Method for producing trimethylcyclododecatriene
View Patent ↗The present invention relates to the preparation of trimethylcyclododecatriene in a continuous or batchwise process by trimerizing isoprene in the presence of a catalyst system and of a solvent. It is possible to isolate the resulting crude trimethylcyclododecatriene by means of distillation. The dimethylcyclooctadiene formed as a by-product may likewise be isolated from the crude product.
1. A process for preparing trimethylcyclododecatriene, comprising:
first charging a solvent comprising 15-1000 ppm of a polar component to a reactor;
charging a catalyst system and at least one organometallic compound to the reactor charged with a solvent comprising 15-1000 ppm of a polar compound;
heating the charged reactor to a reaction temperature;
admitting isoprene to the heated charged reactor; and
reacting the isoprene in the presence of the solvent, catalyst system and at least one organometallic compound to obtain a product mixture comprising
trimethylcyclododecatriene,
wherein
a yield of the trimethylcyclododecatriene is greater than 65% of a theoretical yield calculated on a mass of isoprene admitted to the reactor,
the product mixture comprises linear C15 oligomers and a ratio of trimethylcyclododecatriene to the linear C15 oligomers is greater than or equal to 10:1,
the catalyst system comprises nickel, titanium or a mixture thereof,
a compound containing at least one element of main group 5 of the Periodic Table of the Elements is added to the catalyst system,
the polar component is represented by formula (I)
HO—R (I)
wherein
R is selected from the group consisting of branched and
unbranched C 1 -C 18 -alkyl, C 1 -C 18 -cycloalkyl, C 1 -C 18 -aryl, C 1 -C 18 -aralkyl and H, and
the reaction temperature, in the case of a nickel-containing catalyst system, is less than or equal to 140° C. and, in the case of a titanium-containing catalyst system, is less than or equal to 80° C.
2. The process as claimed in claim 1 ,
wherein
the catalyst system comprises nickel acetylacetonate.
3. The process as claimed in claim 1 ,
wherein
the catalyst system comprises titanium tetrachloride.
4. The process as claimed in claim 1 ,
wherein
the reaction temperature, in the case of a nickel-containing catalyst system, is 60 to 120° C. and, in the case of a titanium-containing catalyst system, is 30 to 70° C.
5. The process as claimed in claim 1 ,
wherein
the component comprising an element of main group 5 of the Periodic Table comprises at least one nitrogen atom.
6. The process as claimed in claim 5 ,
wherein
the component comprising at least one nitrogen atom is selected from the group consisting of a primary amine, a secondary amine, a tertiary amine, ammonia, a pyridine, and a pyridone.
7. The process according to claim 1 ,
wherein
the solvent comprising 15-1000 ppm of a polar component is an aromatic or aliphatic solvent or a mixture thereof.
8. The process as claimed in claim 1 ,
wherein
a concentration of nickel or titanium in the reaction mixture is from 0.01 to 40 mmol of nickel or titanium/1.
9. The process as claimed in claim 1 ,
wherein
a concentration of nickel or titanium in the reaction mixture is from 0.05 to 10 mmol of nickel or titanium/1.
10. The process as claimed in claim 1 ,
wherein the charging is made in the order:
first charging the solvent including polar component,
then the at least one organometallic compound,
then the catalyst system, and
then the at least one compound containing an element from main group 5 of the Periodic Table.
11. The process as claimed in claim 1 ,
wherein the charging is made in the order:
first charging the solvent including polar component,
then the catalyst system,
then the at least one organometallic compound, and
then the at least one compound containing an element from main group 5 of the Periodic Table.
12. The process as claimed in claim 1 ,
wherein
the organometallic compound is an organoaluminum compound.
13. The process according to claim 12 ,
wherein
the organometallic compound is ethoxydiethylaluminum or ethylaluminum sesquichloride.
14. The process according to claim 12 ,
wherein
the catalyst system comprises nickel and a molar ratio of nickel to aluminum is from 1:3 to 1:6.
15. The process according to claim 12 ,
wherein
the catalyst system comprises titanium and a molar ratio of titanium to aluminum is from 1:10 to 1:60.
16. The process as claimed in claim 1 ,
wherein
the product mixture comprises 1,5 and/or 1,6-dimethylcycloocta-1,5-diene (DMCOD) and the process further comprises isolating the 1,5 and/or 1,6-dimethylcycloocta-1,5-diene.
17. A trimethylcyclododecatriene composition which is obtained according to the process of claim 1 .
18. The trimethylcyclododecatriene composition according to claim 17 ,
wherein
the ratio of trimethylcyclododecatriene to linear C15 oligomers is greater than or equal to 15:1.
19. The trimethylcyclododecatriene composition of claim 17 ,
wherein
the ratio of trimethylcyclododecatriene to linear C15 oligomers is equal to or greater than 20:1.
20. A perfume or a fragrance comprising the trimethylcyclododecatriene composition of claim 17 .