Oligomerization reactions using aluminoxanes

Patent metadata

Field	Value
Publication number	US-10464862-B2
Application number	US-201715719107-A
Country	US
Kind code	B2
Filing date	Sep 28, 2017
Priority date	Sep 28, 2017
Publication date	Nov 5, 2019
Grant date	Nov 5, 2019

Abstract

Disclosed are processes for oligomerizing ethylene by contacting a catalyst system, ethylene, and optionally hydrogen to form an oligomer product in a reaction zone, wherein the catalyst system comprises: a chromium component comprising an N 2 -phosphinyl amidine chromium compound complex, an N 2 -phosphinyl formamidine chromium compound complex, and/or an N 2 -phosphinyl guanidine chromium compound complex, and an aluminoxane; wherein the aluminoxane is characterized by 400 MHz proton NMR in which: (a) the ratio of peaks found in the range of −0.86 ppm to −0.74 ppm to peaks found in a range of −0.03 ppm to 0.07 ppm is less than or equal to 2.8:1; (b) the ratio of peaks found in the range of −0.03 ppm to 0.025 ppm to peaks found in a range of 0.025 ppm to 0.07 ppm is less than or equal to 15:1; and/or (c) the ratio of peaks found in a range of −0.86 ppm to −0.78 ppm to peaks found in the range of −0.78 ppm to −0.74 ppm is less than or equal to 6.5:1.

First claim

What is claimed is:

1. A process comprising: contacting a catalyst system, ethylene, and optionally hydrogen to form an oligomer product in a reaction zone, wherein the catalyst system comprises: a chromium component comprising an N 2 -phosphinyl amidine chromium compound complex, an N 2 -phosphinyl formamidine chromium compound complex, an N 2 -phosphinyl guanidine chromium compound complex, or any combination thereof, and a modified methylaluminoxane (MMAO); wherein the MMAO is characterized by 400 MHz proton NMR in which: (a) a ratio of peak areas found in a range of −0.86 ppm to −0.74 ppm to peak areas found in a range of −0.03 ppm to 0.07 ppm is less than or equal to 2.8:1; (b) a ratio of peak areas found in a range of −0.03 ppm to 0.025 ppm to peak areas found in a range of 0.025 ppm to 0.07 ppm is less than or equal to 15:1; and (c) a ratio of peak areas found in a range of −0.86 ppm to −0.78 ppm to peak areas found in the range −0.78 ppm to −0.74 ppm is less than or equal to 6.5:1.

2. The process of claim 1 , further comprising forming a catalyst system mixture by contacting the chromium component, the MMAO, and optionally a solvent to form a catalyst system mixture, aging the catalyst system mixture in the substantial absence of ethylene for a catalyst system mixture aging time to form an aged catalyst system mixture, and contacting the aged catalyst system mixture with the ethylene and optionally hydrogen to form the oligomer product in the reaction zone.

3. The process of claim 2 , wherein relative to the same process utilizing an MMAO having (a) the ratio of peak areas found in the range of −0.86 ppm to −0.74 ppm to peak areas found in a range of −0.03 ppm to 0.07 ppm greater than 2.85; (b) the ratio of peak areas found in the range of −0.03 ppm to 0.025 ppm to peak areas found in a range of 0.025 ppm to 0.07 ppm greater than 16:1; (c) the ratio of peak areas found in the range of −0.86 ppm to −0.78 ppm to peak areas found in the range of −0.78 ppm to −0.74 ppm greater than 6.7:1; or any combination thereof, the catalyst system mixture aging time is reduced.

4. The process of claim 1 , wherein the chromium component is an N 2 -phosphinyl formamidine chromium compound complex having Structure NPFCr1:

wherein R 1 is a C 1 to C 30 organyl group; R 3 is hydrogen or a C 1 to C 30 organyl group consisting essentially of inert functional groups; R 4 and R 5 each independently are C 1 to C 30 organyl groups consisting essentially of inert functional groups; CrX p represents a chromium compound where X is a monoanion, and p is an integer from 2 to 6; Q is a neutral ligand; and q ranges from 0 to 6.

5. The process of claim 1 , wherein the chromium component is an N 2 -phosphinyl amidine chromium compound complex having Structure NPACr1 or Structure NPACr2:

wherein R 1 is a C 1 to C 30 organyl group; R 2 is a C 1 to C 30 organyl groups consisting essentially of inert functional groups; R 3 is hydrogen or a C 1 to C 30 organyl group consisting essentially of inert functional groups; R 4 and R 5 each independently are C 1 to C 30 organyl groups consisting essentially of inert functional groups; L 1 is a C 3 to C 30 organylene group; CrX p represents a chromium compound where X is a monoanion, and p is an integer from 2 to 6; Q is a neutral ligand; and q ranges from 0 to 6.

