Hydrophobicized double layer hydroxide compounds

Novel hydrophobicized double-layer hydroxide compounds, processes for their production by reaction of double-layer hydroxides with aliphatic mono- and/or dicarboxylic acids, and their uses as alkoxylation catalysts for compounds containing active H atoms or for fatty acid esters. The hydrophobicized double-layer hydroxide compounds correspond to formula (I) EQU (M(II).sub.1-x M(III).sub.x (OH).sub.2)A.sub.a B.sub.b * z H.sub.2 O (I) in which PA1 M(II) is a divalent metal cation selected from the group consisting of magnesium, zinc, calcium, iron, cobalt, copper, cadmium, nickel and manganese; PA1 M(III) is a trivalent metal cation selected from the group consisting of aluminum, iron, chromium, manganese, bismuth and cerium; PA1 A is an equivalent of a monoanion of an aliphatic C.sub.2-34 monocarboxylic acid or an equivalent of a dianion of an aliphatic C.sub.4-44 dicarboxylic acid; PA1 B is an anion selected from the group consisting of carbonate, hydrogen carbonate, sulfate, nitrate, nitrite, phosphate, hydroxide, and halide; and wherein PA2 0.1.ltoreq.x.ltoreq.0.5 PA2 0<a.ltoreq.0.5 PA2 0.ltoreq.b.ltoreq.0.5 PA2 0<a+b.ltoreq.0.5 PA2 0.ltoreq.z.ltoreq.10; but excluding compounds containing the combinations of magnesium and aluminum with carbonate and/or sulfate.

FIELD OF THE INVENTION 
This invention relates to new hydrophobicized double layer hydroxide 
compounds, to a process for the production of these compounds by reaction 
of double-layer hydroxides with aliphatic mono- and/or dicarboxylic acids 
in an organic solvent or in a kneader and to the use of the 
hydrophobicized double layer hydroxide layer compounds as alkoxylation 
catalysts for compounds containing active H atoms or for fatty acid 
esters. 
PRIOR ART 
Two-dimensional inorganic polycations with intracrystalline charge 
equalization by mobile interlayer anions are also known as "double layer 
hydroxide compounds" and have been repeatedly described in the literature 
(Chimia 24, 99 (1970)). Chemically, these compounds are mixed hydroxosalts 
of 2- and 3-valent metal cations and may be characterized by the following 
general formula: 
EQU (M(II).sub.1-x M((III).sub.x (OH).sub.2)B * n H.sub.2 O 
in which 
M(II) is at least one divalent metal ion, 
M(III) is at least one trivalent metal ion and 
B is an equivalent of a monobasic and/or polybasic inorganic acid 
and 
x is a number of 0.2 to 0.4 and 
n is a number of 0 to 10. 
Certain properties of this class of compounds, for example their use as a 
catalyst material, as ion exchangers and certain medicinal applications, 
have been summarily described by W. T. Reichle (CHEMTECH, Jan. 1986, 58). 
Various methods for the production of these compounds on an industrial 
scale are described in DE-OS 20 61 156. 
A well-characterized representative of this class of compounds is 
hydrotalcite which occurs naturally as a mineral. Synthetic hydrotalcites 
are also known and are described, for example, in DE-C-15 92 126, DE 33 46 
943 A1, DE 33 06 822 A1 and EP 0 207 811 A1. Hydrotalcite is a natural 
mineral having the following ideal formula: 
EQU (Mg.sub.6 Al.sub.2 (OH).sub.16)CO.sub.3 * 4 H.sub.2 O 
of which the structure is derived from that of brucite (Mg(OH).sub.2). 
Brucite crystallizes in a layer structure with the metal ions in 
octahedral vacancies between two layers of close-packed hydroxyl ions, 
only every second layer of the octahedral vacancies being occupied. In 
hydrotalcite, a few magnesium ions are replaced by aluminium ions so that 
the layer packet receives a positive charge. This is equalized by the 
anions which are present in the interlayers together with zeolitic water 
of crystallization. 
The following are mentioned as other typical representatives of this class 
compounds: 
______________________________________ 
magaldrate (Mg.sub.10 Al.sub.5 (OH).sub.31)(SO.sub.4).sub.2 * n 
H.sub.2 O, 
pyroaurite (Mg.sub.6 Fe.sub.2 (OH).sub.16)CO.sub.3 * 4.5 H.sub.2 O 
and 
hydrocalumite (Ca.sub.2 Al(OH).sub.6)NO.sub.3 * n H.sub.2 O. 
______________________________________ 
Calcined hydrotalcites have already been used with excellent results as 
ethoxylation and propoxylation catalysts (DS 38 43 713 A1). However, they 
are attended by the disadvantage that they have to be converted from the 
natural and synthetic hydrotalcites into a calcined form suitable for 
catalytic purposes by heating for several hours at temperatures of, for 
example, 400.degree. to 600.degree. C. In addition, calcined compounds are 
sensitive to traces of water and to the carbon dioxide from the air 
(reverse reaction of calcination), so that their range of applications and 
their stability in storage are limited due to the loss of activity. 
