Metathesis process

Patent metadata

Field	Value
Publication number	US-9604903-B2
Application number	US-201314383348-A
Country	US
Kind code	B2
Filing date	Mar 18, 2013
Priority date	Mar 18, 2012
Publication date	Mar 28, 2017
Grant date	Mar 28, 2017

Abstract

A process of metathesizing a feedstock in the presence of a metathesis catalyst and at least one catalyst enhancer. The catalyst enhancer can be selected from a sacrificial catalyst or a non-catalyst enhancer. The process exhibits improved reaction times and/or the metathesis catalyst can be used at very low concentrations.

First claim

The invention claimed is:

1. A process of metathesising a feedstock, wherein the feedstock comprises unsaturated fatty acids and/or esters of unsaturated fatty acids, in the presence of a metathesis catalyst and at least one catalyst enhancer compound in a reaction mixture,
wherein the at least one catalyst enhancer is selected from the group consisting of a sacrificial catalyst and a non-catalyst enhancer,
wherein the sacrificial catalyst is selected from the group consisting of dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II), dichloro-(3-phenyl-1H-inden-1-ylidene)bis(isobutylphobane)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium(II), [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitro-phenolyl]chloro-[3-phenyl-indenylidene]ruthenium(II), and [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(2-methylphenyl)imino]methyl]-phenolyl]chloro-(3-phenyl-indenylidene)ruthenium(II),
wherein the non-catalyst enhancer is selected from the group consisting of a Lewis acid and a titanium based compound,
wherein the process is carried out without a solvent or in a solvent consisting of hydrocarbons and/or alcohols, wherein the metathesis catalyst efficiency is less than 100.

2. The process according to claim 1 wherein at least 40 wt. % of the feedstock is metathesized.

3. The process according to claim 1 wherein the process reaches equilibrium in less than 20 minutes.

4. The process according to claim 1 wherein the metathesis catalyst is present in an amount less than 100 ppm with respect to the reaction mixture.

5. The process according to claim 4 wherein the metathesis catalyst is present in an amount less than 10 ppm with respect to the reaction mixture.

6. The process according to claim 1 wherein the metathesis catalyst efficiency is less than 10.

7. The process according to claim 1 wherein the metathesis catalyst retains over 75% of its activity after 30 minutes.

8. The process according to claim 1 wherein no chemical treatment of the feedstock or starting material to remove catalyst poisons is performed.

9. The process according to claim 1 wherein the sacrificial catalyst is a sacrificial metathesis catalyst different from the metathesis catalyst.

10. The process according to claim 1 wherein the sacrificial catalyst is present in an amount ranging from 1 ppm to 100 ppm with respect to the reaction mixture.

11. The process according to claim 1 wherein the non-catalyst enhancer is a Lewis acid.

12. The process according to claim 1 wherein the non-catalyst enhancer is a titanium based compound.

13. The process according to claim 1 wherein the non-catalyst enhancer is selected from the group consisting of titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) propoxide, titanium (IV) isopropoxide, titanium (IV) butoxide, titanium (IV) tert-butoxide, titanium (IV) 2-ethylhexoxide, titanium (IV) 2-ethyl-1,3-hexanediolate, titanium (IV) tetrachloride, titanium (IV) tetrabromide, titanium (IV) tetrafluoride, titanium (IV) tetraiodide, and mixtures thereof.

14. The process according to claim 1 wherein the non-catalyst enhancer is present in an amount ranging from 10 ppm to 1,000 ppm with respect to the reaction mixture.

15. A process of metathesising a feedstock, wherein the feedstock comprises unsaturated fatty acids and/or esters of unsaturated fatty acids, in the presence of a metathesis catalyst and at least one catalyst enhancer compound in a reaction mixture,
wherein the at least one catalyst enhancer is selected from the group consisting of a sacrificial catalyst and a non-catalyst enhancer,
wherein the sacrificial catalyst is selected from the group consisting of dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II), dichloro-(3-phenyl-1H-inden-1-ylidene)bis(isobutylphobane)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium(II), [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitro-phenolyl]chloro-[3-phenyl-indenylidene]ruthenium(II), and [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(2-methylphenyl)imino]methyl]-phenolyl]chloro-(3-phenyl-indenylidene)ruthenium(II),
wherein the non-catalyst enhancer is selected from the group consisting of copper iodide, sodium iodide, tetrabutylgermanium, tetraethylsilicon, tin oxide, tin octoate, tin oxalate, dibutyltin dilaurate, tin(IV) chloridetetrabutyl orthotitanate, palladium acetate, tris(dibenzylideneacetone)palladium, tetrakis(triphenylphosphine)palladium, bis(diphenylferrocenyl)palladium dichloride, nickel chloride, bis(cyclooctadiene)nickel, nickelocene iron chloride, iron bromide, ferrocene, silver chloride, silver iodide, silver oxide, iodine, silver trifluoromethanesulfonate, sodium borohydride, boric acid, zinc ethylhexanoate, zircon (IV) oxide chloride octahydrate, acetic acid, butylated hydroxytoluene (BHT), quinones, activated charcoal, alumina, bleaching earth, titanium compounds having the general formula Ti.[Q] 4 wherein each Q independently represents hydrogen, a C 1 to C 10 alkoxy group, a C 4 to C 8 aryl group, a C 12 to C 18 fatty alcohol, or a C 6 to C 18 fatty acid,
wherein the non-catalyst enhancer is present in an amount ranging from 10 ppm to 1,000 ppm with respect to the reaction mixture.

16. The process according to claim 15 wherein the metathesis catalyst is present in an amount less than 100 ppm with respect to the reaction mixture.

17. The process according to claim 15 wherein the metathesis catalyst efficiency is less than 100.

18. The process according to claim 15 wherein no chemical treatment of the feedstock or starting material to remove catalyst poisons is performed.

19. The process according to claim 15 wherein the sacrificial catalyst is present in an amount ranging from 1 ppm to 100 ppm with respect to the reaction mixture.

20. The process according to claim 15 wherein the non-catalyst enhancer is a titanium compound having the general formula Ti.[Q] 4 wherein each Q independently represents hydrogen, a C 1 to C 10 alkoxy group, a C 4 to C 8 aryl group, a C 12 to C 18 fatty alcohol, or a C 6 to C 18 fatty acid.

21. The process according to claim 15 wherein the non-catalyst enhancer is selected from the group consisting of titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) propoxide, titanium (IV) isopropoxide, titanium (IV) butoxide, titanium (IV) tert-butoxide, titanium (IV) 2-ethylhexoxide, titanium (IV) 2-ethyl-1,3-hexanediolate, and mixtures thereof.

22. A process of metathesising a feedstock, wherein the feedstock comprises unsaturated fatty acids and/or esters of unsaturated fatty acids, in the presence of a metathesis catalyst and at least one catalyst enhancer compound in a reaction mixture,
wherein the at least one catalyst enhancer is selected from the group consisting of a sacrificial catalyst and a non-catalyst enhancer,
wherein the sacrificial catalyst is selected from the group consisting of dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II)

Assignees

• Croda Int Plc

Inventors

• Wels Bastiaan
• Ridderikhoff Hans
• Bergen-Brenkman Tanja Van
• Liminto Dessy

Classifications

• B01J31/128 Primary

  Mixtures of organometallic compounds · CPC title

• B01J31/2278

  Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts · CPC title

• C07C1/213

  by splitting of esters · CPC title

• C10G2300/1014

  of vegetal origin · CPC title

• B01J2531/821

  Ruthenium · CPC title