Process for oligomerization

Patent metadata

Field	Value
Publication number	US-11623209-B2
Application number	US-202217669558-A
Country	US
Kind code	B2
Filing date	Feb 11, 2022
Priority date	Mar 13, 2015
Publication date	Apr 11, 2023
Grant date	Apr 11, 2023

Abstract

The invention relates to oligomerization of olefins, such as ethylene, to higher olefins, such as a mixture of 1-hexene and 1-octene, using a catalyst system that comprises a) a source of chromium b) one or more activators and c) a phosphacycle-containing ligating compound. Additionally, the invention relates to a phosphacycle-containing ligating compound and a process for making said compound.

First claim

What is claimed is:

1. A process for oligomerizing an olefin comprising:
contacting at least one olefin with a catalyst system under olefin oligomerization conditions sufficient to convert at least a portion of the at least one olefin to a product comprising at least one oligomer of the at least one olefin, the catalyst system comprising:
a) a source of chromium;
b) one or more activators; and,
c) at least one phosphacycle-containing ligating compound of the formula:

 or

wherein:
P is phosphorus;
L is C;
q is 1 or 2;
p is 1 or 2;
wherein when p is 1 L 1 is Si; and
when p is 2:
a first of L 1 is Si and a second of L 1 is Si; or
the first of L 1 is N and q is 0 or 1 to give

 and the second of L 1 is Si and q is 1 or 2 to give

 or
the first of L 1 is N and q is 0 or 1 to give

 and the second of L 1 is C and q is 1 or 2 to give

 or
the first of L 1 is C and q is 0 or 1 to give

 and the second of L 1 is Si and q is 1 or 2 to give

R 5 attached to L 1 is independently H, C 1-40 substituted or unsubstituted alkyl, C 1-40 substituted or unsubstituted aryl;
each R 5 attached to the C or L group is independently H, halogen, C 1-40 substituted or unsubstituted alkyl, C 1-40 substituted or unsubstituted aryl;
each R 3 and R 4 is independently an alkyl, substituted alkyl, phenyl, substituted phenyl, furanyl, substituted furanyl, thienyl, substituted thienyl, pyrrolyl, substituted pyrrolyl, pyridinyl, and substituted pyridinyl; and
two or more R 3 , R 4 or R 5 groups are optionally linked together to form cyclic structures containing 4 to 10 ring atoms;
two or more R 5 groups linked to separate L atoms in a phosphacycle moiety are optionally linked together to form a cyclic structure that contains from 3 to 10 ring atoms; and
two R 5 groups attached to the same L atom may be optionally linked together to form a cyclic structure that contains from 3 to 10 ring atoms.

2. The process of claim 1 wherein the olefin comprises ethylene and the product comprises a mixture of 1-octene and 1-hexene in a weight fraction ranging from 85 percent by weight to 100 percent by weight of total product formed.

3. The process of claim 1 wherein the catalyst system is prepared by combining a) the source of chromium, b) one or more activators, and c) at least one phosphacycle-containing ligating compound together in any order.

4. The process of claim 1 comprising contacting a feed stream with the catalyst system wherein the feed stream comprises the olefin.

5. The process of claim 1 , wherein the source of chromium is selected from the group consisting of trichlorotris(tetrahydrofuran)chromium, chromium (III) acetylacetonate, chromium (III) 2-ethylhexanoate, and chromium (III) acetate.

6. The process of claim 1 , wherein the source of chromium and the ligating compound are contacted in proportions to provide Cr:ligating compound ratios from 1000:1 to 1:1000.

7. The process of claim 1 , wherein the catalyst system further includes an activator selected from the group consisting of (hydrocarbyl)aluminum compounds, (hydrocarbyl)gallium compounds, (hydrocarbyl)boron compounds, (hydrocarbyl)zinc compounds, non-coordinating, ion-forming compounds, an organic salt, an inorganic acid and salt.

8. The process of claim 7 , wherein the activator is an alkylaluminoxane.

9. The process of claim 8 , wherein the source of chromium and the aluminoxane are combined in proportions to provide chromium:activator molar ratios from 1:1 to 1:10,000.

10. The process of claim 1 wherein the product comprises polymer byproduct having a total mass fraction with respect to the total mass of products within a range of zero percent by weight to 10 percent by weight.

11. The process of claim 1 , wherein the at least one phosphacycle-containing ligating compound is selected from the group consisting of:

Assignees

• Dow Global Technologies Llc

Inventors

• Klosin Jerzy
• Milbrandt Kara A
• Boelter Scott D
• Wilson David R
• Rosen Mari S
• Welsh Dean M
• Margl Peter M
• Koh Kyoung Moo
• Pearson David M
• Huacuja Rafael

Classifications

• B01J2531/62

  Chromium · CPC title

• B01J2540/444

  Nitrile groups · CPC title

• B01J31/2457

  comprising aliphatic or saturated rings, e.g. Xantphos · CPC title

• B01J2540/225

  comprising perfluoroalkyl groups or moieties · CPC title

• C07F9/65685

  the ring phosphorus atom being part of a phosphine oxide or thioxide · CPC title