According to DE 30 19 632 A1, U.S. Pat. No. 4,761,188, EP 0 142 773 A1, EP 
0 189 899 A1, EP 0 256 872 A1, hydro-phobicized hydrotalcites formed by 
the treatment of hydrotalcite with anions of acids, for example fatty 
acids, have already been used as stabilizers for thermoplastic resins. 
This surface treatment is carried out with anionic surface-active agents 
in a quantity of 1 to 10% by weight, based on the hydrotalcite. 
In addition, it is known from the teaching of DE 37 31 919 A1 that 
compounds having the general formula Al.sub.x Mg.sub.y (OH).sub.35-z 
R.sub.z * n H.sub.2 O, in which R is the anion of a monocarboxylic acid, 
may be used as thickeners, thixotropic agents, stabilizers or 
anti-sedimentation agents. The compounds disclosed in this document are 
prepared by a complete exchange of sulfate ions for monocarboxylic acid 
ions using an aqueous suspension of the alkali salt of the monocarboxylic 
acid. 
DE 40 10 606 A1 describes hydrophobicized hydro-talcite compounds having 
the general formula Mg.sub.x Al(OH).sub.y --(CO.sub.3).sub.m (A).sub.n * z 
H.sub.2 O, in which A stands for a dianion of an aliphatic dicarboxylic 
acid or for two monoanions of an aliphatic monocarboxylic acid, as 
alkoxylation catalysts. 
Now, the problem addressed by the present invention was to provide new 
hydrophobicized double layer hydroxide compounds in which the trivalent 
aluminium or divalent magnesium would be replaced by equivalent metal 
cations and the ratio of the anion B to be exchanged to the 
hydrophobicizing anion A could be varied. 
In addition, known double layer hydroxide compounds, which had never been 
used as alkoxylation catalysts either in pure form or by calcination, were 
to be converted into an active catalyst form by hydrophobicization.

DESCRIPTION OF THE INVENTION 
Accordingly, the present invention relates to hydrophobicized double layer 
hydroxide compounds corresponding to general formula (I) 
EQU (M(II).sub.1-x M(III).sub.x (OH).sub.2)A.sub.a B.sub.b * z H.sub.2 O (I) 
in which M(II) is a divalent metal cation selected from the group 
consisting of magnesium, zinc, calcium, iron, cobalt, copper, cadmium, 
nickel and manganese, 
in which M(III) is a trivalent metal cation selected from the group 
consisting of aluminium, iron, chromium, manganese, bismuth and cerium, 
in which A is an equivalent of a monoanion of an aliphatic C.sub.2-34 
monocarboxylic acid or an equivalent of a dianion of an aliphatic 
C.sub.4-44 dicarboxylic acid, 
in which B is an anion from the group consisting of carbonate, hydrogen 
carbonate, sulfate, nitrate, nitrite, phosphate, hydroxide and halides and 
in which the conditions 
0.1.ltoreq.x.ltoreq.0.5 
0&lt;a.ltoreq.0.5 
0.ltoreq.b.ltoreq.0.5 
0&lt;a+b.ltoreq.0.5 
0.ltoreq.z.ltoreq.10 
apply, compounds containing the combinations of magnesium and aluminium 
with carbonate and/or sulfate being excluded. 
The present invention also relates to a process for the production of 
hydrophobicized double layer hydroxide compounds corresponding to general 
formula (I), characterized in that double layer hydroxide compounds 
corresponding to general formula (II) 
EQU (M(II).sub.1-x M(III).sub.x (OH).sub.2) B * z H.sub.2 O (II) 
in which M(II), M(III), B, x and z are as defined above, excluding 
compounds containing the combinations of magnesium and aluminium with 
carbonate and/or sulfate, are reacted with at least one aliphatic 
C.sub.2-34 monocarboxylic acid and/or at least one C.sub.4-44 aliphatic 
dicarboxylic acid either 
a) in an organic solvent and the solvent is removed by drying at 20.degree. 
to 150.degree. C. or 
b) are directly reacted with one another by stirring or kneading or 
c) the double layer hydroxide compounds corresponding to general formula 
(II) are reacted with an alkali metal and/or alkaline earth metal salt of 
the mono- and/or dicarboxylic acids in aqueous suspension. 
The anions A of the monocarboxylic acids, which may be used for the 
hydrophobicization of double layer hydroxide compounds, are for example 
those of the C.sub.2-34 monocarboxylic acids, preferably C.sub.6-22 fatty 
acids of natural or synthetic origin, more particularly linear, saturated 
or unsaturated fatty acids, including technical mixtures thereof, which 
are obtainable by hydrolysis from animal and/or vegetable fats and oils, 
for example from coconut oil, palm kernel oil, palm oil, soybean oil, 
sunflower oil, rapeseed oil, cottonseed oil, fish oil, beef tallow and 
lard. 
