Catalyst systems containing low valent titanium-aluminum complexes and polymers produced therefrom

Patent metadata

Field	Value
Publication number	US-10428091-B2
Application number	US-201815895084-A
Country	US
Kind code	B2
Filing date	Feb 13, 2018
Priority date	Apr 7, 2017
Publication date	Oct 1, 2019
Grant date	Oct 1, 2019

Abstract

Disclosed herein are methods for synthesizing low valence, titanium-aluminum complexes from half-metallocene titanium compounds and alkylaluminum compounds. The titanium-aluminum complexes can be used as components in catalyst systems for the polymerization of olefins.

First claim

We claim:

1. A method of making a titanium-aluminum complex having the formula:

the method comprising:
contacting a half-metallocene titanium compound having the formula:

with an alkylaluminum compound having the formula Al(R X )(R Y )(R Z ) to form a mixture comprising the titanium-aluminum complex having formula (A); wherein:
X 1 and X 2 independently are a halide;
R 1 , R 2 , and R 3 independently are H or a halide, C 1 to C 36 hydrocarbyl group, C 1 to C 36 halogenated hydrocarbyl group, C 1 to C 36 hydrocarboxy group, or C 1 to C 36 hydrocarbylsilyl group;
Cp is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; and
R X , R Y , and R Z independently are a C 1 to C 10 alkyl group.

2. The method of claim 1 , wherein the alkylaluminum compound comprises trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, or any combination thereof.

3. The method of claim 1 , wherein:
X 1 and X 2 are Cl;
R 1 , R 2 , and R 3 independently are H or C 1 to C 18 hydrocarbyl group; and
Cp is an unsubstituted cyclopentadienyl or indenyl group.

4. The method of claim 1 , wherein R X , R Y , and R Z independently are a C 1 to C 8 alkyl group.

5. The method of claim 1 , wherein the mixture comprising the titanium-aluminum complex is formed in a time period in a range from about 30 minutes to about 36 hours.

6. The method of claim 1 , wherein the mixture comprising the titanium-aluminum complex contains less than 10 wt. % of Ti(IV) compounds.

7. The method of claim 1 , wherein:
the mixture further comprises Ti(II) compounds and/or additional Ti(III) compounds; and
the mixture contains less than 1 wt. % of Ti(IV) compounds.

8. The method of claim 1 , wherein the molar ratio of the alkylaluminum compound to the half-metallocene titanium compound is in a range from about 1:1 to about 5:1.

9. The method of claim 1 , wherein the molar ratio of the alkylaluminum compound to the half-metallocene titanium compound is in a range from about 1.1:1 to about 2:1.

10. A titanium-aluminum complex having the formula:

wherein:
X 1 and X 2 independently are a halide;
R 1 , R 2 , and R 3 independently are H or a halide, C 1 to C 36 hydrocarbyl group, C 1 to C 36 halogenated hydrocarbyl group, C 1 to C 36 hydrocarboxy group, or C 1 to C 36 hydrocarbylsilyl group;
Cp is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; and
R Y and R Z independently are a C 1 to C 10 alkyl group.

11. The complex of claim 10 , wherein:
X 1 and X 2 are Cl;
R 1 , R 2 , and R 3 independently are H or C 1 to C 18 hydrocarbyl group; and
Cp is an unsubstituted cyclopentadienyl or indenyl group.

12. The complex of claim 10 , wherein:
X 1 and X 2 are Cl;
R 1 , R 2 , and R 3 independently are a C 1 to C 8 alkyl group; and
R Y and R Z independently are a C 1 to C 8 alkyl group.

13. A catalyst composition comprising a titanium-aluminum complex, an activator, and an optional co-catalyst, wherein the titanium-aluminum complex has the formula:

wherein:
X 1 and X 2 independently are a halide;
R 1 , R 2 , and R 3 independently are H or a halide, C 1 to C 36 hydrocarbyl group, C 1 to C 36 halogenated hydrocarbyl group, C 1 to C 36 hydrocarboxy group, or C 1 to C 36 hydrocarbylsilyl group;
Cp is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; and
R Y and R Z independently are a C 1 to C 10 alkyl group.

14. The composition of claim 13 , wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

15. The composition of claim 13 , wherein the activator comprises an activator-support, the activator-support comprising a solid oxide treated with an electron-withdrawing anion.

16. The composition of claim 13 , wherein:
the catalyst composition comprises an organoaluminum co-catalyst; and
the activator comprises a fluorided solid oxide and/or a sulfated solid oxide.

17. The composition of claim 13 , wherein the catalyst composition is produced by a process comprising:
(a) contacting a half-metallocene titanium compound having the formula:

with an alkylaluminum compound having the formula Al(R X )(R Y )(R Z ) for a first period of time to form a first mixture, the first mixture comprising the titanium-aluminum complex having formula (A); and
(b) contacting the first mixture with the activator and the co-catalyst for a second period of time to form the catalyst composition; wherein:
X 1 and X 2 independently are a halide;
R 1 , R 2 , and R 3 independently are H or a halide, C 1 to C 36 hydrocarbyl group, C 1 to C 36 halogenated hydrocarbyl group, C 1 to C 36 hydrocarboxy group, or C 1 to C 36 hydrocarbylsilyl group;
Cp is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; and
R X , R Y , and R Z independently are a C 1 to C 10 alkyl group.

18. An olefin polymerization process, the process comprising:
contacting the catalyst composition of claim 13 with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

19. The process of claim 18 , wherein:
the polymerization reactor system comprises a slurry reactor, gas-phase reactor, solution reactor, or a combination thereof; and
the olefin monomer comprises ethylene, and the olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof.

20. The process of claim 18 , wherein:
the olefin polymer comprises an ethylene homopolymer or an ethylene/α-olefin copolymer;
the activator comprises an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof; and
the catalyst composition comprises an organoaluminum co-catalyst.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Cruz Carlos A
• Barr Jared L

Classifications

• C07F5/062

  Al linked exclusively to C · CPC title

• B01J27/125

  with scandium, yttrium, aluminium, gallium, indium or thallium · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F2410/03

  Multinuclear procatalyst, i.e. containing two or more metals, being different or not · CPC title

• C08F2420/04

  Cp or analog not bridged to a non-Cp X ancillary anionic donor · CPC title