Catalysts, catalyst systems, and methods for using the same

Patent metadata

Field	Value
Publication number	US-11440979-B2
Application number	US-201916958891-A
Country	US
Kind code	B2
Filing date	Feb 5, 2019
Priority date	Feb 19, 2018
Publication date	Sep 13, 2022
Grant date	Sep 13, 2022

Abstract

Catalysts, catalysts systems and methods of polymerizing olefins are provided. The catalyst system may contain two catalysts. Polyolefin polymers are also provided.

First claim

We claim:

1. A catalyst represented by formula (Ia):

wherein:
each M is a group 4 metal;
E is N;
each of X 1 , X 2 , X 3 , and X 4 is independently hydrogen, halogen, hydroxyl, —N(C 1 -C 40 hydrocarbyl) 2 , C 1 -C 40 hydrocarbyl, or substituted C 1 -C 40 hydrocarbyl;
each of R 1 , R 2 , and R 3 is independently hydrogen, halogen, C 1 -C 40 hydrocarbyl, substituted C 1 -C 40 hydrocarbyl, C 6 -C 10 aryl, substituted C 6 -C 10 aryl, —NR′ 2 , —SR′, —OR′, —OSiR′ 3 , or —PR′ 2 , wherein each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl or one or both of R 1 and R 2 or R 2 and R 3 are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring;
each of R 4 , R 5 , 105 and 106 is independently hydrogen or Ci-C 40 hydrocarbyl; and
each of R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 is independently hydrogen, halogen, C 1 -C 40 hydrocarbyl, substituted C 1 -C 40 hydrocarbyl, C 6 -C 10 aryl, substituted C 6 -C 10 aryl, —NR′ 2 , —SR′, —OR′, —OSiR′ 3 , or —PR′ 2 , wherein each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl aryl, or one or more of R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 17 and R 18 , R 18 and R 19 , R 17 and R 20 , R 21 and R 22 , R 22 and R 23 , R 23 and R 24 , R 24 and R 25 , and R 21 and R 25 are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring.

2. The catalyst of claim 1 , wherein M is hafnium or zirconium.

3. The catalyst of claim 1 , wherein one or more of R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 17 and R 18 , R 18 and R 19 , R 17 and R 20 are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring.

4. The catalyst of claim 1 , wherein one of R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 are joined to form a saturated ring or unsaturated ring substituted with one or more of halogen, C 1 -C 40 hydrocarbyl, substituted C 1 -C 40 hydrocarbyl, —NR′ 2 , —SR′, —OR′, —OSiR′ 3 , or —PR′ 2 , wherein each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl.

5. The catalyst of claim 4 , wherein one of R 16 and R 17 , R 17 and R 18 , and R 18 and R 19 are joined to form a saturated ring or unsaturated ring substituted with one or more of halogen, C 1 -C 40 hydrocarbyl, substituted C 1 -C 40 hydrocarbyl, —NR′ 2 , —SR′, —OR′, —OSiR′ 3 , or —PR′ 2 , wherein each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl.

6. The catalyst of claim 1 , wherein each of R 1 , R 2 , and R 3 is independently hydrogen, C 1 -C 40 hydrocarbyl, or substituted C 1 -C 40 hydrocarbyl.

7. The catalyst of claim 1 , wherein each of X 1 , X 2 , X 3 , and X 4 is independently halogen or C 1 -C 40 hydrocarbyl.

8. The catalyst of claim 1 , wherein each of R 4 , R 5 , R 15 , and R 16 is hydrogen.

9. The catalyst of claim 1 , wherein each of R 6 , R 7 , R 8 , R 9 , R 17 , R 18 , R 19 , and R 20 is hydrogen.

10. The catalyst of claim 1 , wherein each of R 10 , R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 , R 24 , and R 25 is independently hydrogen or C 1 -C 20 hydrocarbyl.

11. The catalyst of claim 1 , wherein each of R 10 , R 11 , R 12 , R 13 , and R 14 is methyl.

12. The catalyst of claim 1 , wherein the catalyst represented by formula (Ia) is one or more of:

13. The catalyst of claim 1 , wherein the catalyst represented by formula (Ia) is one or more of:

14. A catalyst system comprising the product of the combination of:
(a) the catalyst of claim 1 ;
(b) optionally, a bridged or unbridged metallocene catalyst other than the catalyst of (a); and
(c) an activator.

15. The catalyst system of claim 14 , further comprising a support material; and a molar ratio of activator to catalyst is from 1.5:1 to 5:1.

16. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising:
(a) contacting at least one olefin with the catalyst system of claim 14 ; and
(b) obtaining a polyolefin.

17. The method of claim 16 , wherein contacting occurs at a temperature of 0° C. to 300° C., at a pressure in the range of from 0.35 MPa to 10 MPa, and at a time up to 300 min; and the olefin comprises ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, or mixtures thereof.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Carpenter Alex E
• Singleton Danielle Gold

Classifications

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C07F17/00 Primary

  Metallocenes · CPC title

• C08F4/65916 Primary

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C08F2410/03

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

• C08F210/16

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