Typical examples are caproic acid, caprylic acid, capric acid, lauric acid, 
myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, 
elaidic acid, petroselic acid, linoleic acid, linolenic acid, arachic 
acid, gadoleic acid, behenic acid and erucic acid; also methyl-branched, 
saturated and unsaturated C.sub.10-22 fatty acids which are formed as 
secondary products in the dimerization of the corresponding unsaturated 
fatty acids. However, C.sub.2-5 monocarboxylic acids, such as preferably 
acetic acid or propionic acid, may also be used. Lauric acid and stearic 
acid are particularly preferred. 
Typical examples of dicarboxylic acids A which are suitable for the 
hydrophobicization of double layer hydroxide compounds are succinic acid, 
maleic acid, fumaric acid, adipic acid, pimelic acid, suberic acid, 
sebacic acid and the like; also so-called dimer fatty acids which may be 
obtained, for example, from oleic acid or tall oil fatty acid and may 
contain up to 44 carbon atoms. The dimerization products of saturated, 
mono- and/or polyunsaturated C.sub.16-22 monomer fatty acids, such as 
palmitoleic acid, oleic acid, gadoleic acid, erucic acid, ricinoleic acid, 
linoleic acid, linolenic acid, arachidonic acid and behenic acid, may also 
be used. 
In one preferred embodiment of the present invention, the anions A of 
C.sub.6-22 monocarboxylic acids or C.sub.8-36 dicarboxylic acids, 
including dimer fatty acids, are used for hydrophobicizing the double 
layer hydroxide compounds. 
According to the invention, the anions B are selected from the group 
consisting of carbonate, hydrogen carbonate, sulfate, nitrate, nitrite, 
phosphate, hydroxide and halides, depending on the origin of the double 
layer hydroxide compounds corresponding to general formula II. 
According to the invention, the number ratio of a to b in the 
hydrophobicized double layer hydroxide compounds corresponding to general 
formula (I) should be in the range from 0.49:0.01 to 0.05:0.45 and, more 
particularly, in the range from 0.3:0.02 to 0.05:0.25. A high degree of 
exchange or hydrophobicization is required in the compounds corresponding 
to general formula (I) so that all monobasic or polybasic inorganic anions 
B in the compounds corresponding to general formula (I) are exchanged. 
According to the invention, complete hydrophobicization occurs in 
particular in cases where a&gt;x is achieved. 
Accordingly, hydrophobicized double layer hydroxide compounds of general 
formula (I) which, based on their total weight, contain 15 to 70% by 
weight and more particularly 20 to 50% by weight of the anions A of 
C.sub.6-22 monocarboxylic acids or 10 to 60% by weight and more 
particularly 15 to 50% by weight of the dianions A of the C.sub.8-36 
dicarboxylic acids are also preferred. 
The hydrophobicized double layer hydroxide compounds may be produced by 
various methods, for example by direct reaction of natural or synthetic 
double layer hydroxide compounds with mono- and/or dicarboxylic acids in a 
kneader or in the presence of organic solvents and by reaction of the 
double layer hydroxide compounds with an aqueous suspension of a mono- 
and/or dicarboxylic acid salt. 
In a preferred embodiment of the present invention, the hydrophobicized 
double layer hydroxide compounds are prepared in a low-boiling organic 
solvent, preferably C.sub.1-6 alcohols, open-chain and cyclic ethers 
and/or ketones, by reaction of monocarboxylic acids and/or dicarboxylic 
acids with the double layer hydroxide compounds corresponding to general 
formula (I). In a particularly preferred embodiment, hydrophobicization is 
carried out in isopropanol, diethyl ether, tetrahydrofuran and/or acetone. 
In another preferred embodiment, the molar ratio between the double layer 
hydroxide compound used and the monocarboxylic acid (or dicarboxylic acid) 
is 6:1 (3:1) to 1:10 (1:5) and preferably 3:1 (1.5:1) to 1:3 (1:1.5). As 
known to the expert, the molar ratio will have to be adjusted to those 
anions of the particular double layer hydroxide compounds used which are 
available during the exchange. 
The process according to the invention may be carried out at temperatures 
of 20.degree. to 120.degree. C. and is preferably carried out at 
temperatures of 40.degree. to 100.degree. C., the double layer hydroxide 
compound and the carboxylic acid (or dicarboxylic acid) generally being 
heated under reflux in the particular organic solvent for 0.5 to 8 hours 
and preferably for 1 to 6 hours. 
In another preferred embodiment of the present invention, the organic 
solvent is removed over a period of 0.5 to 3 hours and preferably over a 
period of 1 to 2 hours at temperatures in the range from 20.degree. to 
150.degree. C. and preferably at temperatures in the range from 50.degree. 
to 120.degree. C. 
In addition, the hydrophobicized double layer hydroxide compounds according 
to the invention may also be obtained by direct reaction of double layer 
hydroxide compounds with mono- and/or dicarboxylic acids in the absence of 
a solvent using a stirring unit of any kind, preferably a kneader. 
In principle, the compounds of general formula (I) according to the 
invention may also be prepared analogously to the process known from DE 37 
31 919 A1 by reaction of double layer hydroxide compounds with an aqueous 
suspension of an alkali metal salt and/or alkaline earth metal salt, 
preferably sodium salts of a mono- and/or dicarboxylic acid. 
