EP0433309A1

EP0433309A1 - Use of metallic acetyl acetonates as catalysts for ethoxylation or propoxylation

Info

Publication number: EP0433309A1
Application number: EP89909551A
Authority: EP
Inventors: Uwe Ploog
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1988-09-01
Filing date: 1989-08-23
Publication date: 1991-06-26
Also published as: WO1990002721A1; DE3829751A1; EP0361083A1; KR900701695A

Abstract

L'emploi d'acétylacétonates métalliques de formule générale M(ACAC)n, dans laquelle M est un cation métal du groupe composé de Al3+, Cr3+, Fe3+, Mn2+, Sn2+, Ti4+, Zn2+ et Zr4+, ACAC est un anion de l'acétylacétonate et n est un nombre correspondant au nombre des covalences de charges du cation métal, comme catalyseurs pour l'éthoxylation ou la propoxylation de composés avec des atomes actifs de H permet d'obtenir une répartition serrée des homologues des produits d'alkoxylation.Using metal acetylacetonates of the general formula M (ACAC) n, in which M is a metal cation from the group consisting of Al3 +, Cr3 +, Fe3 +, Mn2 +, Sn2 +, Ti4 +, Zn2 + and Zr4 +, ACAC is an anion of acetylacetonate and n is a number corresponding to the number of charge covalencies of the metal cation, as catalysts for the ethoxylation or propoxylation of compounds with active atoms of H allows to obtain a close distribution of the homologues of the alkoxylation products.

Description

Use of metal acetylacetonates as catalysts for the ethoxylation or propoxylation.

The invention relates to catalysts for the ethoxylation or propoxylation of compounds with active H atoms.

Among compounds with active H atoms in the sense of the invention are e.g. To understand fatty alcohols, Guerbet alcohols, fatty acids and amines, which form non-ionic detergents during ethoxylation or propoxylation. A typical example of this is the reaction of fatty alcohols with usually 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 catalysts for the aforementioned polyalkoxylation include: the following have been used:

Calcium and strontium hydroxides, alkoxides and phenoxides (EP-A 00 92 256),

Calcium alkoxides (EP-A 00 91 146),

Barium hydroxide (EP-B 0 115 083), basic magnesium compounds, e.g. alkoxides (EP-A 00 82 569),

Magnesium and calcium fatty acid salts (EP-A 0 85 167).

Antimony pentachloride (DE-A 26 32 953),

Aluminum isopropylate / sulfuric acid (EP-A 22 81 21),

Oxo compounds containing zinc, aluminum and other metals (EP-A 180 266),

Aluminum alcohols / phosphoric acids (US 4,721,817).

Other common polyalkoxylation catalysts are potassium hydroxide and sodium methylate.

The aforementioned catalysts have i.a. the disadvantage that they are difficult to incorporate into the reaction system and / or are difficult to manufacture. Furthermore, when using alkali hydroxides and alkali alcoholates, the range of the degree of polyalkoxylation that can be achieved, i.e. the

Homolog distribution, which will be discussed in more detail below, large or wide. Acidic catalysts, e.g.

Antimony pentachloride, do cause a closer

Homolog distribution and lower fatty alcohol content of the reaction products, however, show high corrosiveness and are partially toxic. When using mixtures from

Aluminum alcoholates and sulfuric acid can achieve a narrow homolog distribution of the alkoxylation products with good conversion in the case of linear fatty alcohols, but not with branched alcohols, e.g. the so-called

Guerbet alcohols.

The so-called narrow range of degrees of polyalkoxylation is of particular importance for fatty alcohol polyalkoxylates, cf. JAOCS, Vol. 63, 691-695 (1986), and HAPPI, 1986 (5), 52 - 54. The so-called "narrow-rank" alkoxylates therefore have the following advantages in particular:

- low pour points

- higher smoke points

- fewer moles of alkoxide to achieve water solubility

- fewer hydrotopes for introduction into liquid

Universal detergent

- a lesser, free by the presence (not

implemented) odor caused by fatty alcohols

- Reduction of plumings when spray drying

Detergent slurries containing fatty alcohol polyalkoxylate surfactants.

The range or homolog distribution of the fatty alcohol polyalkoxylates depends essentially on the type of used

Catalyst. The measure of the homolog distribution is the so-called Q value according to the relationship

Q = n *. p ² in the n * is the average adduct number (mean

Degree of ethoxylation) and p mean the percentage of the adduct with certain EO degrees, which is predominantly formed. A large Q value therefore means a narrow range of homolog distribution.

Oxethylates with a low content of free fatty alcohols have an increased degree of conversion in the production of ether carboxylic acids by reacting the oxethylates with sodium chloroacetates in the presence of alkali metal hydroxides. Farther are ethoxylates with restricted homolog distribution, highly effective thickeners for surfactant solutions.

