g (3 mol) of chloroacetic acid and 132 was in a 1.5-liter three-necked flask with stirrer and water separator g xylene heated to 150 ° C for 3 hours until no more water separated. The xylene was then distilled off in vacuo. The chloroacetic acid ester was obtained in practically quantitative yield in the form of a light yellow solid.
Cl (ges) = 10.25%
Cl⁻ = 20 ppm.

Preparation of the betainized aminopolyols example 1

Betainization of the aminopolyol from preparation example 1a with a chloroacetic acid ester according to preparation example 1b.

In a 250 ml three-necked flask with stirrer, dropping funnel and Reflux was 93.5 g (0.25 mol) of the aminopolyol heated to 120 ° C and within 20 min. 84.4 g (0.25 mol) of the melted chloroacetic acid ester dripped. Subsequently, 1 hour at 140 ° C. responds. The betainized aminopolyol became practical quantitative yield in the form of a yellow solid receive.

Characteristics of the product

Amine number 0.1
Cl⁻ = 3.63%.

Claims (11)

1. Betainized aminopolyols, obtainable by making epoxy compounds with amino sugars of the formula (I) Z-NH-R ¹ (I) in the
Z for a reduced glycoside or oligoglycoside residue with 1 to 10 glycose units,
R ^{1 represents} hydrogen, an alkyl and / or hydroxyalkyl radical having 1 to 18 carbon atoms,
subject to a ring opening to form an aminopolyol and then betainized the aminopolyol in a conventional manner. 2. Process for the preparation of betainized aminopolyols, in which epoxy compounds with amino sugars of the formula (I) Z-NH-R ¹ (II) in the
Z for a reduced glycoside or oligoglycoside residue with 1 to 10 glycose units,
R ^{1 represents} hydrogen, an alkyl and / or hydroxyalkyl radical having 1 to 18 carbon atoms,
undergoes ring opening to form an aminopolyol and then betainized the aminopolyol in a manner known per se. 3. Process for the preparation of betainized aminopolyols according to claim 2, characterized in that as Amino sugar uses glucamine or N-methylglucamine. 4. A process for the preparation of betainized aminopolyols according to claim 2, characterized in that addition products of oxygen to terminal (alpha-) or internal (i-) olefins which follow the formula (II) are used as epoxy compounds, R ² -CH = CH -R ³ (II) in which R ^{2 represents} a linear or branched alkyl radical having 1 to 22 carbon atoms and R ^{3 represents} hydrogen or R ² . 5. A process for the preparation of betainized aminopolyols according to claim 2, characterized in that the epoxy compounds used are mono- or polyunsaturated fatty acid lower alkyl esters of the formula (III), R ⁴ CO-OR ⁵ (III) in the R ⁴ CO for an unsaturated acyl radical having 16 up to 22 carbon atoms and R ^{5 is} a linear or ver branched alkyl radical having 1 to 4 carbon atoms. 6. A process for the preparation of betainized aminopolyols according to claim 2, characterized in that the epoxy compounds used are epoxides of unsaturated fatty acid glycerol of the formula (IV), in which R ⁵ CO, R ⁶ CO and R ⁷ CO independently of one another represent unsaturated acyl radicals having 16 to 24 carbon atoms, which can be partially or completely epoxidized. 7. The method according to claim 2, characterized in that one as the betainizing agent chloroacetic acid ester, Na triumchloroacetate or acrylic acid. 8. The method according to claim 2, characterized in that aminosugar and betainizing agent in the molar Ratio of 1: 0.5 to 1: 1. 9. The method according to claim 2, characterized in that to betainize at a temperature in the range from 30 to 100 ° C. 10. Aqueous detergent mixtures containing betainized aminopolyols, which are obtainable by making epoxy compounds with amino sugars of the formula (I) Z-NH-R ¹ (I) in the
Z for a reduced glycoside or oligogly coside residue with 1 to 10 glycose units,
R ^{1 represents} hydrogen, an alkyl and / or hydroxyalkyl radical having 1 to 18 carbon atoms,
subject to a ring opening to form an aminopolyol and then betainized the aminopolyol in a manner known per se, and further anionic, nonionic, cationic and / or amphoteric or zwit terionic surfactants. 11. Use of the betainized aminopolyols according to claim 1, for the production of surfactants.