EP0579636A1

EP0579636A1 - Process for producing fatty alcohol polyalkylene glycol ethers

Info

Publication number: EP0579636A1
Application number: EP19920907479
Authority: EP
Inventors: Hans-Christian Raths; Wolfgang Breuer; Ansgar Behler; Elvira Scholz
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1991-04-04
Filing date: 1992-03-26
Publication date: 1994-01-26
Also published as: AU1433992A; TR25779A; JPH06505986A; WO1992017431A1; CA2107684A1; MX9201550A; DE4110834A1

Abstract

On produit des glycoléthers de polyalcène d'alcools gras à propriétés améliorées de filtrage en faisant réagir des alcools gras répondant à la formule R1-OH, dans laquelle R1 désigne un reste hydrocarboné aliphatique ayant 6 à 24 atomes de carbone et 0, 1, 2 ou 3 liaisons doubles avec en moyenne 1 à 20 moles d'oxyde d'éthylène et/ou de propylène par mole d'alcool gras, en présence de composés stratifiés. On mélange le produit de réaction avec de l'eau et avec un adjuvant de filtrage et on sépare le catalyseur et les polyglycoléthers ainsi formés, le cas échéant à des températures et/ou sous des pressions élevées.Polyalcene glycol ethers of fatty alcohols with improved filtering properties are produced by reacting fatty alcohols corresponding to the formula R1-OH, in which R1 denotes an aliphatic hydrocarbon residue having 6 to 24 carbon atoms and 0, 1, 2 or 3 double bonds with on average 1 to 20 moles of ethylene oxide and / or propylene per mole of fatty alcohol, in the presence of layered compounds. The reaction product is mixed with water and with a filter aid and the catalyst and the polyglycol ethers thus formed are separated, if necessary at high temperatures and / or under high pressures.

Description

Process for the preparation of fatty alcohol polyalkylene glycol ethers

The invention relates to a process for the preparation of fatty alcohol polyalkylene glycol ethers with improved filterability by alkoxylation of fatty alcohols in the presence of layered compounds and subsequent workup.

Addition products of ethylene and / or propylene oxide onto primary alcohols, so-called fatty alcohol polyalkylene glycol ethers, are of great importance as nonionic surfactants due to their excellent detergent properties and their high solubility in cold water for the production of washing, rinsing and cleaning agents. In the course of the alkoxylation, which is generally carried out in the presence of readily soluble alkali metal hydroxides or alcoholates, there is, however, no selective attachment of a discrete number of ethylene and / or propylene oxide units to one molecule of the alcohol, the reaction rather follows statistical laws and leads to a mixture of homologous addition products whose degrees of alkoxylation encompass a broad spectrum.

From J.Aβ.Oil.Chea.Soc. 63, 691 (1986) and HAPPI 52 (1986) it is known that the distribution of the degrees of alkoxylation in the mixture of alcohol alkoxylates, the so-called "homolog distribution", determines the properties of the addition products obtained influenced. It was found that products with a "narrow" homolog distribution, so-called "narrow-range alkoxylates", have advantages over comparable products with a "broad" homolog distribution. B .:

lower pour points, higher smoke points, lower number of moles of alkylene oxide to achieve water solubility, lower proportions of unused alcohol and associated with it, a reduced odor load and a reduction in the plu ings when spray drying polyglycol ether-containing detergent slurries.

Suitable processes for the preparation of fatty alcohol polyalkylene glycol ethers with a narrow homolog distribution are known, for example, from German patent application DE-Al-38 43 713 and US Pat. No. 4,962,237. In both cases it is proposed to carry out the alkoxylation of fatty alcohols in the presence of inorganic layer compounds, for example calcined hydrotalcite. The layer compounds which are insoluble in the reaction mixture are colloidally dispersed in the course of the reaction. This means that the separation of the catalyst required after the alkoxylation is associated with considerable difficulties, for example clogging of the filter pores, frequent filter changes, etc.

Another problem in the production of fatty alcohol polyglycol ethers by the processes mentioned is the formation of polyalkylene glycol ethers (PAG) with molecular weights of approximately 400 to 2500, which are inevitably as by-products due to traces of water accumulate and represent self-polymerization products of the alkylene oxide used. Even small amounts of PAG can lead to the formation of a gel structure in the alkoxylation product, which additionally impedes the filtration and sometimes completely comes to a standstill by separating wax-like filter deposits.

