DD281594A5 - METHOD FOR PRODUCING LOW-CARBURATED HYDROCARBONS OF MEDIUM CHAIN LENGTH - Google Patents

Abstract

The invention relates to the production of terminal ungesaettigten hydrocarbons medium chain length by cometathesis of long-chain hydrocarbons with internals double bond with ethylene, which are used as starting materials for the surfactant synthesis, for example for cleaning and disinfecting agents, or aids in the textile industry and the ore treatment. The object of carrying out the cometathesis reaction with an easily accessible catalyst in such a way that achieves a technically useful reaction rate and guarantees a high selectivity is achieved according to the invention by the cometathesis reaction with a catalyst consisting of a tetraalkyltin compound and an alkylaluminum compound of the AlR3 type , X3Al2R3, XAlR2 or X2AlR, wherein X represents a halogen atom and R represents an alkyl group of chain length C1 to C8, at a temperature of 90 to 150C, a reaction time of up to 3 hours and an ethylene pressure of 4.5 to 20 MPa. {Kometathese; ethylene; Hydrocarbons, internal, unsupported; * Tetraalkyltin compound; alkylaluminum; surfactant synthesis}

Description

Field of application of the invention

The invention relates to ") in processes for the preparation of terminally unsaturated hydrocarbons itt nittleror Kettonlänge by Komotathese long-chain hydrocarbons with internastri'ndigcr double bond with ethylene, the ice starting materials for surfactant synthesis - for example, for cleaning and disinfecting agents or aids in the textile industry and the Mineral processing - find application.

Characteristic of the known state of the art

E ι Jstandig unsaturated functionalized hydrocarbons: m medium Kettenlängenberoich 3ind by methods for ACttenlängenverkürzung I ingkottigen olefinic hydrocarbons accessible. A well-known reaction principle for this is olefin metathesis. It involves the reversible cleavage of C-C double bonds in alkylidone units, which are statistically combined into new double bonds. The reaction can be carried out either as a homomethalesis of a single olefin or as a comatatase of an olefinic mixture (reaction scheme!).

^1; 3 ¹ W ^UI 2 ^U V "3 " Λ 1 "2" 3

C Π C C

Λ and B are the products of cometathoso, products C with their cis / trans isomerone are derived from the homometathesis of RiR ₂ C-CRjR ₄ . Corresponding to an equilibrium reaction, the product distribution is dependent on the starting Kunzantrationen. Dio reaction be catalysed ß, depending Jie choice of the catalyst and the reaction conditions of the radicals R, ... R ₄ , which represent hydrogen or hydrocarbon radicals, which may also contain functional groups represent.

A detailed description of the reaction is given in "Olefin Metathesis", Academic Press, London (1983) and Houben-Weyl, "Methods of Organic Chemistry", Thieme · Verlag, Stuttgart-New York, Volume E 18, Part 2, p. 1163 ,

One problem, however, is that the catalyst activity heretofore achievable in the meta. Of these functionalized olefins is lower by a factor of \ 0 ² to 10 ¹ than that realized in the reaction of unfunctionalized model hydrocarbons and insufficient for industrial use (J. Mol Catal. 15 | 1982) 35).

For the invention relevant cometathesis of unsaturated fatty acid derivatives with ethylene are currently droi catalyst types, each consisting of a transition metal compound as a catalyst precursor and a co-catalyst known. Catalyst Type A contains as transition metal compound a WolframlVD halide, the Kalalysatortype B tragerfixiertes rhenium (VII) oxide and the catalyst type C an organyl tungsten compound The catalyst activities can be compared on the basis of the turnover numbers (UZ):

mol of reacted fatty acid derivative mol catalyst hour

Soy oil, oleyl nitrile and, preferably, methyl oleate are used as starting material in the known processes. The main parameters of the most important known processes are summarized in the following table.

C ₂ H ₄ pressure 0.1 React.-temp. UZ Selek tivity [MPAI I ⁰ C) (% L KatalysatortypA 0.2 1.WCI ₁ + Sn (CH,) ₄ - J. Chem. Soc., Chem. Comm. (1981) 1132 5 70 2.6 98 J. Ammil . Chem . Soc . 61 (1981) 425 0.2 70 5.7 60 - EPO 130039 2.3 to 3.83 104 32.7 - 2. WCI, + Al (C ₂ H ₄ ) Cl ₂ - JP125317I1976) 2 60 2.16 - 3. WCI, + AI (CHj) ₁ CIj U.S. Patent 3,974,196 - British Patent 1,485,197 5 25 0.07 - Type of catalyst B 1.Re ₂ O, / AljO, + Sn (CH ₁ J ₄ J.Am.Chem.SocChem.Comm. (1981) 1132 5 25 3.64 98 - J. Am. Oil Chem.Soc. 61 (1984) 425 2. Re ₂ O, / Al ₂ O, + Pb (CHj) ₄ FR 2 521 872 1.55 50 Type of catalyst C Carhonyl-Carbcn-W-Complex + SnCl, + SiCI ₄ 55 0.2 _ - DE-OS 30 45 946

The catalyst types are to be evaluated as follows:

Type A catalyst is cheap, easy to form and reaches at a reaction temperature of 70 ° C, although a high selectivity, as apparent from the sales figures, but only low activity.

