Process for preparing cyclododecatriene
View Patent ↗Preparation of cyclododecatriene in a continuous or discontinuous process by trimerization of butadiene in the presence of a catalyst system and a solvent, the crude cyclododecatriene obtained being able to be isolated by means of distillation. The cyclooctadiene formed as by-product can likewise be isolated from the crude product.
1. A process for preparing cyclododecatriene, comprising:
reacting butadiene in a solvent, in the presence of at least one catalyst system to form a crude cyclododecatriene mixture,
wherein
the process is continuous,
the at least one catalyst system comprises:
one selected from the group consisting of nickel, titanium and a mixture thereof;
ethoxydiethylaluminum or ethylaluminum sesquichloride; and
10 to 200 ppm by mass of the reaction mixture of at least one compound selected from the group consisting of ammonia, a C 1-8 alkyl primary amine and a C 1-8 dialkyl secondary amine;
the solvent comprises, before the addition of the at least one catalyst system, 10-1000 ppm by mass of a polar component of the general formula HO—R, where 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
a temperature of the butadiene reaction is less than or equal to 140° C. in the case of a nickel catalyst system and less than or equal to 80° C. in the case of a titanium catalyst system.
2. The process of claim 1 , wherein
the catalyst system comprises nickel and the nickel is present as nickel acetylacetonate.
3. The process of claim 1 , wherein
the catalyst system comprises titanium and the titanium is present as TiX 4 , where X═F, Cl, Br, I or a mixture thereof.
4. The process of claim 1 , wherein
the reaction temperature is from 60 to 120° C. in the case of a nickel catalyst system and from 30 to 75° C. in the case of a titanium catalyst system.
5. The process of claim 1 , wherein
the catalyst comprises ammonia.
6. The process of claim 1 , wherein
the catalyst comprises a C 1-8 primary amine.
7. The process of claim 1 , wherein
the solvent is an aromatic or aliphatic solvent or a mixture thereof.
8. The process of claim 1 , wherein
a concentration of nickel or titanium of the catalyst system in the reaction mixture is from 0.01 to 40 mmol/l.
9. The process of claim 1 , wherein
an order of addition of reaction mixture components is:
firstly the solvent including polar component,
then the ethoxydiethylaluminum or ethylaluminum sesquichloride,
then the at least one titanium- and/or nickel catalyst,
then the at least one compound comprising an element of main group 5 of the Periodic Table, and
then butadiene.
10. The process of claim 1 , wherein
an order of addition of reaction components is
firstly the solvent comprising a polar component,
then the at least one titanium- and/or nickel catalyst,
then the ethoxydiethylaluminum or ethylaluminum sesquichloride,
then the at least one compound comprising an element of main group 5 of the Periodic Table,
and then butadiene.
11. The process of claim 1 , wherein
the catalyst system comprises nickel and a molar ratio of nickel to aluminum is from 1:3 to 1:6.
12. The process of claim 1 , wherein
the catalyst system comprises titanium and a molar ratio of titanium to aluminum is from 1:10 to 1:60.
13. The process of claim 1 , further comprising:
isolating cycloocta-1,5-diene (COD) and/or vinylcyclohexene (VCH) from the crude cyclododecatriene.
14. A composition obtained by the process of claim 1 .