Phosphinyl formamidine compounds, metal complexes, catalyst systems, and their use to oligomerize or polymerize olefins

Patent metadata

Field	Value
Publication number	US-9962689-B2
Application number	US-201315104185-A
Country	US
Kind code	B2
Filing date	Dec 18, 2013
Priority date	Dec 18, 2013
Publication date	May 8, 2018
Grant date	May 8, 2018

Abstract

N 2 -phosphinyl formamidine compounds and N 2 -phosphinyl formamidine metal salt complexes are described. Methods for making N 2 -phosphinyl formamidine compounds and N 2 -phosphinyl formamidine metal salt complexes are also disclosed. Catalyst systems utilizing the N 2 -phosphinyl formamidine metal salt complexes are also disclosed along with the use of the N 2 -phosphinyl amidine compounds and N 2 -phosphinyl amidinate metal salt complexes for the oligomerization and/or polymerization of olefins.

First claim

What is claimed:

1. A catalyst system comprising
a) an N 2 -phosphinyl formamidine metal salt complex having the formula

or the formula

wherein:
R 1 is a C 1 to C 30 organyl group,
R 3 is hydrogen,
R 4 and R 5 are each independently a C 1 to C 30 organyl group consisting essentially of inert functional groups, wherein each inert functional group independently is a halo group, a nitro group, a hydrocarboxy group, a sulfidyl group, or a hydrocarbyl group,
MX p represents the metal salt where M is a Group 6 transition metal, X is a monoanion and p ranges from 2 to 6, or X is a dianion and p ranges from 1 to 3,
O is a neutral ligand, and
q ranges from 0 to 6, and

b) a metal alkyl.

2. The catalyst system of claim 1 , wherein
R 1 is a C 1 to C 15 alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, or a C 6 to C 20 substituted aryl group, and
R 4 and R 5 are independently a C 1 to C 15 alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 3 to C 15 aliphatic heterocyclic group, a C 3 to C 15 substituted aliphatic heterocyclic group, a C 6 to C 20 aryl group, a C 6 to C 20 substituted aryl group, a C 3 to C 20 heteroaryl group, or a C 3 to C 20 substituted heteroaryl group.

3. The catalyst system of claim 1 , wherein
R 1 is a phenyl group or a C 6 to C 20 substituted phenyl group,
R 4 and R 5 are independently a C 1 to C 15 alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, or a C 6 to C 20 substituted aryl group,
M is chromium,
X is a halide, a C 1 to C 20 carboxylate, a C 1 to C 20 β-diketonate, or a C 1 to C 20 hydrocarboxide,
p is ranges from 2 to 3, and
Q is a C 2 to C 20 nitrile or a C 2 to C 40 either.

4. The catalyst system of claim 3 , wherein the metal alkyl comprises an aluminoxane and the aluminoxane comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof.

5. The catalyst system of claim 4 , wherein a molar ratio of the aluminum of the aluminoxane to the metal of the metal complex is at least 5:1.

6. A method of preparing a catalyst system of claim 1 , comprising forming a catalyst system mixture comprising a) the N 2 -phosphinyl formamidine metal salt complex and h) the metal alkyl.

7. The method of claim 6 , wherein the catalyst system or the catalyst system mixture is aged for at least 20 minutes in the substantial absence of the olefin to form an aged catalyst system.

8. A process comprising:
a) forming a catalyst system mixture according to claim 6 , wherein the metal alkyl is an aluminoxane;
b) contacting the catalyst system mixture with an olefin; and
c) forming an oligomer product.

9. The process of claim 8 , wherein the catalyst system or the catalyst system mixture is aged for at least 20 minutes in the substantial absence of the olefin to form an aged catalyst system.

10. A process comprising:
a) contacting an olefin and the catalyst system of claim 1 , wherein the metal alkyl is an aluminoxane; and
b) forming an oligomer product.

11. The process of claim 10 , wherein
R 1 is a C 1 to C 15 alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, or a C 6 to C 20 substituted aryl group, and
R 4 and R 5 are independently a C 1 to C 15 alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 3 to C 15 aliphatic heterocyclic group, a C 3 to C 15 substituted aliphatic heterocyclic group, a C 6 to C 20 aryl group, a C 6 to C 20 substituted aryl group, a C 3 to C 20 heteroaryl group, or a C 3 to C 20 substituted heteroaryl group.

12. The process of claim 10 , wherein
R 1 is a phenyl group or a C 6 to C 20 substituted phenyl group,
R 4 and R 5 are independently a C 1 to C 15 alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, or a C 6 to C 20 substituted aryl group,
M is chromium,
X is a halide, a C 1 to C 20 carboxylate, a C 1 to C 20 β-diketonate, or a C 1 to C 20 hydrocarboxide,
p is ranges from 2 to 3, and
Q is a C 2 to C 20 nitrite or a C 2 to C 40 ether.

13. The process of claim 12 , wherein the aluminoxane comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butyl aluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof.

14. The process of claim 13 , wherein the olefin comprises ethylene and the ethylene partial pressure ranges from 50 psig to 4,000 psig.

15. The process of claim 14 , wherein the a molar ratio of the aluminum of the aluminoxane to the metal of the metal salt complex is at least 5:1, the oligomer product is formed at a temperature ranging from 20° C. to 150° C., and optionally wherein hydrogen is contacted with the catalyst system mixture and the olefin and the hydrogen partial pressure ranges from 5 psig to 400 psig.

16. The process of claim 15 , wherein a liquid oligomer product comprises at least 70 wt. % C 6 and C 8 olefins.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Carney Michael J
• Small Brooke L
• Sydora Orson L

Classifications

• C07C2531/34

  of chromium, molybdenum or tungsten · CPC title

• B01J31/143

  of aluminium · CPC title

• B01J31/188 Primary

  Amide derivatives thereof · CPC title

• C07F9/5004

  Acyclic saturated phosphines · CPC title

• C08F4/69068

  PN · CPC title