DE1288087B - Process for mixed oligomerization using 1,3-diolefins in the presence of a carbon-oxide-free organometallic complex catalyst of transition metals of subgroup VIII - Google Patents

Description

In Austrian patents 202 933, 210 402, 211 810 and 219 580 and in Belgian patent 619 490, processes for the production of cyclic olefins, in particular of cyclododecatrienes (1,5,9) and cyclooctadienes (1,5), are disclosed 1,3-diolefins. In these processes, organometallic complexes of transition metals of subgroup VIII of the Periodic Table are used as catalysts. Be particularly effective catalysts, ₀ lenoxydfreie complex compounds of nickel have carbon-proven.

Surprisingly, it has now been found that it is not only possible to use the 1,3-diolefins as such to subject this catalytic oligomerization, but that it is also possible to use mixtures of these 1,3-Diolefins with ethylene or butyne- (2) with the formation of oligomeric compounds to react bring. The subject of the process according to the invention is accordingly a mixed oligomerization, using 1,3-diolefins in the presence of a known carbon-free organo-metal complex catalyst the transition metal c

/ ^C \ H / ^CH \
H ₂ CC CH

H ₂ C

the VIII. subgroup of the periodic system; it is characterized by the fact that one as further Reaction partner in the mixed oligomerization ethylene or butyne (2) is used.

In this way, some known, but also hitherto unknown, cyclic and straight-chain olefinic ones are unsaturated compounds from simple technically easily accessible starting materials without Difficulties can be established.

The new type of reaction according to the invention is most easily made from the following comparison of one special process described in the cited patents with the possibility of mixed oligomerization apparent according to the invention. For example, in Austrian patent specification 219 580 described that the action of butadiene on bis-cyclooctadiene- (l, 5) -nickel- (0) practically quantitatively Cyclododecatriene- (1,5,9) is formed. According to the invention, this reaction can, for example, to the effect be diverted that with the simultaneous presence of ethylene in high overall yields the trans-cis-cyclododecadiene (l, 5) and the n-decatriene (1,4,9) arise, which were previously unknown.

CH ₂ = CH

So it can according to the invention with the catalysts of the Austrian patent 219 580 and Belgian patent 619 490 2 molecules of butadiene and 1 molecule of ethylene very much can be combined smoothly both into a ring system with 10 carbon atoms and into h-decatriene- (1,4,9). This is all the more surprising as the ten-ring according to previously known methods only with large ones Difficulties could be synthesized.

This ring system was not technically accessible until now. Reached further new types of olefins you, for example, if in the presence of the catalysts mentioned butadiene and butyne- (2) implements. The result is 1,2-dimethylcyclodecatriene- (1,4,8), which was previously unknown.

In the process according to the invention, isoprene, piperylene and are mainly used as 1,3-diolefins butadiene in particular is used, but other 1,3-diolefins can also be used, such as. B. 3-methylheptatriene- (1,4,6) which can be prepared from butadiene according to Austrian patent specification 219 580.

The unsaturated mixing component in the starting mixture to be oligomerized is in accordance with the invention uses ethylene or butyne- (2).

According to the invention, known carbon-oxide-free complex compounds of the transition metals of Group VIII are used as catalysts. With particular advantage one prepares these complex catalysts in such a way that one z. B. compounds of nickel in the presence of compounds acting as electron donors with organometallic compounds, such as metal alkyls, metal aryls or Grignard compounds or metal hydrides or complex metal hydrides, is implemented. Organometallic compounds or metal — CH =CH _{2 are preferred}

hydride of the I. to III. Group of the Periodic Table used. The resulting mixtures can be used directly as catalysts. The isolated pure complex compounds of the transition metals are used.

Compounds that are used as electron donors are those with the transition metals Able to form complex compounds. In the simplest case, they are necessary for the reaction 1,3-Diolefins themselves are used as electron donors. Furthermore, those which can be produced according to the method can Olefins are used. Generally unsaturated hydrocarbons work with the same success with carbon double or carbon triple bonds, such as. B. Cyclooctadiene (1.5), cyclododecatriene (l, 5.9), Stilbene or butyne- (2), tolane, phenylacetylene, etc.

