Olefin trimerization using a catalyst comprising a source of chromium, molybdenum or tungsten and a ligand containing at least one phosphorous, arsenic or antimony atom bound to at least one (hetero) hydrocarbyl group
View Patent ↗A process for the trimerization of olefins is disclosed, comprising contacting a monomeric olefin or mixture of olefins under trimerization conditions with a catalyst which comprises (a) a source of chromium, molybdenum or tungsten (b) a ligand containing at least one phosphorus, arsenic or antimony atom bound to at least one hydrocarbyl or heterohydrocarbyl group having a polar substituent, but excluding the case where all such polar substituents are phosphane, arsane or stibana groups; and optionally (c) an activator.
1. A process for the trimerization of olefins, comprising contacting a monomeric olefin or mixture of olefins under trimerization reaction conditions in a trimerization reactor with a catalyst to produce a trimerization reaction product, which catalyst comprises:
(a) a source of a Group 3 to 10 transition metal:
(b) a ligand selected from the group consisting of:
(2-methoxyphenyl)(phenyl)PN(Me)P(phenyl) 2 ,
(2-methoxyphenyl) 2 PN(Me)P(phenyl) 2 ,
(2-methoxyphenyl)(phenyl)PN(Me)P(2-methoxyphenyl)(phenyl),
(2-methoxyphenyl) 2 PN(Me)P(2-methoxyphenyl) 2 ,
(2-ethoxyphenyl) 2 PN(Me)P(2-ethoxyphenyl) 2 ,
(2-isopropoxphenyl) 2 PN(Me)P(2-isopropoxyphenyl) 2 ,
(2-hydroxyphenyl) 2 PN(Me)P(2-hydroxyphenyl) 2 ,
(2-nitrophenyl) 2 PN(Me)P(2-nitrophenyl) 2 ,
(2,3-dimethoxyphenyl) 2 PN(Me)P(2,3-dimethoxyphenyl) 2 ,
(2,4-dimethoxyphenyl) 2 PN(Me)P(2,4-dimethoxyphenyl) 2 ,
(2,6-dimethoxyphenyl) 2 PN(Me)P(2,6-dimethoxyphenyl) 2 ,
(2,4,6-trimethoxyphenyl) 2 PN(Me)P(2,4,6-trimethoxyphenyl) 2 ,
(2-dimethoxyphenyl)(2-methylphenyl)PN(Me)P(2-methylphenyl) 2 ,
[2-(dimethylamino)phenyl] 2 PN(Me)P[2-(dimethylamino)phenyl] 2 ,
(2-methoxymethoxyphenyl) 2 PN(Me)P(2-methoxymethoxyphenyl) 2 ,
(2-methoxyphenyl) 2 PN(Ethyl)P(2-methoxyphenyl) 2 ,
(2-methoxyphenyl) 2 PN(Phenyl)P(2-methoxyphenyl) 2 ,
(2-methoxyphenyl) 2 PN(Me)N(Me)P(2-methoxyphenyl) 2 ,
(2-methoxyphenyl) 2 PCH 2 P(2-methoxyphenyl) 2 (2-methoxyphenyl) 2 PCH 2 CH 2 P(2-methoxyphenyl) 2 ,
tri(2-methoxymethoxyphenyl)phosphane; and optionally
(c) an activator.
2. The process according to claim 1 , wherein the catalyst is supported.
3. The process according to claim 2 , wherein the support is selected from the group consisting of silica, alumina, MgCl 2 , zirconia, polyethylene, polypropylene, polystyrene, and poly(aminostyrene).
4. The process according to claim 1 , wherein component (a) is a source of chromium, molybdenum or tungsten.
5. The process according to claim 1 , wherein component (c) is selected from the group consisting of trimethylaluminium (TMA), triethylaluminium (TEA), tri-isobutylaluminium (TIBA), tri-n-octylaluminium, methylaluminium dichloride, ethylaluminium dichloride, dimethylaluminium chloride, diethylaluminium chloride, ethylaluminiumsesquichloride, methylaluminiumsesquichloride, alumoxanes, tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimonate, boroxines, NaBH 4 , trimethylboron, triethylboron, dimethylphenylammonium-tetra(phenyl)borate, trityltetra(phenyl)borate, triphenylboron, dimethylphenylammonium tetra(pentrafluorophenyl)borate, sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate, H +(OEt 2 ) 2 [(bis-3,5-trifluoromethyl)phenyl]borate, trityltetra(pentrafluorophenyl)borate and tris(pentafluorophenyl) boron, and mixtures thereof.
6. The process according to claim 1 , wherein the olefin or mixture of olefins is additionally contacted with a further catalyst (d) suitable for the polymerization, oligomerization or other chemical transformation of olefins, such that the trimerization product is incorporated into a higher polymer or other chemical product.
7. The process according to claim 1 , wherein the monomeric olefin is ethylene.
8. The process of claim 1 , wherein the mixture of olefins comprises ethylene and one or more C 3 –C 36 monoolefin.
9. The process according to claim 8 , wherein the C 3 –C 36 monoolefin is a C 4 –C 20 monoolefin.
10. The process according to claim 9 , wherein the C 4 –C 20 monoolefin is butene, hexene, decene, a C 12 olefin or a C 14 olefin.
11. The process according to claim 1 , wherein at least 85 wt % of the trimerization reaction product is one of the following: 1-hexene, 1-octene, 1-decene, a C 12 olefin, a C 14 olefin, a C 16 olefin, or a C 18 olefin.
12. The process according to claim 1 , wherein the reaction temperature is less than 100° C., and/or the reaction pressure is below 30 bara.
13. The process according to claim 1 , wherein the residence time in the trimerization reactor is less than 4 hours.
14. The process according to claim 1 , wherein the trimerization reaction conditions are solution phase, slurry phase or gas phase.
15. The process according to claim 14 , wherein the reaction is conducted under gas phase fluidized bed conditions.
16. The process according to claim 6 , wherein the trimerization reactor is upstream or downstream of at least one polymerization or oligomerization reactor.
17. The process according to claim 6 , wherein the trimerization reactor is incorporated into a reaction loop of at least one polymerization or oligomerization reactor.
18. The process according to claim 17 , wherein the trimerization reactor is incorporated into a side-stream taken from said reaction loop.
19. The process according to claim 6 , wherein the trimerization reaction product is produced in or introduced into at least one polymerization or oligomerization reactor.
20. The process according to claim 6 , wherein at least one trimerization reaction product is separated from a remainder of the trimerization reaction products prior to (re)introduction into the polymerization or oligomerization reactor.
21. The process according to claim 1 , wherein the trimerization reaction is conducted in the presence of hydrogen and/or a halide source.