DE4238209A1 - New bis:sorbityl amino betaines, their prepn. and detergent mixts. contg. the same - useful for the prepn. of surfactants. - Google Patents

Abstract

Bis-sorbitylaminobetaines of formula (I) are new. Z = sorbityl; R = H or 1-18C (hydroxy)alkyl; and n = 1-2. Also claimed are (i) the prepn. of (I) by betainising bis-sorbitylamine by known methods, and (ii) aq. detergent mixts. contg. (I) and other anionic, nonionic, cationic, and/or amphoteric or zwitterionic surfactants. USE/ADVANTAGE - (I) are useful for the prepn. of surface-active agents (claimed), e.g. universal washing agents, fine washing agents, hand rinsing agents, liquid soap, disinfectants, hair shampoo and bubble bath mixts. (I) show improved cold water solubility, are readily bio-degradable and readily form low viscosity aq. solns.

Description

Field of the Invention

The invention relates to bis-sorbitylaminobetaines, a process to their manufacture, in which one be bis-sorbitylamine tainized, aqueous detergent mixtures, the bis-sorbitylamino betaine contain and the use of these substances for Manufacture 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 its high skin cosmetic tolerance Can be used in a wide range of cleaning agents Find. For example, there are reviews in HAPPI, 70 (1986) or Soap, Cosm. Chem. Spec. 46 (1990). A However, the disadvantage of the surfactants mentioned is that they often have insufficient solubility in cold water and are therefore difficult to dissolve or disperse. Corresponding dispersions or solutions are therefore not always stable in storage and tend to separate.

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 bis-sorbitylaminobetaines Formula (I)

in the
Z for a sorbityl residue,
R ^{1 represents} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 18 carbon atoms and
n for 1 or 2
stands.

Surprisingly, it was found that the inventive Betaines are highly soluble or dispersible in cold water show speed and easily become highly concentrated, Process low-viscosity solutions or dispersions sen. The bis-sorbitylaminobetaines are also characterized by  excellent detergent properties as well as a satisfied exhibiting biodegradability.

Another object of the invention relates to a method for the preparation of bis-sorbitylaminobetaines of the formula (I)

in the
Z for a sorbityl residue,
R ^{1 represents} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 18 carbon atoms and
n for 1 or 2
stands, in which amine sugar is betainized in a manner known per se.

As bis-sorbitylamines, which are used as starting materials for the Her position of the bis-sorbitylaminobetaines according to the invention in Compounds of the formula (II) can be used be put

in which Z and R ^{1 have} the meanings given above. The bis-sorbitylamines are known substances which can be obtained by the relevant processes in preparative organic chemistry. One method for their preparation is, for example, to subject glucose to reductive amination with ammonia or methylamine.

The betainization of the bis-sorbitylamine can be in itself known with the help of sodium chloroacetate or acrylic acid in a closed stirring apparatus or in a pressure reactor. Typically, this will Amino sugar and betainizing agent in a molar ratio from 1: 0.5 to 1: 1, preferably 1: 0.9 to 1: 0.95 used and at a temperature in the range of 30 to 100, preferably 50 to 90 ° C brought to the reaction.

Another object of the invention relates to aqueous De Tergensgemische, containing bis-Sorbitylaminobetaine of For mel (I)

in the
Z for a sorbityl residue,
R ^{1 represents} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 18 carbon atoms and
n for 1 or 2
stands as well as other anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants.

Typical examples of anionic surfactants are alkylbenzene sulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfate fonate, glycerol ether sulfonate, α-methyl ester sulfonate, Sul fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glyce rinether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, sulfosuccinates, Sulfosuccinamates, sulfotriglycerides, ether carboxylic acids, isse thionates, taurides, sarcosinates, alkyl oligoglucoside 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 holpolyglycolether, alkylphenolpolyglycolether, fatty acid po lyglycol ester, fatty acid amide polyglycol ether, fatty amine polygly colethers, alkoxylated triglycerides, alk (en) yloligoglycosides, Fatty acid glucamides, polyol fatty acid esters, sugar esters, Sor bitanester 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 trialkanol aminester.

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

The surfactants mentioned are exclusively known connections. In terms of structure and manufacture these substances are included in relevant reviews for example J.Falbe (ed.), "Surfactants in Consumer Pro ducts ", Springer Verlag, Berlin, 1987, pp. 54-124 or J. Falbe (ed), "Catalysts, surfactants and mineral oil additives", Thieme Verlag, Stuttgart, 1978, pp. 123-217.

The aqueous detergent mixtures can be those according to the invention Bis-sorbitylaminobetaines in amounts of 1 to 99, preferably 2 to 50 and in particular 5 to 25% by weight, based on the Solids content of the mixtures - included.

Industrial applicability

The bis-sorbitylaminobetaines according to the invention are easily in cold water soluble or dispersible and good biological degradable. They can be easily converted into aqueous concentrates process with a low viscosity.  

