DE2914189A1 - METHOD FOR PRODUCING NONADECANDIOLES - Google Patents

Description

29H189

4000 Düsseldorf, April 5, 1979 HENKELKGaA

Henkelstrasse 67 ZR-FE / Patents

Dr. Gla / Ge

Patent application D

"Process for the production of nonadecandlolen"

The invention relates to a method for producing Compound mixtures containing nonadeeandiols by reacting oleyl alcohol: l with hydrogen and carbon monoxide under the conditions of oxo synthesis.

U.S. Patent No. 2,599,468 discloses a process for the preparation of Nonadecandiolen known * Here are ölsäureester lower aliphatic alcohols with carbon monoxide and V / on Hydrogen in the presence of cobalt oleate at 140 to 250 ⁰ C and under a pressure from 150 to 275 atm to the corresponding Pormylstearinsäureestern implemented. In the second stage of the process, the aldehyde-ester obtained in the presence of copper chromite catalysts at from 250 to 35O ⁰ C under a pressure of 175 atm to 300 are to the corresponding diprimary alcohols hydrogenated.

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Ö30G43 / 0173

Patent application ^D 5904 -T HENKELKGaA

^ ZR-FE / Patents

Bulletin de la Socie * te Chimique de France 1969 ₉ pages 2826 to 2830 describes a process in which oleyl alcohol is reacted with carbon monoxide and hydrogen at 190 ° C. and a pressure of at least 150 kg / cm "" in the presence of cobalt acetate. The products of the oxo synthesis are then converted into the corresponding acetates with acetic anhydride, which are then purified by distillation and finally saponified to give the desired diol compounds.

According to the known state of the art, the nonadecanediols which are of interest as valuable intermediates for chemical syntheses can only be obtained via complex, uneconomical processes. The present invention therefore had the object of finding _s to a method which allows to produce in a single stage process with Nonadecandiole economically satisfactory yields. The solution to this problem lies in the method described below.

The invention relates to a method for the production. lung mixtures of Nonadecandiolen of oleyl alcohol under the conditions of the oxo process, which is characterized in that, bar reacting oleyl alcohol hydrogen and carbon monoxide at 110 to 20O ⁰ C under a pressure in 100 to ¹ IOO in the presence of a Rhodlumkatalysators and a tertiary amine to each other .

When carrying out the process according to the invention, technical-grade oleyl alcohol is generally used as the starting material used.

Trialkylamines and their alkyl radicals are suitable as tertiary amines Have 1 to 20 carbon atoms, tertiary

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29U189

Patent application D 59OiJ J? HENKELKGaA

* ZR-FE / patents

aromatic amines, tertiary amines containing aliphatic and aromatic radicals, tertiary diamines and tertiary hydroxy alley amines. Examples of such amine compounds include: trimethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-octylamine, dimethyldecylamine, diethyldodecylamine, diethylstearylamine, didecylmethylamine, didodecyl-n-propylamine, triphenylamine, dimethylaniline, diethylnaphthylamine, naphthylamine, N, N ¹ , N'-Tetramethylhexamethylenediamine, N, N, N ¹ , N ¹ -Tetraethy! Propylenediamine, triethanolamine, tripropanolamine, bis- (2-hydroxyethyl) -methylainine, bis- (2-hydroxypropyl) -butylamine and bis- (2-hydroxyethyl) decylamine. Trialkylamines, in particular triethylamine, are preferably used.

When carrying out the method according to the invention the tertiary amines are expediently employed in amounts such that per mole of oleyl alcohol to be reacted 0.2 to 1.5 moles of amine are present.

In the case of the rhodium catalysts which are effective in the process according to the invention they are rhodium carbonyl complexes, the exact composition of which is not known. One can however, assume that it is rhodium carbonyl complexes in which one or more carbonyl ligands are replaced by amine ligands. The actually effective complex compound is in each case in situ formed under the prevailing reaction conditions. The amount of rhodium required for this can therefore the reaction mixture in the form of rhodium chloride, rhodium oxide, rhodium salts of fatty acids, rhodium chelates, Rhodium carbonyl or dimeric rhodium carbonyl chloride are supplied.

The rhodium compounds are employed advantageously in quantities such that, based on the oleyl alcohol, 5-5000 ppm, preferably 15 to ¹ ppm IOO, calculated as metal, are present. iu

03C043 / 0173

29U189

Patent application D 5904 X HENKELKGaA

£ ZR-FE / patents

In the hydrogen used in the process according to the invention - / carbon monoxide mixture, the molar ratio is expediently in the range from 1.5 * · 1 to 2.5: 1.

When carrying out the method according to the invention is the presence of a solvent is not required. If desired, however, solvents can be used are, especially saturated hydrocarbons such as pentane, hexane, heptane or cyclohexane, aromatic Hydrocarbons such as benzene or toluene, ethers such as tetrahydrofuran or dioxane, and alcohols such as methanol, Ethanol, propanol and isopropanol come into consideration.

The inventive method can be carried out in the usual high-pressure synthesis reactors =

The reaction mixtures obtained are worked up by distillation under reduced pressure Pressure.