Finally, the hydrophobicized double layer hydroxide compounds may also be 
obtained from calcined double layer hydroxide compounds by reaction 
thereof with the mono- or dicarboxylic acids. Carbonate-free or 
carbonate-containing products may be obtained in the absence of air or 
CO.sub.2 or in the presence of carbon dioxide. 
It can be shown with the aid of X-ray diffractograms that the layer 
structure in the hydrophobicized double layer hydroxide compounds has 
remained intact with widening of the layer intervals. 
The stoichiometric water content of the hydrophobicized double layer 
hydroxide compounds can be in the range from 0 to 10 molecules, depending 
on the method of production and the drying conditions. A range of 0 to 4 
molecules is preferred and is generally established when the 
hydrophobicized double layer hydroxide compounds are dried to constant 
weight at temperatures of 100.degree. to 250.degree. C. and preferably at 
temperatures of 150.degree. to 220.degree. C., so that particularly high 
catalytic activity can be guaranteed. 
The present invention also relates to the use of hydrophobicized double 
layer hydroxide compounds corresponding to general formula (I), excluding 
compounds containing combinations of magnesium and aluminium with 
carbonate, as alkoxylation catalysts for compounds containing active H 
atoms or for fatty acid esters. 
The present invention is based in this regard on the observation that 
hydrophobicized double layer hydroxide compounds are suitable for the 
ethoxylation and propoxylation of compounds containing active H atoms and 
fatty acid esters. This observation is surprising because untreated 
natural or synthetic double layer hydroxide compounds, i.e. those in 
non-calcined form, and also a number of calcined compounds are not active 
as ethoxylation or propoxylation catalysts. 
In the context of the invention, compounds containing active H atoms are, 
for example, fatty alcohols, fatty acids and amines which are formed in 
the ethoxylation or propoxylation of nonionic detergents. A typical 
example of this is the reaction of fatty alcohols typically containing 10 
to 18 carbon atoms with ethylene oxide and/or propylene oxide in the 
presence of catalysts, the fatty alcohols reacting with several molecules 
of ethylene oxide and/or propylene oxide. 
The following compounds inter alia have been used as catalysts for the 
above-mentioned polyalkoxylation: 
calcium and strontium hydroxides, alkoxides and phenoxides (EP 0 092 256 
A1) , 
calcium alkoxides (EP 0 091 146 A1). 
barium hydroxide (EP 0 115 083 B1), 
basic magnesium compounds, for example alkoxides (EP 0 082 569 A1), 
magnesium and calcium fatty acid salts (EP 0 085 167 A1). 
The catalysts mentioned above are attended inter alia by the disadvantage 
that they cannot readily be incorporated in the reaction system and/or are 
difficult to produce. Other typical alkoxylation catalysts are potassium 
hydroxide and sodium methylate. 
A narrow range of the degree of polyalkoxylation is of particular 
importance for fatty alcohol polyalkoxylates (JAOCS, 63, 691 (1986), 
MAPPI, 52 (1986)). Accordingly, the so-called "narrow-range" alkoxylates 
have in particular the following advantages: 
low flow points 
relatively high smoke points 
fewer mols alkoxide required to achieve solubility in water 
less hydrotropes for introduction into liquid universal detergents 
a relatively faint odor attributable to the presence of free (unreacted) 
fatty alcohols 
reduction of pluming during the spray drying of detergent slurries 
containing fatty alcohol polyalkoxylate surfactants. 
Using hydrophobicized double layer hydroxide compounds as catalysts in 
accordance with the invention, compounds containing active H atoms and 
fatty acid esters can be polyalkoxylated with high yields in short 
reaction times. The reaction products have a narrow range or homolog 
distribution, the distribution curve coming very close to the curve 
calculated in accordance with Poisson. The hydrophobicized double layer 
hydroxide compounds used in accordance with the invention have the 
advantage that they can readily be incorporated in the alkoxylation 
reaction mixture and can be removed again by simple measures by virtue of 
their insolubility in the reaction mixture. However, they may also remain 
in the reaction mixture providing their presence is not problematical in 
subsequent applications of the reaction products. 
Examples of compounds which can be alkoxylated in accordance with the 
invention using hydrophobicized double layer hydroxide compounds are 
listed in the following: 
C.sub.6-22 fatty acids of natural or synthetic origin, more particularly 
linear, saturated or unsaturated fatty acids, including technical mixtures 
thereof, which can be obtained by hydrolysis from animal and/or vegetable 
fats and oils, for example from coconut oil, palm kernel oil, palm oil, 
soybean oil, sunflower oil, rapeseed oil, cottonseed oil, fish oil, beef 
tallow and lard. Typical examples are caproic acid, caprylic acid, capric 
acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic 
acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic 
acid, arachic acid, gadoleic acid, behenic acid, erucic acid, arachidonic 
acid and clupanodonic acid; also methyl-branched, saturated and 
unsaturated C.sub.10-22 fatty acids, which are formed as secondary 
products in the dimerization of the corresponding unsaturated fatty acids, 
and C.sub.1-7 monocarboxylic acids. 
