Catalyst systems containing low valent titanium compounds and polymers produced therefrom

Patent metadata

Field	Value
Publication number	US-10000595-B1
Application number	US-201715481502-A
Country	US
Kind code	B1
Filing date	Apr 7, 2017
Priority date	Apr 7, 2017
Publication date	Jun 19, 2018
Grant date	Jun 19, 2018

Abstract

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

First claim

We claim:

1. A method of making a bimetallic compound having the formula:

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

with an alkylaluminum compound having the formula Al(R Z ) 3 to form a mixture comprising the bimetallic compound 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
each R Z independently is 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 each R Z independently is a C 1 to C 8 alkyl group.

5. The method of claim 1 , wherein the mixture comprising the bimetallic compound 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 bimetallic compound 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 bimetallic titanium compound having the formula:

wherein:
X 1 and X 2 independently are a halide; and
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.

11. The compound of claim 10 , wherein:
X 1 and X 2 are Cl; and
R 1 , R 2 , and R 3 independently are H or C 1 to C 18 hydrocarbyl group.

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

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

wherein:
X 1 and X 2 independently are a halide; and
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.

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 Z ) 3 for a first period of time to form a first mixture, the first mixture comprising the bimetallic compound 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
each R Z independently is 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

• C08F4/642

  Component covered by group C08F4/64 with an organo-aluminium compound {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F2410/03

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

• C07F9/5355

  Phosphoranes containing the structure P=N- · CPC title

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C07F7/28

  Titanium compounds · CPC title