6. The process of claim 1 , wherein the chromium component is an N 2 -phosphinyl guanidine chromium compound complex having Structure GuCr1, Structure GuCr2, Structure GuCr3, Structure GuCr4, or Structure GuCr5:

wherein R 1 is a C 1 to C 30 organyl group; R 2a and R 2b independently are C 1 to C 30 organyl groups consisting essentially of inert functional groups; R 3 is hydrogen or a C 1 to C 30 organyl group consisting essentially of inert functional groups; R 4 and R 5 each independently are C 1 to C 30 organyl groups consisting essentially of inert functional groups; L 12 and L 2 each independently are C 2 to C 20 organylene groups consisting essentially of inert functional groups; L 22 is a C 3 to C 20 organylene group consisting essentially of inert functional groups; CrX p represents a chromium compound where X is a monoanion, and p is an integer from 2 to 6; Q is a neutral ligand; and q ranges from 0 to 6.

7. The process of claim 1 , wherein relative to the same process utilizing an MMAO having (a) the ratio of peak areas found in the range of −0.86 ppm to −0.74 ppm to peak areas found in a range of −0.03 ppm to 0.07 ppm greater than 2.85; (b) the ratio of peak areas found in the range of −0.03 ppm to 0.025 ppm to peak areas found in a range of 0.025 ppm to 0.07 ppm greater than 16:1; (c) the ratio of peak areas found in the range of −0.86 ppm to −0.78 ppm to peak areas found in the range of −0.78 ppm to −0.74 ppm greater than 6.7:1; or any combination thereof: (a) a catalyst system (C 6 +C 8 ) productivity is increased; (b) a liquid oligomer portion of the oligomer product comprises a reduced amount of C 10 to C 18 oligomers; (c) the oligomer product comprises a polymer having a lower Mw; (d) a Mw maximum peak of the polymer is reduced, (e) a quantity of polymer in the oligomer product is reduced; or (f) any combination thereof.

8. The process of claim 7 , wherein there is (a) at least a 10% increase in the catalyst system (C 6 +C 8 ) productivity; (b) at least a 5% reduction in the C10 to C18 oligomers in the liquid oligomer product; (c) at least a 10% reduction in the polymer Mw; (d) at least a 10% reduction in the molecular weight of the Mw maximum peak of the polymer, (e) a 30% reduction in the quantity of polymer in the oligomer product; or (f) any combination thereof.

9. The process of claim 1 , wherein relative to the same process utilizing an MMAO having (a) the ratio of peak areas found in the range of −0.86 ppm to −0.74 ppm to peak areas found in a range of −0.03 ppm to 0.07 ppm greater than 2.85; (b) the ratio of peak areas found in the range of −0.03 ppm to 0.025 ppm to peak areas found in a range of 0.025 ppm to 0.07 ppm greater than 16:1; (c) the ratio of peak areas found in the range of −0.86 ppm to −0.78 ppm to peak areas found in the range of −0.78 ppm to −0.74 ppm greater than 6.7:1; or any combination thereof, a reaction zone on-line for the process is increased.

10. The process of claim 1 , wherein, relative to the same process utilizing an MMAO having (a) the ratio of peak areas found in the range of −0.86 ppm to −0.74 ppm to peak areas found in a range of −0.03 ppm to 0.07 ppm greater than 2.85; (b) the ratio of peak areas found in the range of −0.03 ppm to 0.025 ppm to peak areas found in a range of 0.025 ppm to 0.07 ppm greater than 16:1; (c) the ratio of peak areas found in the range of −0.86 ppm to −0.78 ppm to peak areas found in the range of −0.78 ppm to −0.74 ppm greater than 6.7:1; or any combination thereof, an amount of 1-hexene in the C 6 fraction of the oligomer product is increased.

11. The process of claim 1 , wherein, relative to the same process utilizing an MMAO having (a) the ratio of peak areas found in the range of −0.86 ppm to −0.74 ppm to peak areas found in a range of −0.03 ppm to 0.07 ppm greater than 2.85; (b) the ratio of peak areas found in the range of −0.03 ppm to 0.025 ppm to peak areas found in a range of 0.025 ppm to 0.07 ppm greater than 16:1; (c) the ratio of peak areas found in the range of −0.86 ppm to −0.78

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Bischof Steven M
• Fern Jared T
• Kilgore Uriah J
• Sydora Orson L

Classifications

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title

• B01J2531/62

  Chromium · CPC title

• B01J31/189

  containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand · CPC title

• C07C2531/14

  of aluminium or boron · CPC title

• B01J31/143 Primary

  of aluminium · CPC title