The present invention relates to an improved process for al- koxylating active hydrogen compounds by reaction with an al¬ kylene oxide of from 2 to 4 carbon atom .

Narrow distribution or "peaked" alkoxylates having a narrow molecular weight or homolog distribution are becoming in- creasingly important, since they have better application properties than the ordinary, broad distribution alkoxylates which are normally prepared using alkali metal hydroxides or alkoxides as catalysts. They find use in the main as surfac¬ tants in detergent and cosmetic compositions, but also in the paper and the textile fiber industries. There is there¬ fore an urgent need for efficient processes for synthesizing such narrow distribution alkoxylates.

US-A-3,957,922 (1) relates to a process for preparing alkox- ylated products using aluminum or iron compounds as cata¬ lysts. The iron compounds mentioned are iron salts of cus¬ tomary mineral acids such as iron(III) chloride, iron(III) sulfate, iron(II) chloride, iro (II) sulfate, iron(II) ni¬ trate and iron(III) phosphate, iron salts of fatty acids, iron powders, hydrates of iron(III) chloride and iron(II) chloride and sulfate and also commercial iron-coated cata¬ lyst materials.

EP-B-090,445 (2) relates to a process for polymerizing epox- ides using double metal cyanide complexes as catalysts.

These complexes may contain iron(III) and iron(II) atoms. It is also possible for water-soluble iron(III) salts to be present.

US-A-4,727,199 (3) describes heterogeneous alkoxylation cat¬ alysts consisting of a metal oxide bonded to an anion. One of the metal oxides mentioned is iron oxide. The anion-bound metal oxide catalysts are amorphous or predominantly amor¬ phous.

The narrow distribution alkoxylates prepared as described in references (1) to (3) are still in need of improvement as regards their homolog distribution and their application

properties. It is an object of the present invention to pro¬ vide a process' for preparing alkoxylates having improved properties.

We have found that this object is achieved by a process for preparing alkoxylates of active hydrogen compounds by react¬ ing the active hydrogen compounds with an alkylene oxide of from 2 to 4 carbon atoms, which comprises using iron oxides as alkoxylation catalysts.

The iron oxide used can be any known iron oxide. The most important iron oxides are iron(II) oxide of the formula FeO, iron(III) oxide of the formula Fe ₂ θ ₃ and iron(II,III) oxide of the formula Fea0. Particularly good results are obtained with iron(III) oxide, which occurs in the two modifications α-Fe ₂ 0 ₃ (hematite), and γ-Fe ₂ 0 ₃ (maghemite) . Preference is given to α-Fe ₂ 0 ₃ which has a corundum structure. The iron oxides used are in general polycrystalline.

The catalytic activity of iron oxides is crucially deter¬ mined by their surface area. Brunauer-Emmett-Teller (BET) surface areas of below 100 m ² /g give only inadequate re¬ sults, in particular an excessively high level of uncon¬ verted active hydrogen starting compound. Values within the range from 120 m ² /g to 135 m ² /g give the best results. Iron oxides having a BET surface area of greater than 135 m ² /g are virtually impossible or very difficult to prepare, so that this value must be deemed a reasonable upper limit.

The iron oxides described can be prepared in a conventional manner, for example iron(II) oxide may be prepared by heat¬ ing iro (III) oxalate in the absence of air or iron(II) ox¬ ide by thermal dehydration of iron(III) hydroxide. A pre¬ ferred method for preparing iron(III) oxide is the oxidation of iron pentacarbonyl by means of atmospheric oxygen at about 600°C.

The alkoxylation process, or oxyalkylation process as it is often called, according to the present invention is custo - arily carried out at 50-230°C, preferably at 100-180°C.

Above 230°C there is a distinct drop in catalyst activity, probably because the total surface area shrinks due to bak¬ ing together of the particles. Particularly good results in

respect of a sharply peaked homolog distribution are ob¬ tained at 140-160°C.