It has now been found that using metal acetylacetonates of the general formula I

M (ACAC) _n (I)

in the

M is a metal cation from that of Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Mn ²⁺ ,

Sn ²⁺ , Ti ⁴⁺ , Zn ²⁺ and Zr ⁴⁺ formed group,

ACAC is an anion of the acetylacetonate and n is a number corresponding to the charge number of the

Metal cations mean as catalysts for the ethoxylation or

Propoxylation of compounds with active H atoms resulted in a surprisingly narrow homologous distribution of the

Polyalkoxylation products is coming.

The metal acetylacetonates of the general formula I to be used according to the invention which are known compounds and for the most part are commercially available include:

AI (ACAC) ₃

Cr (ACAC) ₃

Fe (ACAC) ₃

Mn (ACAC) ₂

Sn (ACAC) ₂

Ti (ACAC) ₄

Zn (ACAC) ₂

Zr (ACAC) ₄ . Instead of the aforementioned acetylacetonates can also

Mixtures of salts of the aforementioned metals with acetyl acetone, which the respective acetylacetonates "in situ".

form, are used, e.g. Zinc sulfate / acetylacetone or tin (II) oxalate / acetylacetone mixtures.

Metal acetylacetonates from the above list are particularly advantageous, in which the metal cation M is selected from the groups formed by Al ³⁺ , Fe ³⁺ , Zn ²⁺ and Zr ⁴⁺ ; Such metal acetylacetonates are physiologically harmless and can therefore, if desired, remain in the alkoxylation products.

According to a preferred embodiment of the process of the invention, the catalysts are added in an amount of 0.1 to 2% by weight, based on the end product of the ethoxylation or propoxylation.

The invention is explained in more detail below on the basis of preferred exemplary embodiments. All percentages are in percent by weight.

1. Preparation of the catalysts.

The reaction mixtures are advantageously carried out by

Mixing of the amounts of acetylacetonates listed in Table 1 with the material to be polyalkoxylated, in particular the fatty alcohols according to Table 1. However, the catalysts e.g. in the form of a concentrated solution in the fatty alcohols, from which aliquots are used.

Instead of the finished catalysts, their starting materials can also be used, e.g. a mixture of

Zinc sulfate heptahydrate and acetylacetone (6 mmol / 30 mmol per 100 g end product of the ethoxylation) and a mixture of

Tin (II) oxalate and acetylacetone (10 mmol / 30 mmol per 100 g end product of the ethoxylation).

2. Conditions of the oxyalkylation.

The fatty alcohols to be alkoxylated according to Table 1 were mixed with the specified catalysts and transferred to a suitable autoclave. After approximately 30 minutes of evacuation at 100 ° C. and flushing with nitrogen, the temperature was raised to approximately 180 ° C. and the desired amount of ethylene oxide was pressed in at a maximum of 5 bar. After a reaction time of 30 min, unreacted alkylene oxide was drawn off at 100 ° C./14 mbar.

The OH number and the polyglycol content (PG) of the alkoxylates formed were determined; continued to be a

Gas chromatogram to determine the homolog distribution or the Q value based on the measured area percentages. Examples 1 to 4.

In these examples, the procedure above for the ethoxylation of fatty alcohols with 2 moles of ethylene oxide was followed. In Table 1, the fatty alcohols and catalysts used, the amount of catalyst used (in mmol / 100 g of ethoxylation product), the reaction time, the reaction temperature, the Q value determined, the OH numbers of the

Ethoxylation products (found / calculated), the content of free fatty alcohols (FFA,%) and the polyglycol content (PG,%) summarized.

Comparative tests.

The results with catalysts known from the prior art are summarized in Table 2.

The fatty alcohols mentioned in the tables were commercial, technical fatty alcohol mixtures with the following composition:

C 12/14: fatty alcohol of chain length distribution 0 - 2% C 10, 70 - 75% C 12, 20 - 30% C 14, 0 - 2% C 16; Iodine number less than 0.3, average molecular weight 194, hydroxyl number 285-293.

C 12: fatty alcohol of the chain length distribution 0-2% C 10, at least 97% C 12, 0-3% C 14, iodine number less than 0.3, average molecular weight 188, hydroxyl number 295 - 301.

Claims

Use of metal acetylacetonates of the general formula I

M (ACAC) _n (I) in the

M is a metal cation from that of Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Mn ²⁺ ,

Ni ²⁺ , Sn ²⁺ , Ti ⁴⁺ , Zn ²⁺ and Zr ⁴⁺ formed group,

Metal cations mean, as catalysts for the ethoxylation or propoxylation of compounds with active H atoms.

2. Use according to claim 1, characterized in that one uses metal acetylacetonates of the general formula I in which M is a metal cation from the group formed by Al ³⁺ , Fe ³⁺ , Zn ²⁺ and Zr ⁴⁺ and ACAC and n as are defined above.

3. Use according to claim 1 or 2, characterized in that the catalysts in an amount of 0.1 to

2 wt .-%, based on the end product of the ethoxylation or propoxylation.