Amphiphilic compounds with a plurality of hydrophilic and hydrophobic groups based on carbonic acid derivatives

The invention relates to amphiphilic compounds of the general formula I ##STR1## which have at least two hydrophilic and at least two hydrophobic groups and are based on carbonic acid derivatives. The spacer A is an aliphatic, cyclic or acyclic or an aromatic di-, oligo- or polycarbonate of the formula II: ##STR2## The amphiphilic compounds according to this invention are mostly surface-active and are suitable as emulsifiers, demulsifiers, detergents, dispersants and hydrotropes for industrial and domestic use, in particular in the fields of metalworking, ore extraction, surface finishing, plastics processing, washing and cleaning, cleaning of hard surfaces, manual dishwashing compositions, cosmetics, medicine and food processing and preparation.

The invention relates to amphiphilic compounds containing a plurality of 
hydrophilic and hydrophobic groups, based on carbonic acid derivatives. 
Known amphiphilic substances encompass a wide variety of anionic, cationic, 
nonionic and zwitterionic compounds. By far the majority of these 
substances consist of a hydrophilic head group and at least one 
hydrophobic part. 
With amphiphilic substances there is a need, for ecological reasons, for 
example reduction packaging and transportation, to achieve an increasingly 
greater effect per unit mass of substance employed. Since optimization by 
mixing amphiphilic substances produces only very limited advances, novel 
amphiphilic substances with greater effectiveness are required. It is 
therefore necessary in particular to find substances with lower critical 
micelle concentrations and/or lower surface tensions in order to be able 
to reduce markedly the amounts of active substance employed. Initial 
approaches to a solution in the direction of higher-performance 
amphiphilic substances by doubling one part of the structure (hydrophilic 
head group, hydrophobic group) are already known. Thus, cationic 
surface-active compounds can be obtained by adding long-chain alkyl 
halides onto permethylated alkylenediamines [R. Zana, M. Benrraou, R. 
Rueff, Langmuir, 7 (1991)1072; R. Zana, Y. Talmon, Nature, 362 (1993) 228; 
E. Alami, G. Beinert, P. Marie, R. Zana, Langmuir, 9 (1993) 1465]. 
Anionic surface-active compounds containing at least two hydrophilic groups 
and at least two hydrophobic groups have to date been prepared only on the 
basis of diglycidyl ethers (U.S. Pat. No. 5,160,450, JP 01 304 033, JP 4 
124 165). However, diglycidyl ethers are regarded as toxicologically 
objectionable and are rather costly. Furthermore, epichlorohydrin is used 
for their preparation, which leads to large amounts of residues so that 
these compounds are no longer up to date from ecotoxicological and 
economic viewpoints. 
The object was therefore to find amphiphilic compounds which have at least 
two hydrophilic groups and at least two hydrophobic groups, are very 
effective relative to the amount used, and furthermore can be prepared 
from raw materials which are readily available industrially and without 
large amounts of unwanted by-products being formed. In addition, the 
compounds should be easy to cleave again. 
The object is achieved according to the invention by amphiphilic di-, 
oligo- or polycarbonates whose basic skeleton can be prepared from di-, 
oligo- or polycarbonic acid derivatives and alkoxylated fatty amines and 
fatty acid amides. The corresponding di-, oligo- or polycarbonates are 
nonionic surfactants which, nevertheless, can be further reacted to give 
anionic amphiphilic compounds. In this context, suitable reactions are 
sulfonation, carboxymethylation and conversion to, for example, 
isethionates, taurates and sulfosuccinates. 
The amphiphilic compounds according to the invention are thus compounds of 
the general formula I: 
##STR3## 
in which R.sup.1 and R.sup.2, independently of one another, are an 
unbranched or branched, saturated or unsaturated hydrocarbon radical 
having from 1 to 22, preferably from 6 to 18, carbon atoms and an 
unbranched or branched, saturated or unsaturated acyl radical having from 
2 to 23, preferably from 7 to 19, carbon atoms, n and m, independently of 
one another, are at least 1 and the sum of n and m is a number from 2 to 
200, preferably from 2 to 100 and particularly preferably from 2 to 10. 
a, b, c, d, e, f, g and h are, independently of one another, numbers from 0 
to 15, and the sum of a and b, c and d, e and f and g and h must in each 
case be at least 1. The alkoxide units are incorporated randomly or 
blockwise, and the sequence is arbitrary. Y and Z. independently of one 
another, are hydrogen or functional groups. Functional groups which may be 
mentioned are --CH.sub.2 COOM, --SO.sub.3 M, --C.sub.2 H.sub.4 SO.sub.3 M, 
--C(O)C.sub.2 H.sub.3 (SO.sub.3 M)COOM', --P(O)(OM).sub.2, where M and M' 
are alkali metal, ammonium, alkanolammonium or 1/2 alkaline earth metal. 
Specific radicals which may be mentioned as substituents R.sup.1 and 
R.sup.2 are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, 
n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, 
n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, 
n-eicosyl, n-uneicosyl, n-docosyl and their branched-chain isomers, and 
the corresponding mono-, di- or triunsaturated radicals and the 
corresponding acyl compounds. 
The spacer A is an aliphatic, cyclic or acyclic or an aromatic di-, oligo- 
or polycarbonate of the formula II: 
##STR4## 
R originates from a di-, oligo- or polyol which, preferably, does not tend 
toward cyclization, in which r hydroxyl groups are esterified with 
carbonic acid derivatives. r is a number from 2 to 200, preferably from 2 
to 20, particularly preferably from 2 to 10. Examples thereof which may be 
mentioned here are alkylenediols, preferably having from 2 to 8 carbon 
atoms, di- to tetraethylene glycols, di- to tetrapropylene glycols, 
polyalkylene glycols, such as, for example polyethylene glycols, oligo- or 
polyglycerols, sorbitol, polyvinyl alcohol, trimethylolpropane and acetals 
such as 2,2'-methylene-bis(1,3-dioxolane-5-methylene)diol. For 
stoichiometric reasons, r=n+m. 
The amphiphilic compounds according to the invention are distinguished by 
extremely low critical micelle concentrations (CMCs) and very low surface 
tensions, which must be attributed to their special structure--at least 
two hydrophilic groups and at least two hydrophobic groups. Furthermore, 
most of them have a rather high hydrophilic suspension capacity which is 
about halfway between that of conventional surfactants and that of 
pentasodium tripolyphosphate. Some of these compounds are extremely rapid 
wetting agents. They all have very high hardness stability and good 
solubility in water. 
The amphiphilic compounds according to this invention are particularly 
suitable as emulsifiers, demulsifiers, detergents, dispersants, 
hydrotropes and antistatics in industry and domestically, for example in 
the areas of metalworking, ore extraction, textile auxiliaries, surface 
finishing, plastics processing, washing and cleaning, cleaning of hard 
surfaces, in particular as a manual dishwashing detergent, cosmetics, 
medicine and foods processing and preparation. 
In these cases they can be combined with all customary anionic, nonionic, 
cationic and ampholytic surface-active substances.