Hydroxyfatty acids of natural or synthetic origin, more particularly 
containing 16 to 22 carbon atoms, for example ricinoleic acid or 
12-hydroxystearic acid. 
Fatty acid amides. Derivatives of the above-mentioned linear, saturated or 
unsaturated fatty acids with ammonia or primary aliphatic amines 
containing 1 to 4 carbon atoms in the aliphatic substituent. 
Alkanols. Saturated or unsaturated monoalkanols, more particularly 
hydrogenation products of the above-mentioned linear, saturated or 
unsaturated fatty acids or derivatives thereof, such as methyl esters, or 
glycerides; aliphatic or cyclic alkanols containing 2 to 6 carbon atoms, 
for example ethanol, propanol, butanol, hexanol and cyclohexanol; 
including the Guerbet alcohols derived from the above-mentioned 
monoalkanols. 
Alkyl phenols. Mono-, di- or trialkyl phenols, more particularly containing 
4 to 12 carbon atoms in the alkyl groups. 
Polyglycols. Polyethylene or polypropylene glycols (average degree of 
polymerization 2 to 2000). 
Fatty amines. More particularly primary fatty amines obtainable from 
nitriles of the above-mentioned linear, saturated or unsaturated fatty 
acids or the corresponding fatty alcohols; also mono- and dialkyl amines 
containing C.sub.1-6 alkyl groups. 
Fatty acid alkanolamides. Derivatives of the above-mentioned linear, 
saturated or unsaturated fatty acids with mono- or dialkanolamines, more 
particularly mono- or diethanolamine. 
Vicinally hydroxy- or alkoxy-substituted alkanes. Ring opening products of 
1,2-epoxyalkane mixtures containing 12 to 22 carbon atoms in the chain 
with polyfunctional alkanols containing 2 to 12 carbon atoms and 2 to 6 
hydroxyl groups; but only if they are reacted with ethylene oxide or first 
with ethylene oxide and then with propylene oxide. 
Fatty acid esters formed from the optionally methyl-branched fatty acids or 
monocarboxylic acids and hydroxyfatty fatty acids listed above and the 
alkanols listed above; also esters of these acids with polyols, for 
example with ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 
neopentyl glycol, glycerol, diglycerol, triglycerol, tetraglycerol, 
trimethylol propane, di-trimethylol propane, pentaerythritol, 
dipentaerythritol, and sugar alcohols, more particularly sorbitan. 
As mentioned at the beginning, esters of the above-mentioned fatty acids 
with the above-mentioned polyols may also be present as partial esters or 
as technical ester mixtures containing partial esters, more particularly 
in the form of glycerides. 
Preferred fatty acid esters for the ethoxylation and/or propoxylation 
according to the invention are formed from saturated or unsaturated, 
optionally methylbranched or optionally hydroxy-substituted C.sub.8-22 
fatty acids with C.sub.1-4 alkanols or with glycerol. 
The structure of the ethoxylated or propoxylated fatty acid esters obtained 
in accordance with the invention cannot always be clearly determined. 
Whereas esters of fatty acids and monoalkanols or full esters thereof 
would appear to react with polyols with insertion of ethyleneoxy and/or 
propyleneoxy units into the ester bond, it is not possible to determine 
the reaction products to which the reaction of ethylene oxide and/or 
propylene oxide with partial esters of fatty acids and polyols or of 
hydroxysubstituted fatty acids and mono-alkanols leads; in this case, 
reactions could also take place at the free OH groups, particularly at 
free primary OH groups. 
The derivatives to be produced in accordance with the invention using 
hydrophobicized double layer hydroxide compounds are commercially 
available products so that they need not be described in any more detail. 
They are all obtained by ethoxylation and/or propoxylation of starting 
compounds containing active hydrogen atoms or of fatty acid esters. 
Typical representatives are, for example, an addition product of 9 mol 
ethylene oxide with coconut oil fatty acid, an addition product of 2 mol 
ethylene oxide with a C.sub.12-14 fatty alcohol mixture, an addition 
product of 3 mol ethylene oxide and S mol propylene oxide with a 
C.sub.12-18 fatty alcohol mixture, an addition product of 10 mol ethylene 
oxide with nonyl phenol, an addition product of 7.3 tool ethylene oxide 
with glycerol, an addition product of 10 mol ethylene oxide with a diol 
mixture obtained by reaction of a C.sub.12-16 1,2-epoxyalkane mixture with 
ethylene glycol, an addition product of 12 mol ethylene oxide with a 
C.sub.10-18 fatty amine mixture and an addition product of 4 mol ethylene 
oxide with coconut oil fatty acid monoethanolamide; also addition products 
of 41 mol ethylene oxide with castor oil, addition products of 25 mol 
ethylene oxide with hydrogenated castor oil, addition products of 7 parts 
by weight ethylene oxide with 10 parts by weight of a palmitic 
acid/stearic acid mono-/diglyceride mixture containing 40 to 45% by weight 
monoglyceride and addition products of 20 mol ethylene oxide with sorbitan 
monostearate. 