Another large group of electron donors is compounds, the atoms containing lone pairs of electrons, such as B. alkyl and aryl phosphines, alkyl and aryl phosphites as well as the corresponding compounds of arsenic and antimony.

While the electron donors with C - C double or C - C triple bonds can be used in any large molar excess in relation to the transition metal of group VIII, it is advisable to use the electron donors of the second group mentioned in molar ratios of transition metal of group VIII. Group to donor such as 1: 1 to 1: 8, with triphenylphosphine even in molar ratios 1: 1 to 1: 4, since the results are not improved or even worsened by higher molar ratios, but the catalysts are not

become more economical. In the case of triphenylphosphine, for. B. at a molar ratio of 1: 8 (Austrian Patent specification 219 580, Example 26) no reaction at all between ethylene and butadiene takes place.

Such nickel compounds are used with particular advantage for the production of the catalysts, which are readily soluble in the solvents used, but it can also come from in the solvents sparingly soluble compounds catalysts are obtained, but in these cases decreases Formation of the catalysts from their components takes a long time. Because of this, have According to the method, those nickel compounds in which the nickel is organic Remnants is bound, such as. B. acetylacetonates, acetoacetic ester enolates, alcoholates, salts of organic acids or dimethyl glyoxime compounds.

The process can be carried out in the presence of solvents. Used in this case one solvent, of which neither the catalysts nor the organometallic components or metal hydrides are attacked. As such, there are aliphatic or aromatic hydrocarbons, aliphatic or cycloaliphatic ethers in question. With particular advantage, however, are already the olefins which can be prepared according to the process are used as solvents in the catalyst production, see above that no other compounds have to be separated from the reaction product.

The process can be carried out under normal pressure or under positive pressure. The vote the pressure range is strongly influenced by the desired direction of reaction.

The process can be carried out at temperatures from -10 to 200 ° C. Used preferably temperatures from 30 to 100 ° C.

The compounds that can be prepared according to the process are valuable starting materials for further syntheses, so z. B. the cyclooctadiene for the production of suberic acid or caprylolactam, the cyclodecadiene (l, 5) for the production of sebacic acid or the corresponding 11-membered lactam, the n-decatriene ( 1,4,9) or its 1-phenyl derivative for the production of ω, ίο-bifunctional compounds. As well as the dicarboxylic acids and the lactams are valuable monomers for the production of polyesters or polyamides.

example 1

6.3 g = 48 mmol of diethylethoxyaluminum are added at 20 ° C. to a mixture of 6.18 g = 24 mmol of nickel acetylacetonate and 12.9 g = 24 mmol of tri-o-oxydiphenyl phosphite in 100 ecm of cyclooctadiene (1.5). A clear, orange-colored solution results, which is poured into a 2-1 autoclave equipped with a magnetic stirrer. The autoclave is also charged with 100 g of butadiene and placed under 60 atmospheres of ethylene pressure. The temperature is raised to 8O ⁰ C. A further 350 g of butadiene are injected in the course of 1.5 hours. In the course of the reaction, the pressure drops to 45 atm. The autoclave is cooled and unreacted ethylene is blown off. The reaction product is precipitated. All volatile compounds are distilled off in a vacuum (at the end at 10 ~ ⁴ mm Hg and a bath temperature of 60 ° C.) in a cooled receiver. Practically only the catalyst used remains.

In addition to the cyclooctadiene (1.5) 11 used as solvent, the distillate contains Ig = 2.3% vinylcyclohexene, 7g = 1.4% n-decatriene (1,4,9), 239 g = 48.5% Cyclooctadiene- (1.5), 225 g = 45.7% trans-cis - cyclodecadiene - (1.5) (bp. ₈ 62.5 ° C, n'g 1.4960), 5.3 g = 1 , 1% all - trans - cyclododecatriene (1,5,9). The yield of cyclic compounds is over 97% of theory, based on converted butadiene and ethylene. In addition to the catalyst, the residue contains 5 g of higher polymers.