Another object of the invention therefore relates to their Use for the production of surface-active agents, as described in the following example:

• - Universal powder detergent containing 10 to 30 % By weight - based on the average - of the invention Bis-sorbitylaminobetaines of formula (I) as well as given if 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 average - of the invention Bis-sorbitylaminobetaines of formula (I) as well as given if 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 Bis-Sor according to the invention bitylaminobetaine of formula (I) and optionally further anionic, nonionic, cationic, amphoteric or zwitterionic surfactants and usual auxiliaries and Additives.
• - Hand dishwashing detergent, containing 10 to 50% by weight - based on the agent - the Bis-Sor according to the invention bitylaminobetaine of formula (I) and optionally further anionic, nonionic, cationic, amphoteric or zwitterionic surfactants and usual auxiliaries and Additives.  
• - Rinse aid, containing 10 to 50% by weight, based on the Agent - the bis-sorbitylaminobetaines of the invention of formula (I) and optionally further anionic, non-ionic, cationic, amphoteric or zwitterioni tensides as well as usual auxiliaries and additives.
• - Containing liquid detergents and disinfectants 10 to 30% by weight, based on the average, of the invented bis-sorbitylaminobetaines of the formula (I) according to the invention such as further anionic, nonionic, cationic, amphoteric or zwitterionic surfactants and usual auxiliaries and additives.
• - Hair shampoos containing 10 to 30% by weight based on the agent - the bis-sorbitylamino according to the invention betaine of the formula (I) and optionally further ionic, nonionic, cationic, amphoteric or zwitterionic surfactants as well as usual auxiliary agents and additives fabrics.
• - Conditioners containing 10 to 30% by weight, based on the agent - the bis-sorbitylamino according to the invention betaine of the formula (I) and optionally further ionic, nonionic, cationic, amphoteric or zwitterionic surfactants as well as usual auxiliary agents and additives fabrics.
• - Bubble baths containing 10 to 30% by weight based on the agent - the bis-sorbitylamino according to the invention betaine of the formula (I) and optionally further ionic, 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 bis-Sorbitylaminobetaine according to auxiliary and Zu 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, Ni trilotriacetate, citric acid and / or polycarboxylates. When Salts or adjusting agents come, for example, sodium sulfate, Sodium carbonate or sodium silicate (water glass) into consideration. Typical examples for other additives are Sodium borate, starch, sucrose, polydextrose, TAED, style benverbindungen, methyl cellulose, toluenesulfonate, cumolsul fonat, long chain soaps, silicones, mixed ethers, lipases and To name proteases.

Hair shampoos, hair lotions or bubble baths based on Bis-sorbitylaminobetaines according to the invention can be used as auxiliary and additives, for example emulsifiers, oil components, Fats and waxes, thickeners, superfats, biogenic agents, film formers, fragrances, dyes, Pearlescent agents, preservatives and pH regulators contain.

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, mon  wax, paraffin and cetylstearyl alcohol are used. Substances such as, for example, can be used as superfatting agents polyethoxylated lanolin derivatives, lecithin derivatives and fat 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 pyrro lidon and electrolytes such as table salt and ammonium chloride. Among the biogenic active substances are, for example, plant ex tracts to understand protein hydrolyzates and vitamin complexes. Common film formers are, for example, polyvinyl pyr rolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers the acrylic acid series, quaternary cellulose derivatives and the like connections. Are suitable as preservatives for example formaldehyde solution, p-hydroxybenzoate or Sorbic acid. Gly, for example, comes as pearlescent agent coldistearic acid esters such as ethylene glycol distearate, but also Fatty acid monoglycol esters. As dyes can the suitable and approved sub punching can be used, such as in the pub liking "Cosmetic Dyes" of the Dye Commission the German Research Foundation, published in Ver lay Chemie, Weinheim, 1984. This Dyes are usually found in concentrations of 0.001 up to 0.1 wt .-%, based on the total mixture used.

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

Examples example 1

Betainization of bis-sorbitylmethylamine with sodium chlorine acetate. In a 1 liter three-necked flask with stirrer, dropping funnel and a reflux condenser, a mixture of 360 g (1 mol) of bis- Sorbitylmethylamin submitted in 500 ml of water and with stirring heated to 70 ° C. 110 g (0.95 mol) sodium chloroacetate added dropwise in 200 ml of water. To The addition was complete and the mixture was stirred at 90 ° C for a further 2 h stirred and unreacted sodium chloroacetate by addition destroyed by 4 g (0.05 mol) of glycine. The yield of betaine was 95% of theory.

Example 2

Betainization of bis-sorbitylmethylamine with acrylic acid. In a 1 l three-necked flask with stirrer, dropping funnel and back a cooler was a mixture of 360 g (1 mol) of bis-Sorbi Tylmethylamine submitted in 500 ml of water and stirring 90 ° C heated. 68 g (0.95 mol) of acrylic became within 2 h acid added dropwise. After the end of the addition, the Mi Schung stirred at 80 ° C for a further 2 h. The yield of betaine was 94% of theory.

Claims (8)

1. Bis-sorbitol-vinyl betaines of the formula (I) in the
Z for a sorbityl residue,
R ^{1 represents} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 18 carbon atoms and
n for 1 or 2
stands. 2. Process for the preparation of bis-sorbitylaminobetaines of the formula (I) in the
Z for a sorbityl residue,
R ^{1 represents} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 18 carbon atoms and
n for 1 or 2
is, in which one betaines bis-sorbitylamine in a known manner. 3. The method according to claim 2, characterized in that bis-sorbitylamines of the formula (II) are used, in which Z and R ^{1 have} the meanings given above. 4. The method according to claim 2, characterized in that one as betainizing agent sodium chloroacetate or Acrylic acid is used. 5. The method according to claim 2, characterized in that bis-sorbitylamine and betainizing agent in the molar Ratio of 1: 0.5 to 1: 1. 6. The method according to claim 2, characterized in that to betainize at a temperature in the range from 30 to 100 ° C. 7. Aqueous detergent mixtures containing bis-sorbitylamino betaine of the formula (I) in the
Z for a sorbityl residue,
R ^{1 represents} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 18 carbon atoms and
n for 1 or 2
stands as well as other anionic, nonionic, cationic and / or zwitterionic surfactants. 8. Use of the bis-sorbitylaminobetaines according to claim 1 for the production of surfactants.