Examples which may be mentioned of nonionic surface-active substances which 
can be used for a combination are: fatty acid glycerides, fatty acid 
polyglycerides, fatty acid esters, ethoxylates of higher alcohols, 
polyoxyethylene fatty acid glycerides, polyoxy-ethylene/propylene glycol 
fatty acid esters, polyoxy-ethylene sorbitan fatty acid esters, 
polyoxyethylene castor oil or hydrogenated castor oil derivatives, 
polyoxyethylene lanolin derivatives, polyoxyethylene fatty acid amides, 
polyoxyethylene alkylamines, alkanolamines, alkylamine oxides, derivatives 
of protein hydrolysates, hydroxy-mixed ethers, alkylpolyglycosides, amine 
oxides and alkylglucamides. 
Examples which may be mentioned of anionic surface-active substances which 
can be used for combinations are: soaps, ether carboxylic acids and salts 
thereof, alkyl-sulfonates, .alpha.-olefinsulfonates, .alpha.-sulfofatty 
acid derivatives, sulfonates of higher fatty acid esters, higher alcohol 
sulfates, alcohol ether sulfates, hydroxy-mixed ether sulfates, salts of 
phosphate esters, taurides, isethionates, linear alkyl-benzenesulfonates, 
cumenesulfonate, alkylarylsulfonates, sulfates of polyoxyethylene fatty 
acid amides and salts of acylamino acids. 
Examples which may be mentioned of customary cationic surface-active 
substances which can be used for combinations are: alkyltrimethylammonium 
salts, dialkyl-dimethylammonium salts, alkyldimethylbenzylammonium salts, 
alkylpyridinium salts, alkylisoquinolinium salts, benzethonium chlorides 
and cationic acylamino acid derivatives. 
Examples which may be mentioned of ampholytic surface-active substances 
which can be used for combinations are: amino acids, betaines, 
sulfobetaines, imidazoline derivatives, soybean oil lipids and lecithin. 
Furthermore, the amphiphilic compounds according to the invention can be 
also be combined together on their own. 
It is likewise possible to add conventional additives to the amphiphilic 
compounds according to the invention. Such additives are specifically 
selected for a formulation and for example comprise inorganic salts, such 
as sodium chloride and sulfate, and builders, hydrotropes, UV absorbers, 
softening agents, chelating agents, viscosity modifiers and fragrances. 
The abovementioned compounds can be prepared from di-, oligo- or 
polycarbonates and at least two equivalents of alkoxylated fatty amines 
and/or alkoxylated fatty acid amides. The precursors used here are the 
di-, oligo- or polyols which can be reacted with one equivalent of diethyl 
carbonate per hydroxyl group. There must be at least two equivalents of 
diethyl carbonate, in the case of oligo- or polyols the properties of the 
molecule can be adjusted more exactly by the degree of conversion with 
carbonate or amine ethoxylate or amide ethoxylate in the last step. Both 
of the esterification and transesterification reactions described above, 
can be carried out using known catalysts, such as, for example, titanates, 
mixtures of antimony trioxide and calcium acetate, stannates, zinc acetate 
and alkali metal oxides. Titanates have, however, proven to be 
particularly favorable as regards reaction times and colour quality. The 
anionic amphiphilic compounds can be prepared by reacting the 
aforementioned products with, for example, amidosulfonic acid, 
chloroacetic acid salts, isethionates or maleic anhydride, and 
neutralizing the resulting mixture with aqueous alkali metal or alkaline 
earth metal hydroxides, aqueous ammonia or alkanolamines. If required, the 
products are bleached in aqueous solution with hydrogen peroxide (0.1 to 
2.0%, based on solid).