In a preferred embodiment of the invention, the compounds containing active 
H atoms ethoxylatable or propoxylatable using the hydrophobicized double 
layer hydroxide compounds are selected from the group consisting of fatty 
acids, hydroxyfatty acids, fatty acid amides, alkanols, alkyl phenols, 
polyglycols, fatty amines, fatty acid alkanolamides or vicinally hydroxy- 
or alkoxy-substituted alkanes. 
In another preferred embodiment, the hydrophobicized double layer hydroxide 
compounds are used in a quantity of 0.1 to 3% by weight and preferably in 
a quantity of 0.5 to 2% by weight, based on the end product of the 
ethoxylation or propoxylation reaction. 
In another preferred embodiment of the invention, the reaction between 
compounds containing active hydrogen atoms or fatty acid esters on the one 
hand and ethylene and/or propylene oxide on the other hand is carried out 
in the presence of the hydrophobicized double layer hydroxide compounds 
according to the invention at a temperature of 125.degree. to 180.degree. 
C. and preferably 150.degree. to 160.degree. C. and under a pressure of 1 
to 5 bar. The time required is determined by the desired degree of 
alkoxylation and is normally between 0.5 and 5 hours. 
The following Examples are intended to illustrate the invention without 
limiting it in any way. 
EXAMPLES 
Example 1 
Reaction of magaldrate with sodium laurate. 20 g magaldrate (commercial 
product of Giulini, Ludwigshafen, Germany) having the ideal formula 
(Mg.sub.10 Al.sub.5 (OH).sub.31)(SO.sub.4).sub.2 * z H.sub.2 O were 
suspended in 200 ml water and, after the addition of a solution of 7.6 g 
sodium laurate in 70 ml water, the resulting suspension was stirred for 15 
hours at 70.degree. C. After filtration and washing, the white precipitate 
was dried at 200.degree. C./100 mbar. 
______________________________________ 
Yield: 20.2 g hydrophobicized magaldrate 
Analyses: 17.7% by weight Mg 
9.5% by weight Al 
18.7% by weight C 
1.8% by weight SO.sub.4 
Mg/Al ratio: 2.1 
Al/laurate ratio: 
2.71 
______________________________________ 
25.9% by weight laurate, x=0.33; a=0.14; b=0.04 
Example 2 
Reaction of chloride-containing hydrotalcite with sodium laurate. 20 g 
chloride-containing hydrotalcite (Mg.sub.6 Al.sub.2 (OH).sub.16)Cl.sub.2 * 
4 H.sub.2 O were suspended in 200 ml water and, after the addition of a 
solution of 15 g sodium laurate in 100 ml water, the resulting suspension 
was stirred for 3 hours at 70.degree. C. After filtration and washing, the 
precipitate was dried at 105.degree. C./100mbar. As a catalyst, the 
product was redtied at 200.degree. C./100 mbar. 
______________________________________ 
Yield: 26.3 g hydrophobicized hydrotalcite 
Analyses: 12.7% by weight Mg 
7.6% by weight Al 
25.7% by weight C 
0.5% by weight Cl 
Mg/Al ratio: 1.9 
Al/laurate ratio: 
1.58 
______________________________________ 
35.5% by weight laurate, x=0.35; a=0.22; b=0.02 
Example 3 
Reaction of nitrate-containing hydrotalcite with sodium laurate. 20 g of a 
dried nitrate-containing hydrotalcite having the ideal formula (Mg.sub.6 
Al.sub.2 (OH).sub.16) (NO.sub.3).sub.2 * n H.sub.2 O, prepared by 
precipitation of a magnesium and aluminium nitrate solution with excess 
ammonia, were suspended in 200 ml water and, after the addition of a 
solution of 13.4 g sodium laurate in 100 ml water, the resulting 
suspension was stirred overnight at 70.degree. C. After filtration and 
washing, the precipitate was dried at 105.degree. C./100 mbar. 
______________________________________ 
Yield: 27.4 g hydrophobicized hydrotalcite 
Analyses: 17.3% by weight Mg 
6.9% by weight Al 
27.1% by weight C 
6.8% by weight H 
3.0% by weight NO.sub.3 -- 
Mg/Al ratio: 2.78 
Al/laurate ratio: 
1.36 
______________________________________ 
37.5% by weight laurate, x=0.26; a=0.19; b=0.05 
Example 4 
Reaction of pyroaurite with lauric acid. 10 g of a synthetic pyroaurite 
having the ideal formula (Mg.sub.6 Fe.sub.2 (OH).sub.16)CO.sub.3 * 4.5 
H.sub.2 O, were suspended in 150 ml isopropanol and 6.05 g lauric acid in 
50 ml isopropanol were added to the resulting suspension at room 
temperature. The suspension was then heated to the reflux temperature and 
kept at that temperature for 5 h. After filtration and washing with 
isopropanol, the product was dried at 105.degree. C./100 mbar. 