In these cases, the use of conventional filter aids, such as cellulose acetate or diatomaceous earth, leads to a shortening of the filtration times, but since the adsorption takes place unselectively, considerable amounts of the desired alkoxylation product are bound in addition to the PAG, which is naturally undesirable and the economy of the process limited. In addition, the filtrates obtained usually become turbid immediately after the filtration or become cloudy over time.

The object of the invention was therefore to develop a process for the preparation of fatty alcohol polyalkylene glycol ethers which is free from the disadvantages described.

The invention relates to a process for the preparation of fatty alcohol polyalkylene glycol ethers with improved filterability by alkoxylation of fatty alcohols in the presence of catalysts which are insoluble in the reaction mixture, which is characterized in that

Fatty alcohols of the formula (I),

Ri-OH (I) in which R represents an aliphatic hydrocarbon radical with 6 to 24 carbon atoms and 0, 1, 2 or 3 double bonds, in the presence of layered compounds with an average of 1 to 20 moles of ethylene and / or propylene oxide per mole of fatty alcohol, the reaction product with water and one Treated filter aids and separates the catalyst and formed polyglycol ether, optionally at elevated temperatures and / or elevated pressures.

Surprisingly, it was found that both the insoluble catalyst and the majority of the polyglycol ethers formed can be separated off if the alkoxylation products are treated together with a filter aid and water. It has proven particularly advantageous to carry out the separation in the heat. In this way, clear, storage-stable alkoxylation products can be obtained in very short times with minimal product loss.

Suitable starting materials for the preparation of the fatty alcohol polyalkylene glycol ethers are fatty alcohols having 6 to 24 carbon atoms and 0, 1, 2 or 3 double bonds. Typical examples of this are capronic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, gadoleyl alcohol, behenyl alcohol or erucyl alcohol. Saturated fatty alcohols with 8 to 18 carbon atoms, in particular lauryl alcohol, are preferably used.

As usual in fat chemistry, these alcohols can also be in the form of technical mixtures, such as those found in B. by high pressure hydrogenation of fatty acid methyl ester cuts vegetable or of animal origin or by hydrogenation of technical aldehyde fractions from Roelen's oxosynthesis. Technical coconut alcohol, a mixture of fatty alcohols having 12 to 18 carbon atoms, is preferably used.

In the context of the method according to the invention, layered compounds are to be understood as natural or synthetic, optionally chemically modified hydrotalcites. Hydrotalcites are known chemical compounds and can be prepared, for example, by reacting aqueous slurries of aluminum hydroxide gel, basic magnesium carbonate and magnesium hydroxide or oxide at temperatures between 70 and 85 ° C. [DE-Bl-33 06 822].

For the purposes of the process according to the invention, calcined hydrotalcites which in particular follow the formula (II) before calcination are suitable as catalysts,

M (π) _χ M (πi) θH) _y (Cθ3) _z • n H2O (II)

in the

MC ¹ *) trivalent for a divalent metal and M (III) {f j _re i _n metal ion is

and for which the conditions 1 <x <5, y> z, (y + 2z) - (2x + 3) and 0 <n <10 are fulfilled.

Suitable divalent metal ions are Ca ²⁺ , Sr ²⁺ , Ba ⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ , Cu ²⁺ and in particular Mg ²⁺ . Under trivalent metal ions are to be understood as Ga ³⁺ , Fe ^{3 * 1 "} , La ³⁺ , Cr ³⁺ , Mo ³⁺ and in particular Al ³⁺ .

Calcined hydrotalcites can be produced by heating natural or synthetic hydrotalcites at temperatures above 450 ° C [DE-Al-3843713].

In a further embodiment of the process according to the invention, hydrophobicized hydrotalcites which follow the formula (III) can also be used as catalysts,

_M (II) _aH (III) (0H) _b (C0 ₃ ) _c (A) _d - m H ₂ 0 (III)

in the

Mf ¹¹ ) for a divalent metal ion,

H (^ Π for a trivalent metal ion and

A represents the dianion of an aliphatic dicarboxylic acid having 4 to 44 carbon atoms or two anions of aliphatic monocarboxylic acids having 2 to 34 carbon atoms

and the conditions 1 <a <5, b> (2a + 2), [b + 2 (c + d)] = (2a + 3), (c + d) <0.5, c> 0, d> 0 and 0 <m <10 are satisfied.