The temperature increase to 104 ⁰ C allows for maintaining a ethylene pressure of 2-3 MPa a significant increase in activity, but at the same time side reactions such as Doppelbindungsisomorisierung and the metathesis of the Isomorisierungsprodukte be catalyzed, so that there is an increased by-product formation and the decrease in the yield (J.Jap. Oil Chem. Soc. (Yukagaku) 25 [1976 | 779].

A further disadvantage of this type of catalyst is that in each case the undesired homometathesis products are formed in the case of the ethylene endonone used. Thus, at an ethylene pressure of 0.2 MPa 40% and at 5 MPa 2% Homometatheseprodukt.

When using organylaluminum halides instead of the tetraalkyltin compounds as cocatalyst, the maximum product yields are only 5 to 18% and the conversion figures are also low.

Although type B catalyst is characterized by favorable reaction conditions such as low temperature and easily separable wedge and is limited regenerable. However, the activity is not higher than the catalyst type A, so that the high catalyst price must be considered a disadvantage.

Catalyst C is only accessible by a multi-step synthesis with exclusion of air and also shows such a low activity.

Object of the invention

The invention has for its object a process for the preparation of terminally unsaturated hydrocarbons and intermediate chain carboxylic acid esters by cometathesis of long-chain natural and synthetic hydrocarbons having an internal double bond with ethylene, which has a significantly higher catalyst activity and is suitable for use on an industrial scale.

Explanation of the essence of the invention

The object of the invention is dcrin, durchzufuhren the cometathesis reaction with an easily accessible catalyst so that a technically recoverable reaction rate achieved and a high selectivity is guaranteed. The object is achieved in that the cometathesis reaction with a catalyst consisting of a tungsten! Vl) halide, a TeUaalkyizinnverbindig and a Alky aluminum before bonding of the type AIRj, X ₁ AiJ R ₁ , XAIR, or XjAIR, wherein X cm is halogen atom and R is a AlkylMst the chain length C, to C ₉ , at a temperature of 90 -150 C. a reaction time of up to 3 hours and an ethylene pressure of 4.5 to 20 MPa is performed.

According to the invention, the catalyst contains the tungsten (VI) halide, the tetraalklytin compound and the Alkylaluminum compound preferably in a ratio of 1: 0.9 to 3.5: 0.5 to 1.2 and is by mixing in one

A suitable organic solvent is, for example, chlorobenzene, but other halogen-substituted aromatic and aliphatic compounds may also be used

Hydrocarbons such as 1,2-dichlorobenzene and CH] Cl] or saturated aliphatics such as η-hexane can be used. Of the tungsten (VI) halides, it is suitable. Particularly the tungsten (VI) chloride as a catalyst component. Suitable cetraalkyltin compounds are tetramethyltin and tetra-n-butyltin. As Alumir 'umvorbindungen triethylaluminum and ethylaluminum chloride are preferred. Decisive for the fulfillment of the task is the application of a suitable, in comparison to the prior art

increased reaction temperature, the oino ensures high catalyst activity.

The addition of the alkylaluminum compound ensures high selectivity at this temperature. The high catalyst activity, combined with high selectivity, makes it possible to use very short reaction times

in the literature compared to the literature, the turnover is much higher.

For the process of this invention, both synthetic and natural long chain hydrocarbons are known

internal double bond, which may also contain functional groups, are suitable as starting materials.

Furthermore, the intrinsically monounsaturated fatty acids and derivatives occurring in Plsnzone oils are for bois-diol

their esters and nitriles - but also polyunsaturated unsaturated fatty acid derivatives such as linoleic acid esters and esters containing the

Double bond contained in the alcohol radical, such as the oleyl acetate, can be used as starting materials. Also from the most important dor

in the native vegetable oils contained fatty acids, the oil · and l.inoUäure each with 18 and the Erucasäuro with22 carbon atoms in the chain are, according to the inventive method, the terminally unsaturated

Hydrocarbons in the middle Kottenlängenbereich of 10 to 15 carbon atoms, which oin property optimum for violo Have surfactant applications, with high yield and selectivity to produce. The process according to the invention is characterized by very short reaction times. The setting of a defined Ethyklendruckes above 4.5MPa must be no special attention gowidmet

which simplifies roughening.