The products of the process are mixtures of 2-alkylver- ■ branched c *> £ O-alkanediols are obtained. As the main products these mixtures contain the compounds 2-octylundecanediol-1,11 and 2-nonyldecanediol-l, 10. The mixtures also contain minor amounts as by-products other 2-alkyl branched alkanediols of carbon number C, indicating a double bond isomerization occurring during the reaction go back.

Those produced by the process of the invention

■ Nonadecanediol mixtures are valuable intermediates for a number of organic syntheses darο you can ZoB. with ethylene oxide and / or propylene oxide to the corresponding surface-active polyalkylene glycol ethers and with sulfuric acid to the surface-active ones as well

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0 3 004 3/0173

29U189

Patent application D 59O ¹ I & / HENKELKGaA

ZR-FE / Paterite

Mono- and Dlsulfaten are implemented. These compound mixtures are also suitable as diol components the production of polycondensates.

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

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Patent application D 59O4 '"6 ^ f. HENKELKGaA

ZR-FE / Patenta

Examples example 1

540 g (2 mol) of oleyl alcohol, 202 g (2 mol) of triethylamine and 0.1 g (0.44 mol) of RhCl, 3 H ₃ O were mixed with one another in a 5 l stainless steel reciprocating stirrer autoclave. The autoclave was purged with carbon monoxide. Then carbon monoxide was injected up to a pressure of 75 ^bar and a pressure of 200 bar was set by adding hydrogen gas. The autoclave contents were heated with stirring to 13O ⁰ C. The mixture was then heated for a further 5 hours with continued stirring, the temperature initially being increased gradually (by about 10 ° C./30 min) to 180 ° C. and then left at this value.

After cooling to room temperature, the reaction mixture obtained (612 g) was distilled in vacuo under a nitrogen atmosphere. After the amine and the unreacted, partially hydrogenated oleyl alcohol had been separated off, 460 g of nonadecanediols (76 % of theory) were passed over ^{at 190 to 202 ° CO, 4 m bar.} The OH number of the product was 369 (theoretical 373), the CO number was found to be 0.3.

Example 2

540 g (2 mol) of oleyl alcohol, 286 g (2 mol) of tri-n-propylamine and 0.1 g (0.44 mol) of RhCl, .3 H ₃ O were mixed with one another in a 5 l reciprocating stirrer autoclave. The autoclave was purged with carbon monoxide. Then carbon monoxide was injected up to a pressure of 75 bar and a pressure of 200 bar by admixing hydrogen gas

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03CC43 / 0173

Patent application D 590A-f

ZR-FE / patents

set. The contents of the autoclave were heated ^{to 130 ° C. with stirring.} 6 hours further heated subsequently, with continued stirring, the temperature first gradually (by about 10 ° C / 30 minutes) was raised to 180 ⁰ C and then left at this value.

The reaction mixture obtained was distilled in vacuo under a nitrogen atmosphere. After the amine and the unreacted oleyl alcohol had been separated off, 428 g of nonadecanediols (71 % of theory) were obtained. The OH number of the product was 367 (theoretical 373). The CO number was 0.

Example 3

540 g (2 mol) of oleyl alcohol, 370 g (2 mol) of tri-n-butylamine and 0.1 g (0.44 mol) of RhCl? · 3 H ₂ O mixed together _? After the autoclave had been flushed with carbon monoxide, carbon monoxide was injected up to a pressure of 75 bar. A pressure of 200 bar was set by mixing in hydrogen gas. The contents of the autoclave were then heated ^{to 130 ° C. with stirring.} The mixture was then heated for a further 6 hours with continued stirring, the temperature initially being increased gradually (by about 10 ° C./30 minutes) to 180 ° C. and then left at this value.

The reaction mixture obtained was distilled in vacuo under a nitrogen atmosphere. After the amine and the unreacted oleyl alcohol had been separated off, 43O g of nonadecanediols (71 % of theory) were obtained. The OH number of the product was 355 (theoretical 373). The CO number was 0.

03G043 / 0173

Claims (6)

Patent application D 5904 tf HENKELKGaA ZR-FE / patents "Process for the production of nonadecanediols" Claims A process for the preparation of mixtures of Nonadecandiolen of oleyl alcohol under the conditions of the oxo process, characterized in that Oleylalkoholj hydrogen and carbon monoxide at 110 to 200 ⁰ C under a pressure of 100 to iOO ^ bar a rhodium catalyst and a tertiary amine transposed together in the presence 2. The method according to claim 1, characterized in that that the reaction in the presence of trialkylamines, the alkyl radicals of which have 1 to 10 carbon atoms. 3. Process according to Claims 1 and 2 _f, characterized in that the reaction is carried out in the presence of triethylamine * ' * i. Process according to Claims 1 to 3, characterized in that the reaction is carried out in the presence of 0.2 to 1.5 mol of tertiary amine per column of oleyl alcohol. 5. Process according to claims 1 to 4, characterized in that the reaction is carried out in the presence of 5 to 5,000 ppm of rhodium, calculated as metal and based on oleyl alcohol. 6. The method according to claims 1 to 5 *, characterized in that that the reaction with a hydrogen / carbon monoxide mixture in a molar ratio of 1.5: up to 2.5: 1. 030043/0173 ORIGINAL INSPECTED