The ions already mentioned are again suitable as divalent and trivalent metal ions. Typical examples of the nature of the ionic group A are the dianions of malonic acid, maleic acid, succinic acid or adipic acid and the anions of lauric acid, stearic acid or oleic acid. Hydrophobicized hydrotalcites can be obtained, for example, by stirring hydrotalcite into isopropyl alcohol, adding a fatty acid to the suspension and then filtering. The hydrophobicized hydrotalcites are at most dried, but not calcined, before being used.

Alkoxylation is a large-scale process known per se. To prepare the fatty alcohol polyalkylene glycol ethers, the fatty alcohols are in the presence of 0.1 to 5, preferably 0.5 to 1% by weight, based on the expected alkoxylation product, of the layered compound with 1 to 20, preferably 2 to 10, mol of ethylene - and / or propylene oxide implemented. Preference is given to adding 1 to 10 mol of ethylene and / or propylene oxide oxide to saturated fatty alcohols having 8 to 18 carbon atoms.

The alkoxylation can be carried out in a pressure vessel, for example an autoclave, in a manner known per se at temperatures from 120 to 220, in particular 160 to 200 ° C. and pressures from 1 to 5, in particular 2 to 4 bar.

The crude alkoxylation product, which contains the layer compound used as catalyst and the polyglycol ethers formed in colloidal disperse form, is mixed with water and a filter aid after the alkoxylation.

Suitable filter aids include, for example, diatomaceous earth (Celite ( ^R )), wood flour (Arbocel (R)), finely divided cellulose (LigaocellC *)) or cellulose acetate (Primisil ( ^R )). The filter aids can be used in concentrations of 0.1 to 10, preferably 0.5 to 5% by weight, based on the alkoxylation product become. The amount of water to be used together with the filter aid can be 0.1 to 15, preferably 5 to 10% by weight, based on the alkoxylation product. The weight ratio between water and filter aid is not critical and can be, for example, 1: 5 to 5: 1.

The insoluble catalyst and the polyglycol ethers formed can be separated off, for example, by centrifugation, but especially by filtration. For this purpose, z. B. flow filters (filter cartridges, Seitz filters etc.) filter presses or rotary filters.

The filtration rate is significantly influenced by the nature of the filter cake. In the sense of the method according to the invention, filter cakes are formed which have a loose to almost crystalline structure and can be easily detached from the filter.

The filtration conditions are limited by the solidification points of the products. In principle, the filtration can be carried out at temperatures from 0 to 100, preferably 25 to 70 ° C. and pressures of 1 to 10 bar. In view of a short filtration time, low product losses and high storage stability, it has proven to be optimal to carry out the filtration at temperatures from 50 to 70 ° C. and pressures from 1 to 5 bar.

In a preferred embodiment of the process, the alkoxylation product is cooled to 70 to 90 ° C. immediately after leaving the pressure vessel, with 7 to 10% by weight of water and 1 to 3% by weight of filter aids, in each case based on the alkoxy l product - mixed and filtered hot. The fatty alcohol polyalkylene glycol ethers obtainable by the process according to the invention are easy to filter, are clear and are suitable for the production, for example, of detergents and cleaning agents and for products for hair and body care, in which they are used in amounts of 0.1 to 25% by weight. -% - based on the solids content of the agents - may be included.

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

Examples

I. Manufacture of raw materials

Calcined hydrotalcite. A commercially available synthetic hydrotalcite was calcined at 500 ° C. for 8 hours.

Ci2 / i4 coconut fatty alcohol + 2.5 mol EO (A). 250 g (1.3 mol) of Ci2 / 14 coconut oil alcohol (Lorol ( ^R ) S, hydroxyl number 290, from Henkel KGaA) were placed in a pressure reactor and 3 g, corresponding to 0.5% by weight, - based on the expected alkoxylation product - the previously prepared calcined hydrotalcite. The reactor was purged with nitrogen and evacuated at a temperature of 100 ° C for 30 minutes. The temperature was then increased to 180 ° C. and 143 g (3.25 mol) of ethylene oxide were injected in portions over a period of 90 minutes at a pressure of 4 bar. After the addition of ethylene oxide had ended, the mixture was left to react for 30 minutes. After the autoclave had been let down, approx. 390 g of an adduct of an average of 2.5 mol of ethylene oxide with coconut oil alcohol were obtained.

II. Carrying out the filtration experiments

The corresponding amounts of filter aid and water were stirred into 500 g of an adduct of an average of 2.5 mol of ethylene oxide with a coconut fatty alcohol (A) at a temperature of 25 to 90 ° C. The alkoxylation catalyst and a large part of the PAG formed were then filtered off under pressure.

