Supported transition metal bis(phenolate) complexes and their use as catalysts for olefin polymerization

Patent metadata

Field	Value
Publication number	US-11225539-B2
Application number	US-202016787837-A
Country	US
Kind code	B2
Filing date	Feb 11, 2020
Priority date	Feb 12, 2019
Publication date	Jan 18, 2022
Grant date	Jan 18, 2022

Abstract

This invention relates to supported catalyst compositions of transition metal complexes of a dianionic, tridentate ligand that features a central neutral heterocyclic Lewis base and two phenolate donors, where the tridentate ligand coordinates to the metal center to form two eight-membered rings. Preferably the bis(phenolate) complexes are represented by Formula (I):where M, L, X, m, n, E, E′, Q, R1, R2, R3, R4, R1′, R2′, R3′, R4′, A1, A1′, A3A2, and A2′A3′ are as defined herein, where A1QA1′ are part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms that links A2 to A2′ via a 3-atom bridge with Q being the central atom of the 3-atom bridge.

First claim

What is claimed is:

1. A supported catalyst composition comprising a support and a catalyst compound represented by the Formula (I):

wherein:
M is a group 3, 4, 5, or 6 transition metal or a Lanthanide;
E and E′ are each independently O, S, or NR 9 where R 9 is independently hydrogen, a C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl or a heteroatom-containing group;
Q is group 14, 15, or 16 atom that forms a dative bond to metal M;
A 1 QA 1′ are part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms that links A 2 to A 2 ′ via a 3-atom bridge with Q being the central atom of the 3-atom bridge, A 1 and A 1′ are independently C, N, or C(R 22 ), where R 22 is selected from hydrogen, C 1 -C 20 hydrocarbyl, C 1 -C 20 substituted hydrocarbyl;
A 3 A 2 is a divalent group containing 2 to 40 non-hydrogen atoms that links A 1 to the E-bonded aryl group via a 2-atom bridge;
A 2′ A 3′ is a divalent group containing 2 to 40 non-hydrogen atoms that links A 1′ to the E′-bonded aryl group via a 2-atom bridge;
L is a Lewis base;
X is an anionic ligand;
n is 1, 2 or 3;
m is 0, 1, or 2;
n+m is not greater than 4;
each of R 1 , R 2 , R 3 , R 4 , R 1′ , R 2′ , R 3′ , and R 4′ is independently hydrogen, a C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group,
and one or more of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1′ and R 2′ , R 2′ and R 3′ , R 3′ and R 4′ may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings;
any two L groups may be joined together to form a bidentate Lewis base;
an X group may be joined to an L group to form a monoanionic bidentate group;
any two X groups may be joined together to form a dianionic ligand group.

2. The composition of claim 1 , where the catalyst compound is represented by the Formula (II):

wherein:
M is a group 3, 4, 5, or 6 transition metal or a Lanthanide;
E and E′ are each independently O, S, or NR 9 , where R 9 is independently hydrogen, a C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, or a heteroatom-containing group;
each L is independently a Lewis base;
each X is independently an anionic ligand;
n is 1, 2 or 3;
m is 0, 1, or 2;
n+m is not greater than 4;
each of R 1 , R 2 , R 3 , R 4 , R 1′ , R 2′ , R 3′ , and R 4′ is independently hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1′ and R 2′ , R 2′ and R 3′ , R 3′ and R 4′ may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings; any two L groups may be joined together to form a bidentate Lewis base;
an X group may be joined to an L group to form a monoanionic bidentate group;
any two X groups may be joined together to form a dianionic ligand group;
each of R 5 , R 6 , R 7 , R 8 , R 5′ , R 6′ , R 7′ , R 8′ , R 10 , R 11 , and R 12 is independently hydrogen, a C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 5′ and R 6′ , R 6′ and R 7′ , R 7′ and R 8′ , R 10 and R 11 , or R 11 and R 12 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings.