______________________________________ 
Yield: 13.5 g hydrophobicized pyroaurite 
Analyses: 16.8% by weight Mg 
12.7% by weight Fe 
34.9% by weight C 
6.8% by weight H 
&lt;0.1% by weight CO.sub.3.sup.2- 
Mg/Fe ratio: 3.04 
Fe/laurate ratio: 
0.94 
______________________________________ 
48.3% by weight laurate, x=0.25; a=0.26 
Example 5 
Reaction of the Zn/A1 l phase with lauric acid. The Zn/A1 phase having the 
ideal formula (Zn.sub.1-x Al.sub.x (OH).sub.2)(CO.sub.3).sub.x/2 * n 
H.sub.2 O with x=0.17 was synthesized by reaction of zinc oxide with an 
aqueous aluminium nitrate solution containing sodium carbonate. After 
filtration and washing, the product was dried. 40 g of this phase were 
reacted with 18.8 g lauric acid in 300 ml isopropanol below the reflux 
temperature. After filtration and washing with isopropanol, the product 
was dried at 105.degree. C./100 mbar. 
______________________________________ 
Yield: 51.9 g hydrophobicized Zn/Al phase 
Analyses: 39.1% by weight Zn 
3.3% by weight Al 
30.4% by weight C 
5.8% by weight H 
&lt;0.1% by weight CO.sub.3.sup.2- 
Zn/Al ratio: 4.89 
Al/laurate ratio: 
0.58 
______________________________________ 
42% by weight laurate, x=0.17; a=0.29 
Example 6 
Reaction of hydrocalumite with laurie acid. Hydrocalumite having the ideal 
formula (Ca.sub.2 Al(OH).sub.6)NO.sub.3 * n H.sub.2 O was synthesized by 
reaction of calcium and aluminium nitrate in alkaline solution in the 
absence of air. After filtration and washing, 20 g of the dried product 
were reacted with 12.2 g lauric acid in 300 ml water for 5 h at 70.degree. 
C., washed and dried at 110.degree. C./100 mbar. 
______________________________________ 
Yield: 27.3 g hydrophobicized hydrocalumite 
Analyses: 30.5% by weight Ca 
9.7% by weight Al 
34.5% by weight C 
7.2% by weight H 
Ca/Al ratio: 2.12 
Al/laurate ratio: 
1.50 
______________________________________ 
47.7% by weight laurate, x=0.32; a=0.21 
Example 7 
Preparation of a Zn/A1 phase and reaction with laurie acid. A solution of 
178.5 g zinc nitrate (0.6 mol) and 75.0 g aluminium nitrate (0.2 mol) was 
added to an alkaline sodium carbonate solution so that the pH value was 
always above 9. After the addition, the solution was heated for 5 hours to 
70.degree. C., filtered and washed. The colorless product was dried to 
constant weight at 110.degree. C. 
______________________________________ 
Yield: 70 g colorless powder 
Analyses: 33.5% by weight Zn 
16.5% by weight Al (x = 0.5) 
______________________________________ 
10 g of the powder were reacted under reflux with 1.25 g lauric acid for 5 
h at 70.degree. C. in 200 ml tetrahydrofuran, filtered, washed and dried 
at 110.degree. C./100 mbar. 
______________________________________ 
Yield: 10.9 g partly hydrophobicized Zn/Al phase 
Analyses: 30.5% by weight Zn 
15.3% by weight Al 
7.0% by weight C 
8.0% by weight CO.sub.3.sup.2- 
Al/laurate ratio: 
11.76 
______________________________________ 
9.61% by weight laurate, x=0.5; a=0.05; b=0.24 
Example 8 
Example 3 was repeated using 8.2 g sodium caproate. 
______________________________________ 
Yield: 24.6 g hydrophobicized hydrotalcite 
Analyses: 22.5% by weight Mg 
7.0% by weight Al 
5.1% by weight C 
8.5% by weight NO.sub.3 -- 
Al/caproate ratio: 
3.66 
______________________________________ 
8.17% by weight caproate, x=0.22; a=0.08; b=0.12 
Example 9 
Example 3 was repeated using 18.4 g sodium stearate. 
______________________________________ 
Yield: 35.4 g hydrophobicized hydrotalcite 
Analyses: 12.9% by weight Mg 
4.0% by weight Al 
32.6% by weight C 
4.7% by weight NO.sub.3 -- 
Al/stearate ratio: 
0.98 
______________________________________ 
42.85 by weight stearate, x=0.22; a=0.22; b=0.10 
Example 10 
Example 3 was repeated using 36.1 g the sodium salt of a C.sub.36 dimer 
fatty acid. 
______________________________________ 
Yield: 30.7 g hydrophobicized hydrotalcite 
Analyses: 21.1% by weight Mg 
6.5% by weight Al 
11.1% by weight C 
7.8% by weight NO.sub.3 -- 
Al/dicarboxylate ratio: 
9.38 
______________________________________ 
14.5% by weight dicarboxylate, x=0.22; a=0.06; b=0.16 
Example 11 
Reaction of a Zn/Al phase with stearic acid in a kneader. 60 g (Zn.sub.1-x 
Al.sub.x (OH).sub.2)(CO.sub.3).sub.x/2 * z H.sub.2 O with x=0.24 were 
reacted with 20.1 g stearic acid in a kneader for 3 h at 80.degree. C. A 
colorless powder was obtained. 