Filter: 2.21 SEITZ pressure filter, type EF 14/2 with an outer jacket tempered by a HAAKE F3 thermostat \

Pressure: 2.5 bar

Filter layer: BEGEROW filter layer KD7 (diameter: 12 cm)

The results are summarized in Tab. 1.

Tab. 1: Filtration of coconut fatty alcohol-2.5 EO

Percentages as% by weight based on (A)

E.g. FHM cFHM cH? 0 I KH K PV KV Ft%% ° C mm g% ml / g min

1 Primisil 2.0

2 Primisil 2.0

3 Primisil 2.0

4 Primisil 2.0

5 Primisil 2.0

VI without

V2 Primisil 2.0

V3 Primisil 2.0

Legend: FHM: filter aid cFHM: concentration of filter aid

CH2O: water concentration

T: filtration temperature

KH: height of the filter cake

KG: weight of the filter cake

PV: product loss

KV: Specific volume of the filter cake

Ft: filtration time

The filtrates according to Examples 1 to 5 were clear both in the heat and at room temperature.

Claims

1. A process for the preparation of fatty alcohol polyalkylene glycol ethers with improved filterability by alkoxylation of fatty alcohols in the presence of catalysts insoluble in the reaction mixture, characterized in that

Fatty alcohols of the formula (I),

Ri-OH (I)

in which R ^{1 represents} an aliphatic hydrocarbon radical having 6 to 24 carbon atoms and 0, 1, 2 or 3 double bonds, in the presence of layered compounds with an average of 1 to 20 moles of ethylene and / or propylene oxide per mole of fatty alcohol, the reaction products are reacted with Water and a filter aid are added and the catalyst and polyglycol ethers formed are separated off, if appropriate at elevated temperatures and / or elevated pressures.

2. The method according to claim 1, characterized in that one uses saturated fatty alcohols with 8 to 18 carbon atoms.

3. Process according to claims 1 and 2, characterized in that calcined hydrotalcites are used as layer compounds which follow the calcination of the formula (II),

M (II) _χ M (HI) (OH) _y (Cθ3) _z ^• n H ₂ 0 (II)

in the M *) stands for a divalent metal ion and M (IH) for a trivalent metal ion

and for which the conditions 1 <x <5, y> z, (y + 2z) = (2x + 3) and 0 <n <10 are fulfilled.

4. Process according to claims 1 and 2, characterized in that hydrophobicized hydrotalcites are used as layer compounds, which follow the formula (III),

_M (II) _aM (III) (0H) _b (C0 ₃ ) _c (A) d ^• m H ₂ 0 (III)

in the

Mf ¹¹ ) for a divalent metal ion,

M (HI) for a trivalent metal ion and

A stands for the dianion of an aliphatic dicarboxylic acid with 4 to 44 carbon atoms or two anions of aliphatic monocarboxylic acids with 2 to 34 carbon atoms

and for which the conditions 1 <a <5, b> 2a + 2, [b + 2 (c + d)] = (2a + 3), (c + d) <0.5, c> 0, d> 0 and 0 <m <10 are satisfied.

5. The method according to at least one of claims 1 to 4, characterized in that the layer compounds are used in concentrations of 0.1 to 5% by weight, based on the expected alkoxy product.

6. The method according to at least one of claims 1 to 5, characterized in that one carries out the alkoxylation with 1 to 10 moles of ethylene and / or propylene oxide per mole of fatty alcohol.

7. The method according to at least one of claims 1 to 6, characterized in that one carries out the alkoxylation at temperatures of 120 to 220 ° C and pressures of 1 to 5 bar.

8. The method according to at least one of claims 1 to 7, characterized in that substances are used as filter aids, which are selected from the group consisting of diatomaceous earth, Holz¬ flour, cellulose or cellulose acetate.

9. The method according to at least one of claims 1 to 8, characterized in that the filter aid is used in amounts of 0.1 to 10 wt .-% - based on the alkoxylation product.

10. The method according to at least one of claims 1 to 9, characterized in that water is used in amounts of 0.1 to 15 wt .-% - based on the alkoxylation product.

11. The method according to at least one of claims 1 to 10, da¬ characterized in that one carries out the separation at temperatures from 0 to 100 ° C.

12. The method according to at least one of claims 1 to 11, da¬ characterized in that one carries out the separation at pressures of 1 to 10 bar.

13. The method according to at least one of claims 1 to 12, da¬ characterized in that the catalyst and polyglycol ether formed are separated by filtration.