The reaction is in general carried out under superatmos- pheric pressure, for example in an autoclave at 3-6 bar. The reaction is advantageously carried out without a solvent, but an inert solvent may be present. Under the conditions mentioned, the reaction normally takes 5-10 hours.

The alkoxylation catalyst, which is preferably composed of one but may also be composed of more than one iron oxide, is used in an amount of from 0.1 to 25% by weight, preferably from 0.5 to 15% by weight, based on the amount of active hy¬ drogen compound. Especially preferred is an amount of from 2 to 10% by weight, in particular with respect to a low level of unconverted active hydrogen starting compound.

The active hydrogen compound used can be any compound which has one or more acidic hydrogen atoms capable of reaction with alkylene oxides. There may be mentioned here in partic¬ ular alcohols, phenols, carbohydrates, carboxylic acids, carboxamides, amines and mercaptans, which fall within the general formula II

R-[-X-H] _m II

where R is a customary hydrocarbon radical which may contain hetero atoms and carry further functional groups, X is 0, S, NH or NR, and m is 1, 2, 3 or more.

Depending on m, R is monovalent, divalent or trivalent. Preference is given to monovalent and divalent radicals, es¬ pecially the former.

Particular meanings of R are: straight-chain or branched Cι-C ₃ o-alkyl and C ₃ -C ₃ o-alkenyl, which may each be interrupted by one or more nonadjacent oxygen atoms and may carry additional hydroxyl groups, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-ethylhexyl, n-octyl, isononyl, decyl, n-dodecyl, isotridecyl, myristyl, cetyl, stearyl, eicosyl, 2-propenyl, oleyl, linolyl, linolenyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 4-methoxybutyl, 4-(4'-methoxybutyloxy)-butyl, 2-hydroxyethyl

or 4-hydroxybutyl; Cι-C ₃ o~ cyl, which may additionally carry hydroxyl groups, e.g. for yl, acetyl, propionyl, butyryl, valeryl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl or lactyl; monovalent carbohydrate radicals of mono- or disaccharides if X is 0, e.g. of glucose, mannose, fructose, sucrose, lac¬ tose or maltose; aryl having in total from 6 to 20 carbon atoms, which may additionally be substituted by C_ _. -C ₄ -alkyl, hydroxyl, Cι-C ₄ -alkoxy or amino, e.g. phenyl, tolyl, xylyl, hydroxy- phenyl, methoxyphenyl, aminophenyl or naphthyl; arylcarbonyl having in total from 7 to 21 carbon atoms, which may additionally be substituted by Cι~C -alkyl, hy¬ droxyl, Cι-C ₄ -alkoxy or amino, e.g. benzoyl; divalent radicals derived for example if X is 0 from diols, dihydroxy aromatics or bisphenols, such as 1,2-ethylene, 1,3-propylene, 1,4-butylene, phenylene or the radical of bisphenol A; trivalent radicals derived for example if X is 0 from triols such as glycerol.

In a preferred embodiment, the active hydrogen compound II, is a Cι-C ₃ o-alka ol or a C ₃ -C ₃ _-alkenol, in particular a Cs-C ₃ o-alkanol or -alkenol (a fatty alcohol) ,

The process according to the present invention produces from the active hydrogen compounds II alkoxylation products of the general formula I

R-[-X-(A-0) _n -H] _I

where A is 1,2-alkylene of from 2 to 4 carbon atoms, prefer¬ ably of 2 or 3 carbon atoms, and the degree of alkoxylation, n, is from 1 to 100, preferably from 1 to 20, in particular from 2 to 15. The narrowest homolog distribution of the alk- oxylaton products is obtained when n is from 3 to 10.

The alkylene oxide used is in particular propylene oxide or ethylene oxide, in particular the latter, but it is also possible to use a butylene oxide such as ethyloxirane, 1,2-dimethyloxirane or 1,1,-dimethyloxirane.