Example 2

The catalyst is used as in Example 1, but in 250 ecm benzene. One works according to Example 1, however, presents only 50 g of butadiene and splashes every 15 minutes in the course of the reaction 50 g of butadiene in each case, a total of 580 g. The temperature is raised to 75 ° C and the pressure to 80 bis 100 at held. In addition to the benzene used, Hg = 1.7% vinylcyclohexene, 37.8 g = 5.8% n-decatriene ( 1,4,9), 269 g = 41.2% cyclooctadiene (1.5), 312 g = 47.8% cyclodecadiene (1.5), 15 g = 2.3% all-trans-cyclododecatriene (l, 5.9). In addition to the catalyst, 8 g = 1.2% remain in the distillation residue higher polymers.

Example 3

20 g of bis-cyclooctadiene- (1.5) -nickel- (0), produced according to German patents 1,140,569 and 1,191,375, are suspended in 300 ecm cyclooctadiene. 50 g of butadiene are added, during which the crystals dissolve. The solution is filled into a 5 l autoclave and a further 1.65 kg of butadiene is added. Are pressed at 100 to 150 ethylene and heats up to 30 ⁰ C. During the reaction, the ethylene pressure is maintained at 110 to 150 atmospheres by injecting further. After 16 hours, unreacted ethylene and butadiene are blown off and the reaction product is worked up as in Example 1. 5.8 g = 0.9% vinylcyclohexene, 120g = 18.3% n-decatriene (1,4,9), 5g = 0.8% cyclooctadiene (1.5), 443 g = 67 are obtained. 5% trans-cis-cyclododecadiene- (1,5), 66.5 g = 10.1% all-trans-cyclododecatriene- (1,5,9), 3.9 g = 0,6% trans-trans- cis-cyclododecatriene (l, 5.9) and 12.2 g = 1.9% higher polymers.

Example 4

20.6 g = 80 mmol of nickel acetylacetonate are suspended in 300 cc Cyclooktadien- (1.5) and reacted with 2OG = 15OmMoI Diäthyläthoxyaluminium at 0 ⁰ C. The catalyst solution is mixed with 100 g of butadiene in the 5-1 autoclave. It presses 180 and 200 at ethylene and heats up to 6O ⁰ C. During the reaction, a further 100 g of butadiene are injected per hour, a total of 700 g. The procedure is as in Example 1 and 8.5 g = 0.9% vinylcyclohexene, 398 g = 43.8% n-decatriene (1,4,9), 21 g = 2.3% cyclooctadiene (1 , 5), 462 g = 50.9% cyclodecadiene - (1.5), 12.2 g = 1.3% all-trans-cyclododecadiene (1,5,9) in addition to 5 g = 0.6% higher polymers. The butadiene conversion is 90%.

Example 5

The catalyst is prepared as in Example 1. In the catalyst solution are at 60 ° C and Normal pressure introduced 230 g of butadiene with stirring, at the same time 90 g of butyne- (2) are instilled (during one hour). Work up as in Example 1

and contains 4g = 1.4% vinylcyclohexane 142g = 49.1% Cyclooctadiene - (1.5), 124.6 g = 43.1% transcis - cis - 4.5 - dimethylcyclodecatriene - (1,4.7), 0.8 g = 0.3% cyclododecatriene - (1.5.9) in addition to 17.7 g = 6.1% higher polymers. The yield of cyclic Olefins is 94% of theory, based on on converted butadiene and butyne- (2). The butyne- (2) has converted to 66%.

Claims (3)

Patent claims: 1. Process for mixed oligomerization using 1,3-diolefins in the presence of a known carbon-oxide-free organometallic complex catalyst of the transition metals of the VIII. Subgroup of the Periodic Table, characterized in that as further reactants in the mixed oligomerization ethylene or butyne- (2) are used. 2. The method according to claim 1, characterized in that one is used as a mixed oligomerization component Butadiene or its simple substitution products are used. 3. The method according to claim 1 and 2, characterized in that in the presence of a Nickel catalyst works.