Ligands for production of 1-octene in chromium assisted ethylene oligomerization process
Processes to produce tunable mixtures of 1-hexene and 1-octene are described. The process includes contacting a mixture of a 1-hexene catalyst and a 1-octene catalyst with ethylene under conditions sufficient to produce a composition that includes a desired amount 1-hexene and 1-octene are described.
1. A catalyst composition for the production of 1-hexene and 1-octene, the catalyst composition comprising a 1-hexene catalyst and a 1-octene catalyst, wherein the 1-hexene catalyst and the 1-octene catalyst comprise a nitrogen, phosphorous, nitrogen, phosphorous, nitrogen (NPNPN) ligand, and wherein the 1-hexene catalyst comprises a ligand having a structure of:
where R 1 and R 2 are the same or different and are selected from the group consisting of (i) C 3 to C 4 non-cyclic aliphatic groups, (ii) C 5 to C 10 aliphatic groups which may be cyclic or non-cyclic, linear or branched, substituted or unsubstituted, and (iii) any combination thereof, and wherein n is 0 or 1, and m=n+3.
2. The catalyst composition of claim 1 , wherein catalyst composition further comprises:
a chromium (III) species; and
an activator or co-catalyst.
3. The catalyst composition of claim 1 , wherein the 1-octene catalyst comprises a ligand having a structure of:
where Ar 1 and Ar 2 are each independently an aromatic group or a substituted aromatic group, n is 0 or 1 and m=n+3.
4. The catalyst composition of claim 3 , wherein the Ar 1 and Ar 2 are each independently a phenyl group or an alkyl substituted phenyl group.
5. The catalyst composition of claim 4 , wherein the ligand of the 1-octene catalyst has the structure of:
6. The catalyst composition of claim 4 , wherein the ligand of the 1-octene catalyst has the structure of:
7. The catalyst composition of claim 1 , wherein R 1 and R 2 are each independently a C 5 to C 10 cyclic hydrocarbon group or a substituted C 5 to C 10 cyclic hydrocarbon group.
8. The catalyst composition of claim 7 , wherein the 1-hexene ligand has the structure of:
9. The catalyst composition of claim 7 , wherein the 1-hexene ligand has a structure of:
10. The catalyst composition of claim 1 , wherein the 1-octene catalyst comprises a ligand having the structure of:
and the 1-hexene catalyst comprises ligand having the structure of:
11. A process to produce a composition comprising 1-hexene and 1-octene from olefins, the process comprising contacting a reactant stream comprising ethylene with a solution comprising the catalyst composition of claim 1 under conditions sufficient to oligomerize the ethylene and produce an oligomer composition comprising the 1-hexene and 1-octene.
12. The process of claim 11 , wherein a weight ratio of the 1-hexene catalyst to 1-octene catalyst is from 10:1 to 1:10.
13. The process of claim 11 , wherein the weight ratio of 1-hexene to 1-octene in the oligomer composition is greater than 0.5:1.
14. The process of claim 11 , wherein the weight ratio of 1-hexene catalyst to 1-octene catalyst is about 1:1, and the weight ratio of 1-hexene to 1-octene in the oligomer composition is at least 2.5:1.
15. The process of claim 11 , wherein the weight ratio of 1-hexene catalyst to 1-octene catalyst is about 1:2.3, and the weight ratio of 1-hexene to 1-octene in the oligomer composition is at least 1.5:1.17.
16. The process of claim 11 , wherein the weight ratio of 1-hexene catalyst to 1-octene catalyst is about 1:4, and the weight ratio of 1-hexene to 1-octene in the oligomer composition is 1:1 or greater; or the weight ratio of 1-hexene catalyst to 1-octene catalyst is about 1:8, and the weight ratio of 1-hexene to 1-octene in the oligomer composition is greater than 1:1.3.
17. The catalyst composition of claim 2 , wherein the chromium (III) species is selected from the group consisting of chromium (III) acetylacetonate, Cr(2,2,6,6,-tetramethyl-3,5-heptadionate) 3 , chromium (III) 2-ethylhexanoate, chromium trichloride tris-tetrahydrofuran, (benzene) tricarbonyl chromium, chromium (III) octanoate, chromium hexacarbonyl, and chromium (III) naphthenate.
18. The catalyst composition of claim 2 , wherein the activator or co-catalyst is a methylaluminoxane compound.
19. The catalyst composition of claim 18 , wherein the methylaluminoxane compound is a methyl iso-butyl aluminum oxide compound.
20. The catalyst composition of claim 4 , wherein Ar 1 and Ar 2 are phenyl.
21. The catalyst composition of claim 7 , wherein R 1 and R 2 are each a cyclohexyl group.
22. The catalyst composition of claim 1 , wherein the weight ratio of 1-hexene catalyst to 1-octene catalyst is about 1:1 to about 1:9.