Alicyclic polycarboxylic ester mixtures with a high trans proportion and method for the production thereof
View Patent ↗The present invention relates to the preparation of alicyclic polycarboxylic esters by ring-hydrogenation of the corresponding aromatic polycarboxylic esters on a catalyst which comprises at least one metal from the triad iron, cobalt, nickel, and at least one metal of the IInd, IIIrd, IVth, Vth, and/or VIth transition group of the Periodic Table. An alicyclic carboxylic ester mixture with a proportion above 10 mol % of the trans isomers. The use of the alicyclic polycarboxylic ester mixtures. Mixtures made from plastics and from alicyclic polycarboxylic ester mixtures.
1. An alicyclic polycarboxylic acid ester mixture, comprising:
at least two isomers of an alicyclic polycarboxylic acid ester whose structures are determined by the positions of the ester groups on the ring system of the ester compound, wherein the proportion of the trans isomers in the isomer mixture is above 10 mol %, the alicyclic polycarboxylic acid ester mixture being prepared by hydrogenating the corresponding aromatic polycarboxylic acid ester isomers over a catalyst which comprises at least one metal selected from the triad of elements consisting of iron, cobalt and nickel, together with at least one metal selected from the group consisting of the IInd, IIIrd, IVth, Vth and VIth transition group of the Periodic Table.
2. The alicyclic polycarboxylic acid ester mixture as claimed in claim 1 , wherein the ring system is a compound of one or more C 6 rings.
3. The alicyclic polycarboxylic acid ester mixture as claimed in claim 1 , wherein the polycarboxylic esters have 2, 3 or 4 ester groups.
4. The alicyclic polycarboxylic acid ester mixture as claimed in claim 1 , wherein the alcohol components of the alicyclic polycarboxylic esters are alkoxyalkyl, cycloalkyl, and/or alkyl groups having from 1 to 25 carbon atoms, branched or unbranched, and in each instance identical or different.
5. The alicyclic polycarboxylic acid ester mixture as claimed in claim 1 , wherein the alicyclic polycarboxylic ester mixture comprises the isomers of the cyclohexane-1,2-, 1,3-, 1,4-dicarboxylic acid esters, and/or of the cyclohexane-1,2,3-, 1,2,4- or 1,3,5-tricarboxylic acid esters.
6. A process for preparing alicyclic polycarboxylic acid esters, comprising:
hydrogenating an aromatic polycarboxylic acid ester isomer mixture in a mixed liquid/gas phase or liquid phase in three phase reactors in the presence of a catalyst which comprises at least one metal selected from the triad of elements consisting of iron, cobalt and nickel, together with at least one metal of the IInd, IIIrd, IVth, and/or Vth transition group of the Periodic Table, thereby preparing an alicyclic polycarboxylic acid ester isomer mixture that has a trans isomer content of greater than 10 mol %.
7. The process as claimed in claim 6 , wherein the metal of the IInd, IIIrd, IVth, and/or Vth transition group of the Periodic Table comprises zinc and/or chromium.
8. The process as claimed in claim 6 , wherein the catalyst further comprises an inert component.
9. The process as claimed in claim 8 , wherein the inert component comprises at least one metal selected from the group consisting of Al, Mg, Ti, Zr and Si in the form of the oxides and/or mixed oxides.
10. The process as claimed in claim 6 , wherein the content of iron, cobalt and/or nickel in the catalyst ranges from 1 to 60% by weight.
11. The process as claimed in claim 6 , wherein the aromatic polycarboxylic acid ester is the alkyl, cycloalkyl or alkoxyalkyl ester of benzene-1,2-, 1,3-, 1,4-dicarboxylic acid, and/or of benzene-1,2,3-, 1,2,4- and/or 1,3,5-tricarboxylic acid.
12. The process as claimed in claim 6 , wherein the alcohol components of the aromatic polycarboxylic esters are alkoxyalkyl, cycloalkyl and/or alkyl groups having from 1 to 25 carbon atoms, branched or unbranched, and in each instance identical or different.
13. The process as claimed in claim 6 , wherein dinonyl phthalate or a mixture of isomeric dinonyl phthalates is hydrogenated to give an isomeric mixture of dinonyl cyclohexanedicarboxylates.
14. The process as claimed in claim 6 , wherein decyl phthalate or a mixture of isomeric decyl phthalates is hydrogenated to give an isomeric mixture of decyl cyclohexanedicarboxylates.
15. The process as claimed in claim 6 , wherein di(octyl) phthalate or a mixture of isomeric di(octyl) phthalates is hydrogenated to give an isomeric mixture of di(octyl) cyclohexanedicarboxylates.
16. The process as claimed in claim 13 , wherein the hydrogenated mixtures have a proportion above 10 mol % of the trans isomers with respect to the position of the carboxy groups on the cyclohexane ring.
17. A mixture prepared from a plastic and the alicyclic polycarboxylic acid ester mixture as claimed in claim 1 .
18. The mixture as claimed in claim 17 , wherein the proportion of the alicyclic polycarboxylic acid ester in the mixture is at least 5% by weight.
19. A plastic, comprising: an alicyclic polycarboxylic acid ester mixture as claimed in claim 1 .
20. The process as claimed in claim 6 , wherein the three reactors are operated at liquid flow rates of 15 to 120 m 3 per m 2 per hour.
21. A process for preparing alicyclic polycarboxylic acid esters, comprising:
continuously hydrogenating an aromatic polycarboxylic acid ester isomer mixture over a fixed catalyst bed which comprises at least one metal selected from the triad of elements consisting of iron, cobalt and nickel, together with at least one metal of the IInd, IIIrd, IVth, and/or Vth transition group of the Periodic Table, thereby preparing an alicyclic polycarboxylic acid ester isomer mixture that has a trans isomer content of greater than 10 mol %.