3. The composition of claim 1 , wherein the M is Hf, Zr or Ti.

4. The composition of claim 1 , wherein E and E′ are each O.

5. The composition of claim 1 , wherein R 1 and R 1′ is independently a C 4 -C 40 tertiary hydrocarbyl group.

6. The composition of claim 1 , wherein R 1 and R 1′ is independently a C 4 -C 40 cyclic tertiary hydrocarbyl group.

7. The composition of claim 2 , wherein R 1 and R 1′ is independently a C 4 -C 40 polycyclic tertiary hydrocarbyl group.

8. The composition claim 1 , wherein each X is, independently, selected from the group consisting of substituted or unsubstituted hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, and a combination thereof, (two X's may form a part of a fused ring or a ring system).

9. The composition claim 1 , wherein each L is, independently, selected from the group consisting of: ethers, thioethers, amines, phosphines, ethyl ether, tetrahydrofuran, dimethylsulfide, triethylamine, pyridine, alkenes, alkynes, alenes, and carbenes and a combinations thereof, optionally two or more L's may form a part of a fused ring or a ring system).

10. The composition of claim 1 , wherein the support is silica, M is Zr or Hf, Q is nitrogen, both A 1 and A 1′ are carbon, both E and E′ are oxygen, and both R 1 and R 1′ are C 4 -C 20 cyclic tertiary alkyls.

11. The composition of claim 1 , wherein M is Zr or Hf, Q is nitrogen, both A 1 and A 1′ are carbon, both E and E′ are oxygen, and both R 1 and R 1″ are adamantan-1-yl or substituted adamantan-1-yl.

12. The composition of claim 1 , wherein M is Zr or Hf, Q is nitrogen, both A 1 and A 1′ are carbon, both E and E′ are oxygen, and both R 1 and R 1′ are C 6 -C 20 aryls.

13. The composition of claim 1 , wherein Q is nitrogen, A 1 and A 1′ are both carbon, both R 1 and R 1′ are hydrogen, both E and E′ are NR 9 , where R 9 is selected from a C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, or a heteroatom-containing group.

14. The composition of claim 1 , wherein Q is carbon, A 1 and A 1′ are both nitrogen, and both E and E′ are oxygen.

15. The composition of claim 1 , wherein Q is carbon, A 1 is nitrogen, A 1′ is C(R 22 ), and both E and E′ are oxygen, where R 22 is selected from hydrogen, C 1 -C 20 hydrocarbyl, C 1 -C 20 substituted hydrocarbyl.

16. The composition of claim 1 , wherein the heterocyclic Lewis base is selected from the groups represented by the following formulas:

where each R 23 is independently selected from hydrogen, C 1 -C 20 alkyls, and C 1 -C 20 substituted alkyls.

17. The composition of claim 2 , wherein M is Zr or Hf, both E and E′ are oxygen, and both R 1 and R 1′ are C 4 -C 20 cyclic tertiary alkyls.

18. The composition of claim 2 , wherein M is Zr or Hf, both E and E′ are oxygen, and both R 1 and R 1′ are adamantan-1-yl or substituted adamantan-1-yl.

19. The composition of claim 2 , wherein M is Zr or Hf, both E and E′ are oxygen, and each of R 1 , R 1′ , R 3 and R 3′ are adamantan-1-yl or substituted adamantan-1-yl.

20. The composition of claim 2 , wherein M is Zr or Hf, both E and E′ are oxygen, both R 1 and R 1′ are C 4 -C 20 cyclic tertiary alkyls, and both R 7 and R 7′ are C 1 -C 2

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Harlan Charles J
• Lambic Nikola S
• Hagadorn John R
• Canich Jo Ann M

Classifications

• B01J2531/48

  Zirconium · CPC title

• B01J2531/0225

  Complexes comprising pentahapto-cyclopentadienyl analogues · CPC title

• C07F7/00 Primary

  Compounds containing elements of Groups 4 or 14 of the Periodic Table · CPC title

• B01J2531/49

  Hafnium · CPC title

• C08F4/64158

  ONO · CPC title