DE1643045C3 - Process for the dimerization of lower alpha olefins - Google Patents

Description

Examples

1. In a pressure vessel of 4 l capacity, which is sensed with pure nitrogen and is provided with a stirrer, 271 g of a Cg-Olenn isomer mixture, as obtained according to patent 14 93 170 according to Example 2, and in which Vm mmol nickel acetylacetonate and Vi mmol triphenylphosphine are dissolved, entered. Propene is passed through to displace nitrogen. With the help of a heating / cooling jacket, the contents of the autoclave are heated to 30 ° C and propene is pressed on while stirring until 1.58 atmospheres are displayed. About 24 g of propene are then _{dissolved in the C 6} oil. Using a pressure lock, 2 mmoles of ethylaluminum sesquichloride, dissolved in 50 ml of C ₀ -OIeHn, are added, the pressure which drops immediately being kept at 1.58 atmospheres by pressing samples again. The resulting heat is dissipated by the cooling medium and the reactor contents are kept at 30 ° C. The propene uptake has ended after 31.5 hours.

The total reaction product is 2447 g, composed of 221 g of unconverted propene and 2.226 g of C ₀ olefins, the latter still containing small amounts of C _B olefins.

2. In a pressure vessel purged with pure nitrogen of 121 contents, which is fitted with a stirrer

isi, 400 ml of C ₆ oils, in which Vi »mmol of nickel acetylacetonate and ¹ Iz mmol of triphenylphosphine are dissolved, are entered. Propene is passed through to displace nitrogen. The contents of the autoclave are increased with the help of a heating and cooling jacket

ίο 30 ° C heated up and propene pressed while stirring until 3.19 atmospheres are displayed. About 48 g of propene are now dissolved in the C _{6 oil.} After entering a solution of 2 mmol of ethylaluminum sesquichloride in 50 ml of C ₆ -OIeBn through the lock

an immediate reaction occurs, the pressure being kept at 3.19 atmospheres by constantly pushing in propene. The resulting heat is removed by the cooling jacket and maintaining the reactor contents at 30 ⁰ C. The propene uptake is after 31 h

ao ended. 7080 g of total reaction product are obtained, of which 1245 g are unconverted propene and 5835 g C ₀ olefins which still contain small amounts of C ₉ olefins.

Claims (2)

1 2 run «of propene and toluene as solvents per t claims: Dimer product about 0.2 t of toluene can be recovered, but also from an extreme drying 1. Process for the dimerization of the lower process, which the toluene, since the entire reaction Λ-olefins in the presence of a catalyst system 5 piodukt before the distillation to remove the caoutic nickel compounds, halogen-containing, alumi- talysator secondary products including aqueous behanniumorganisrhen compounds and electron delt will, must be subjected. That in itself donators in organic solvents, whereby already very cheap dimensioning processes one as the nickel compound nickel acetylacetonate could be simplified and thus made even cheaper and as an organoaluminum compound an io, if it were possible, the reac of the general formula AU R, R 'Cl ₃ We have now surprisingly found that the remainder means, begins and a molar ratio of dimer product itself is a well-suited solution of nickel compound to electron donor of medium represents for the dimerization process, provided that 1: 6 to 1:18 and from electron donor to 15 is excluded only in its work-up and recovery carefully organoaluminum compound from 1: 2 to oxygen. Apparently 1: 6 is used, according to Patent 14 93 170, with small amounts of hydroper being present in the presence of oxygen, characterized in that the oxides that destroy the organoaluminum compounds in the dimerization product or the catalyst formed are destroyed. When carried out without the use of foreign solvents, 20 dimerization with the use of foreign solutions leads to. and the dimerization with the use of 2. The method according to claim 1, characterized in that the dimer product is a certain solvent indicates that a difference can be determined with continuous variation. When using external procedures because * the solvent that occurs at the reactor outlet runs in a discontinuous process Dimer product used as a solvent. 25 seek the dimerization faster in the beginning and thus brings more reaction product based on the catalyst unit in this initial period. This however, initial excess production will occur in the Dimerization using dimer product 30 as a solvent compensated for by the fact that the somewhat lower production over a long period of time almost remains constant. The bottom line is that According to the process of the main patent, production based on the catalyst unit in lower <\ - olefins can be achieved using a catalyst in both cases in the same amount,
gate systems based on nickel compounds and 35 the subject of the invention is therefore a halogen-containing organoaluminum compounds for the dimerization of lower "olefins in the presence of organic solvents dimerize, the presence of a catalyst system made of nickel, the nickel compound being nickel acetonyl compounds, halogen-containing organoaluminum acetonate and organoaluminum Compounds see compounds and electron donors in the general formula Al ₂ -R ₂ -R ^ CI ₃ , in which R 40 organic solvents, where one uses as nickel an alkyl radical, R 'an alkyl or alkoxy radical compound nickel acetylacetonate and as aluminum means, and a molar one Ratio of organic compound one of the general formula nickel compound to electron donor from 1: 6 to Al ₂ R ₂ R 'Cl ₃ , in which R is an alkyl radical and R' is 1:18 and of electron donor to aluminum-alkyl- "or alkoxy radical, and an organis a connection from 1: 2 to 1: 6. 45 molar ratio of nickel compound to elec- The reaction takes place without pressure or with an electron donor from 1: 6 to 1:18 and from an electric ring pressure and at temperatures of -80 and an aluminum donor to organoaluminum compound + 120 ° C, preferably -40 to + 80 ° C. from 1: 2 to 1: 6, according to patent 14 93 170, For the dimerization reaction after the main which is characterized in that one of the patent will be solvents such as. B. benzene, 50 dimerization required in the dimerization product itself without toluene, chlorobenzene or dichloroethane. Use of foreign solvents.
Discontinuous experiments in which from earlier Due to this surprising new finding It has now become possible to use the dimer product obtained from experiments as a solution, as a technical means was used, always brought instead of one to simplify driving and thus noticeably price yellow-orange colored catalyst solution to make a white 55 cheaper. The catalyst components, Precipitation. A system that is active in dimerization has been considered to be the corresponding not formed. The suitability of the Dimerproduktcs amounts of foreign solvents continuously dissolved in if the reaction space did not have to be entered even with extreme drying, then and the most careful removal of the dissolved acid in the substance by the method according to the invention. It was therefore initially assumed that 60 recovered reaction product itself dissolved and in the use of one of the solvents mentioned can be added to this form. Unite the process necessary condition for the formation of the compartment itself further by looking for the solution talysators or for the reaction to take place. the catalyst components already the reactor The process according to the main patent is therefore the starting raw products, possibly according to Abim Work-up oil with the separation and regeneration of the olefin used for dimerization, ration of the solvent polluted. This effort used. This also eliminates the need for distillation and does not only consist of the distillery to be expended - any subsequent cleaning z. B. Drying the in the tive separation work, in the case of the dimerization process re-used dimer product.