______________________________________ 
Yield: 79.0 g hydrophobicized Zn/Al phase 
Analyses: 38.6% by weight Zn 
5.1% by weight Al 
20.7% by weight C 
Al/stearate ratio: 
1.97 
______________________________________ 
27.1% by weight stearate, x=0.24; a=0.13 
Example 12 
Reaction of nitrate-containing hydrotalcite with stearic acid in a kneader. 
40 g of the hydrotalcite phase (Mg.sub.1-x Al.sub.x 
(OH).sub.2)(NO.sub.3).sub.x * z H.sub.2 O with x=0.25 were kneaded with 40 
ml isopropanol to a paste-like consistency and 8.5 g stearic acid were 
added to the resulting paste. After addition of 5 ml concentrated ammonia 
(25%), the kneader was heated to 80.degree. C. and kneaded to dryness. 
______________________________________ 
Yield: 47.0 g hydrophobicized hydrotalcite 
______________________________________ 
To decompose the ammonium nitrate, the product was carefully dried at 
200.degree. C. 
______________________________________ 
Analyses: 18.3% by weight Mg 
6.9% by weight Al 
15.5% by weight C 
7.0% by weight NO.sub.3 -- 
Al/stearate ratio: 
3.57 
______________________________________ 
20.3% by weight stearate, x=0.25; a=0.07; b=0.11 
Example 13 
Preparation of an Mg/Bi phase and reaction with laurie acid. A solution of 
237 g bismuth nitrate (0.6 mol) in dilute nitric acid was combined and 
stirred with a solution of 461.5 g magnesium nitrate (1.8 mol). The 
resulting mixture was added with intensive stirring to an alkaline sodium 
carbonate solution which was always present in excess. A yellow 
precipitate was formed, becoming colorless during the reaction. To 
complete the reaction, the suspension was heated to 80.degree. C. After 
cooling, the suspension was filtered, washed and dried. 285 g of a 
colorless powder were obtained. 
______________________________________ 
Analyses: 10.0% by weight Mg 
56.0% by weight Bi, x = 0.39 
______________________________________ 
135 g of the powder were suspended in 400 ml isopropanol and a solution of 
56.1 g lauric acid in 200 ml isopropanol were added to the resulting 
suspension. The suspension obtained was heated for 5 h to the reflux 
temperature and subsequently filtered, washed and dried. 
______________________________________ 
Yield: 180 g hydrophobicized Mg/Bi phase 
Analyses: 7.4% by weight Mg 
47.2% by weight Bi 
23.2% by weight C 
Bi/laurate ratio: 
1.40 
______________________________________ 
32.1% by weight laurate, x=0.43; a=0.30 
General procedure for the production of alkoxylates of compounds containing 
active H atoms using the catalysts according to the invention 
The compound to be alkoxylated was introduced into a stirred pressure 
reactor and the catalysts produced in accordance with Examples 1 to 8, 
which had been predried at 200.degree. C./100 mbar, were added. The 
reactor was purged with nitrogen and evacuated for 30 minutes at a 
temperature of 100.degree. C. The temperature was then increased to 
approx. 150.degree.-160.degree. C. and ethylene oxide or propylene oxide 
was introduced under a maximum pressure of 4 to 5 bar. The temperature of 
the exothermic reaction should not exceed 180.degree. C. On completion of 
the reaction, the reaction mixture was left to react for 30 minutes after 
which the reactor was evacuated for another 30 minutes at 120.degree. C. 
The desired reaction product was obtained after cooling and removal of the 
heterogeneous catalyst by filtration. 
Using a commercially available C.sub.12/14 fatty alcohol cut (Lorol.RTM. 
Spezial, hydroxyl value 280, a product of Henkel KGaA, batch size 300 g 
fatty alcohol), a fatty alcohol ethoxylate was prepared in accordance with 
the above procedure by addition of 3 mol ethylene oxide per mol fatty 
alcohol. 
The particular catalysts used, the concentration used, the reaction time 
and the hydroxyl values of the reaction products are listed in Table 1 
below. In addition, the corresponding product distributions obtained by GC 
analysis are shown in the accompanying Figures of Examples 1 to 6. 
TABLE 1 
______________________________________ 
c (Cat) t 
Catalyst 
% by weight h OHV HLD FIG. 
______________________________________ 
Ex. 1 0.5 0.75 174 Good 1 
Ex. 2 0.5 1 170 Good 2 
Ex. 3 0.5 0.8 173 Good 3 
Ex. 4 0.5 2.75 176 Moderate 
4 
Ex. 5 0.5 3.5 178 Good 5 
Ex. 6 0.5 2.3 178 Moderate 
6 
______________________________________ 
Legend: c (Cat) = catalyst concentration 
t = reaction time 
OHV = hydroxyl value 
HLD = homolog distribution