The alkoxylates produced by the process according to the present invention have a sufficiently narrow molecular weight distribution; that is, the proportion of homologs having a low or high degree of alkoxylation is small. In general about 75%, advantageously about 85% or more, of the homologs are within a range of 5 alkylene oxide units.

Owing to the narrow molecular weight or homolog distribu¬ tion, alkoxylates from the process according to the present invention which are used as surfactants in aqueous detergent formulations are sufficiently soluble and do not make the solutions undesirably viscous, two properties which are dif¬ ficult to obtain at one and the same time from the customary alkoxylates having a broad molecular weight distribution.

Furthermore, the alkoxylates produced by the process accord¬ ing to the present invention contain only small residual concentrations of the active hydrogen starting compounds, for example fatty alcohol, which in many cases, if present in excessively high concentration, lead to odor problems in the alkoxylates and make it difficult to work up these prod¬ ucts, for example by spray drying.

The use of iron oxides which are highly active as alkoxyla- tion catalysts but otherwise inert has further advantages. The iron oxides used, being insoluble and having a certain particle size distribution, are easy to filter out of the liquid products or reaction mixtures. The products obtained are colorless and have a neutral pH. In principle, the re- movable iron oxides are regenerable and hence re-employable for further alkoxylations.

Example 1

Preparation of n-dodecanol ethoxylate having a homolog peak at 3 mol of ethylene oxide

250 g (1.34 mol) of n-dodecanol and 12.5 g of α-iron(III) oxide having a BET surface area of 135 m ² /g (corresponding to 5% by weight, based on n-dodecanol) were introduced into a 2-liter steel autoclave. The autoclave was flushed twice with nitrogen and then heated to 150°C. Ethylene oxide in an amount of 177 g (4.02 mol) was injected over the course of

4 hours during which the pressure did not exceed 6 bar. Thereafter the contents were stirred at 150°C for 3 hours until the pressure was constant.

The product obtained was filtered while still hot. The fil¬ trate was a colorless, clear liquid having neutral pH. Fig. 1 shows the homolog distribution of the alkoxylation product.

Examples 2a to 2d

Effect of BET surface area of catalyst

Example 1 was repeated, except that 250 g of n-dodecanol were reacted with 177 g of ethylene oxide in the presence of 5 g each time of α-iron(III) oxides (corresponding to 2% by weight, based on n-dodecanol) having different BET surface areas. Table 1 shows the residual level of unconverted n-do¬ decanol as a function of the BET surface area.

Table 1

not according to the present invention

Examples 3a to 3e

Effect of catalyst concentration

Example 1 is repeated, except that 250 g of n-dodecanol were reacted with 177 g of ethylene oxide in the presence of dif¬ ferent amounts of α-iron(III) oxide having a BET surface area of 135 m ² /g. Table 2 shows the residual level of uncon¬ verted n-dodecanol as a function of the amount of catalys .

Table 2

Example 4

Preparation of n-dodecanol ethoxylate having a homolog peak at 5 mol of ethylene oxide

Example 1 is repeated, except that 250 g (1.34 mol) of n-do¬ decanol were reacted with 354 g (8.04 mol) of ethylene oxide in the presence of 5 g of α-iron(III) oxide having a BET surface area of 135 m ² /g (corresponding to 2% by weight, based on n-dodecanol) . Filtration left a colorless, viscous liquid. Fig. 2 shows the homolog distribution of the alkox¬ ylation product.

Examples 5a to 5d

Effect of reaction temperature

Example 4 is repeated, except that 250 g of n-dodecanol were reacted with 354 g of ethylene oxide in the presence of 5 g of α-iron(III) oxide having a BET surface area of 135 m ² /g at various temperatures. Table 3 shows the maximum attain¬ able level of the peak homolog in the product mixture, namely the reaction product with 5 mol of ethylene oxide, as a f nction of the reaction temperature.

Table 3