There are no homomotathesis products in the applied printing press. The significantly over the known processes increased catalyst activity and the good Reproduzierbarkoit dos

orfindungsgumäßon method allow a continuous reaction.

embodiments

Boissiol 1

Under anorobic conditions, the following volumes of solutions of the catalyst components in chlorobenzone and

mixed the substrate: tungsten (VI) chloride, 1 ml 0.1 M solution = 0.1 mmol; Totramethyltin, 1 ml 0.17 m solution - 0.17 mmol;

Triethylaluminum, 1 ml of 0.1 M solution = 0.1 mmol; Erucic acid, 2,14ml - 5,2mmoi. These amounts corresponded to a catalyst / ester ratio of 1:52. Finally, the addition of 0.5 ml - 0.379 g n-Hoxadecan is carried out as standard for the gas chromatographic analysis. The Reaction solution is introduced in an autoclave. Pressed ethylene, heated to 140 ° C and 3 hours at this Temperature maintained. At an initial pressure of 7.0 MPa of ethylene, a pressure of about

14MPa oin.

After removal from the autoclave, the reaction mixture is immediately with 1 ml of concentrated aqueous ammonia solution

staggered and shaken vigorously for 10 minutes. The organic phase is separated, dried with magnesium sulfate and analyzed by gas chromatography.

The calculation of the content of dec-ion formed and of unreacted erucic acid methyl ester takes place under Help note of correction factors that were determined with test gigs.

rnol formed docen

Yield 100%

number of moles of ester used

_. ,. , moles of decene, "."

Selectivity -_- 100%

(used mole number tstor

unreacted number of moles of ester)

The table shows the comparison between the catalyst of the invention and the known tungsten / tin catalyst without Tr i et hy la Ium in iumzu sz.

invention known catalyst catalyst WCI ₆ f 1,7Sn (CH _1), WCI ₄ 1,7Sn f (CM ₁ I ₄ AK AKCjH.lj yield 36% 25% selectivity 75% 50%

Example 2

The experiments were carried out with twice the volume of the catalyst components, corresponding to a catalyst / ester ratio = 1:26 and otherwise identical to those of Example 1.

orfindungsgemäßer known

Catalyst catalyst

Yield 47% 40%

Selectivity 67% 54%

Example 3

The experiments were carried out wio in Example 2. They showed the suitability and the advantage of the catalyst system according to the invention with the use of shorter reaction times, whereby high turnover numbers are achieved and in comparison to Rt = 3h a higher selectivity increase can be observed.

Inventive catalyst 5 known catalyst Time (min) 30 15 68 83 30 Yield (%) selectivity {%) 70 70 86 86 45 60

IP 40.7 81.4 238 37.5 *

The indication of a turnover is sensible only in the case of an elective reaction.

Example 4

The experiments were carried out as in Example 2 with variation of the ethylene pressure.

Pc H | MPa | Yield (%) selectivity (%)

5 72 86

10.2 70 83

19 70 86

example

The experiments were carried out wio in Example 2 with variation of the reaction temperature.

TI ⁰ C) Yield (%) Solctivity (%)

100 65 69

120 64 83

150/1 82

Examples

The experiments are carried out as in Example 2. As Organoaluminiumverbindung Ethylaluniiniumdichlorid is used. A yield of 85% and a selectivity of 90% are determined.

Claims (5)

Anspruch [en] A process for the preparation of medium chain terminal unsaturation hydrocarbons by cometathesis of long chain double bond hydrocarbons with ethylene in the presence of a catalyst, characterized in that the cometathesis reaction is carried out with a catalyst consisting of a tungsten (VI) halide, a tetraalkyltin compound and an organyl substituted Aluminum compound of the type AIR ₃ , XAIR ₂ , XsAI ₇ R ₃ or X ₂ AIR, where X is a halogen and R is an n-alkyl radical of chain length Ci to C ₈ , at temperatures of 90-150 ⁰ C, a reaction time of up to 3 hours and an ethylene pressure of 4.5 to 20 MPa is performed. 2. The method according to claim 1, characterized in that the catalyst, the components of tungsten (VI) halide, tetraalkyltin and organoaluminum compound in a Molve. ratio 1: 0.9 to 3.5: 0.5 to 1.2. 3. The method according to claim 1 and 2, characterized in that the catalyst preferably) as tungsten (VI) halide tungsten (VI) chloride, as Tetraalkylzinnverbindung tetramethyltin uno Hs organo-A'uminiumverbindung triethylaluminum or ethylaluminum dichloride. 4. The method according to claim 1 to 3, characterized in that the ratio of catalyst to starting material is preferably 1:25 to 1:50. 5. The method according to claim 1 to 4, characterized in that the reaction time is preferably 0.1 to 0.5 hours.