Salenol catalyst

Patent metadata

Field	Value
Publication number	US-9200099-B2
Application number	US-201414289186-A
Country	US
Kind code	B2
Filing date	May 28, 2014
Priority date	Jun 20, 2013
Publication date	Dec 1, 2015
Grant date	Dec 1, 2015

Abstract

Catalysts comprising salenol ligands are disclosed herein. Also, catalyst systems comprising the catalyst and an activator; methods to prepare the ligands, catalysts and catalyst systems; processes to polymerize olefins using the catalysts and/or catalyst systems; and the olefin polymers prepared according to the processes.

First claim

What is claimed is:

1. A catalyst compound represented by the formula:

wherein each solid line represents a covalent bond and each dashed line represents a bond having varying degrees of covalency and a varying degree of coordination;
wherein M is a Group 3, 4, 5 or 6 transition metal;
wherein N 1 and N 2 are nitrogen and O 1 and O 2 are oxygen;
wherein n is 1 or 2;
wherein each X is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a functional group comprising elements from Groups 13-17 of the periodic table of the elements, or where n is 2 each X may join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
wherein Y is selected from the group consisting of divalent C 1 to C 20 hydrocarbyl radicals, divalent functional groups comprising elements from Groups 13-17 of the periodic table of the elements, and combinations thereof; and
wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is, independently, a hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Group 13-17 of the periodic table of the elements, or two or more of R 1 to R 10 and Y may independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure.

2. The catalyst compound of claim 1 , wherein n is 2 and comprising [O 1 ,N 1 ,N 2 ]—[N 1 ,N 2 ,O 2 ] in a fac-mer, a mer-fac, or a fac-fac arrangement.

3. The catalyst compound of claim 1 , wherein M is Ti, Hf or Zr.

4. The catalyst compound of claim 1 , wherein X is a benzyl radical.

5. The catalyst compound of claim 1 , wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is, independently, hydrogen, a halogen, or a C 1 to C 10 hydrocarbyl radical.

6. The catalyst compound of claim 1 , wherein Y comprises a phenylene divalent radical.

7. The catalyst compound of claim 1 , wherein Y and R 9 join together to form a C 4 to C 62 cyclic or polycyclic ring structure, represented by the formula:

8. The catalyst compound of claim 1 wherein:
each X is a benzyl radical;
at least one of R 2 , R 4 , R 5 , R 6 and R 9 is independently selected from the group consisting of: C 1 -C 10 alkyl, C 1 -C 10 cycloalkyl, C 1 -C 10 alkenyl, C 1 -C 10 alkoxy, aryl substituted C 1 -C 10 alkyl, C 1 -C 10 aryl, halo and combinations thereof; and
R 1 , R 3 , R 7 , R 8 and R 10 are hydrogen.

9. The catalyst compound of claim 8 , wherein at least one of R 2 , R 4 , R 5 , R 6 and R 9 is independently selected from the group consisting of: methyl, ethyl, isopropyl, isobutyl, tertiary-butyl, isopentyl, 2-methyl-2-phenylethyl; methoxy, benzyl, phenyl, adamantyl, chloro, bromo, iodo, perfluoro C 1 to C 10 alkyl, and combinations thereof.

10. The catalyst compound of claim 1 , wherein:
R 2 , R 4 , R 5 , R 6 , R 9 or a combination thereof is chloro, bromo, iodo, a bulky ligand substitution or a combination thereof;
the bulky ligand substitution comprises a molecular volume greater than or equal to the molecular volume of a tertiary-butyl substitution; and
the bulky ligand substitution comprise a C 4 to C 20 hydrocarbyl radical, —SR 10 , —NR 11 2 , —PR 12 2 , or a combination thereof, where each R 10 , R 11 and R 12 is independently a C 1 to C 30 hydrocarbyl.

11. The catalyst compound of claim 1 represented by the formula:

wherein R 5 is different than R 6 ; R 7 is different than R 8 , or a combination thereof.

12. A catalyst system, comprising an activator and a catalyst compound represented by the formula:

wherein each solid line represents a covalent bond and each dashed line represents a bond having varying degrees of covalency and a varying degree of coordination;
wherein M is a Group 3, 4, 5 or 6 transition metal;
wherein N 1 and N 2 are nitrogen and O 1 and O 2 are oxygen;
wherein n is 1 or 2;
wherein each X is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a functional group comprising elements from Groups 13-17 of the periodic table of the elements, or where n is 2 each X may join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
wherein Y is selected from the group consisting of divalent C 1 to C 20 hydrocarbyl radicals, divalent functional groups comprising elements from Groups 13-17 of the periodic table of the elements, and combinations thereof; and
wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is, independently, a hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Group 13-17 of the periodic table of the elements, or two or more of R 1 to R 10 and Y may independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure.

13. The catalyst system of claim 12 , wherein n is 2 and comprising [O 1 ,N 1 ,N 2 ]—[N 1 ,N 2 ,O 2 ] in a fac-mer, a mer-fac, or a fac-fac arrangement; or wherein activation rearranges [O 1 ,N 1 ,N 2 ]—[N 1 ,N 2 ,O 2 ] into a fac-mer, a mer-fac, or a fac-fac arrangement.

14. The catalyst system of claim 12 , wherein the activator comprises alumoxane, a non-coordinating anion activator, or a combination thereof.

15. The catalyst system of claim 12 , wherein the activator comprises alumoxane and the alumoxane is present at a ratio of 1 mole aluminum or more per mole of catalyst compound.

16. The catalyst system of claim 12 , wherein the activator is represented by the formula:
(Z) d + (A d− )
wherein Z is (L-H), or a reducible Lewis Acid, wherein L is a neutral Lewis base, H is hydrogen and (L-H) + is a Bronsted acid;
A d− is a non-coordinating anion having the charge d − ; and
d is an integer from 1 to 3.

17. The catalyst system of claim 12 , wherein the activator is represented by the formula:
(Z) d + (A d− )
wherein A d− is a non-coordinating anion having the charge d − ;
d is an integer from 1 to 3, and
Z is a reducible Lewis acid represented by the formula: (Ar 3 C + ), where Ar is aryl radical, an aryl radical substituted with a heteroatom, an aryl radical substituted with one or more C 1 to C 40 hydrocarbyl radicals, an aryl radical substituted with one or more functional groups comprising elements from Groups 13-17 of the periodic table of the elements or a combination thereof.

18. A process to activate a catalyst system, comprising combining an activator with a catalyst compound represented by the formula:

wherein each solid line represents a covalent bond and each dashed line represents a bond having varying degrees of covalency and a varying degree of coordination;
wherein M is a Group 3, 4, 5 or 6 transition metal;
wherein N 1 and N 2 are nitrogen and O 1 and O 2 are oxygen;
wherein n is 1 or 2;
wherein each X is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a functional group comprising elements from Groups 13-17 of the periodic table of the elements, or where n is 2 each X may join together to for

Assignees

• Exxonmobil Chem Patents Inc
• Univ Ramot

Inventors

• Kol Moshe
• Press Konstantin
• Holtcamp Matthew W

Classifications

• C07F7/006

  Chemistry & Metallurgy · mapped topic

• C08F110/06 Primary

  Propene · CPC title

• C08F4/60189

  ONNO · CPC title

• C08F4/64189

  ONNO · CPC title

• C07F7/003

  without C-Metal linkages · CPC title