Heterocycle-heterocycle-based group IV transition metal catalysts for olefin polymerization

Patent metadata

Field	Value
Publication number	US-12252573-B2
Application number	US-201917415365-A
Country	US
Kind code	B2
Filing date	Dec 20, 2019
Priority date	Dec 21, 2018
Publication date	Mar 18, 2025
Grant date	Mar 18, 2025

Abstract

The polymerization process of this disclosure includes includes polymerizing ethylene and one or more olefins in the presence of a catalyst system under olefin polymerization conditions to form an ethylene-based polymer. The catalyst system comprising a metal-ligand complex according to formula (I).

First claim

The invention claimed is:

1. A polymerization process comprising:
polymerizing ethylene and one or more olefins in the presence of a catalyst system under olefin polymerization conditions to form an ethylene-based polymer, the catalyst system comprising a metal-ligand complex according to formula (I):

where:
M is a metal chosen from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4;
each X is a monodentate or bidentate ligand independently chosen from unsaturated (C 2 -C 20 )hydrocarbon, unsaturated (C 2 -C 50 )heterohydrocarbon, (C 1 -C 50 )hydrocarbyl, (C 6 -C 50 )aryl, (C 6 -C 50 )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C 4 -C 12 )diene, halogen, —N(R N ) 2 , and —NCOR C ;
m is 1 or 2;
n is 2 or 3;
m+n=4;
each A is independently chosen from —C(R 3a )C(R 4a )C(R 5a )C(R 6a )—, —C(R 3a )C(R 4a )C(R 5a )N—, —C(R 3a )C(R 4a )NC(R 6a )—, —C(R 3a )NC(R 5a )C(R 6a )—, —NC(R 4a )C(R 5a )C(R 6a )— or —NC(R 4a )NC(R 6a )—, in which optionally R 3a and R 4a , or R 4a and R 5a , or R 5a and R 6a are covalently connected to form an aromatic ring or a non-aromatic ring, or —C(R 3b )C(R 4b )G- or -GC(R 4c )C(R 5c )—, wherein G is N(R 3c ), N(R 5b ), O or S, and optionally R 3b and R 4b , or R 4c and R 5c are covalently connected to form an aromatic ring or a non-aromatic ring, and;
each z 1 is independently selected from N or C(R 1 );
each z 2 is independently selected from N or C(R 2 );
each R 11 is anthracene-9-yl substituted with R S or more than one R S , wherein each R S is independently selected from (C 1 -C 12 )alkyl, (C 6 -C 15 )aryl, or (C 3 -C 12 )cycloalkyl;
each R 1 , R 2 , R 3a , R 3b , R 3c , R 4a , R 4b , R 4c , R 5a , R 5b , R 5c , and R 6a is independently selected from the group consisting of (C 1 -C 50 ) hydrocarbyl, (C 1 -C 50 ) heterohydrocarbyl, (C 6 -C 50 ) aryl, (C 4 -C 50 ) heteroaryl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, —P(O)(R P ) 2 , R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, halogen, and —H, wherein each R N , R C , and R P is independently selected from the group consisting of (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl, and —H;
when z 1 is C(R 1 ), R 1 and R 11 are not linked to form an aromatic ring or a non-aromatic ring:
when z 2 is C(R 1 ) and z 2 is C(R 2 ), R 1 and R 2 are optionally linked to form an aromatic ring or a non-aromatic ring:

provided that:
when z 1 is CR 1 and z 2 is CR 2 , where R 1 and R 2 are not covalently connected to form an aromatic ring or a non-aromatic ring, m is 1 and n is 3.

2. The polymerization process of claim 1 , wherein A is —C(R 3a )C(R 4a )C(R 5a )C(R 6a )—, in which optionally R 3a and R 4a , or R 4a and R 5a , or R 5a and R 6a are covalently connected to form an aromatic ring or a non-aromatic ring, and the metal-ligand catalyst has a structure according to formula (II):

where each z 1 , z 2 , R 11 , R 3a , R 4a , R 5a , R 6a , X, n, m, and M are defined as in formula (I).

3. The polymerization process of claim 1 , wherein A is -GC(R 4c )C(R 5c )— in which G is N(R 3c ), and optionally R 4c and R 5c are covalently connected to form an aromatic ring or a non-aromatic ring, and the metal-ligand catalyst has a structure according to formula (III):

where each z 1 , z 2 , R 11 , R 3c , R 4c , R 5c , X, n, m, and M are defined as in formula (I).

4. The polymerization process of claim 1 , wherein A is —C(R 3b )C(R 4b )G- in which G is N(R 5b ), and optionally R 3b and R 4b are covalently connected to form an aromatic ring or a non-aromatic ring, and the metal-ligand catalyst has a structure according to formula (IV):

where each z 1 , z 2 , R 11 , R 3b , R 4b , R 5b , X, n, m, and M are defined as in formula (I).

5. The polymerization process of claim 1 , wherein A is -GC(R 4c )C(R 5c )— in which G is S, and optionally R 4c and R 5c are covalently connected to form an aromatic ring or a non-aromatic ring, and the metal-ligand catalyst has a structure according to formula (V):

where each z 1 , z 2 , R 11 , R 4c , R 5c , X, n, m, and M are defined as in formula (I).

6. The polymerization process of claim 1 , wherein m is 1.

7. The polymerization process of claim 1 , wherein z 1 is N.

8. The polymerization process of claim 1 , wherein X is benzyl, phenyl, or chloro.

9. The polymerization process of claim 1 , wherein R 11 is a radical of formula (VI):

wherein R 12 , R 13 , R 14 , R 15 , and R 16 is chosen from (C 1 -C 10 )alkyl, (C 6 -C 10 )aryl, or —H.

10. The polymerization process of claim 9 , wherein R 12 , R 13 , R 14 , R 15 , and R 16 is chosen from tert-butyl, 3,5-di-tert-butylphenyl, or —H.

11. The polymerization process of claim 1 , wherein z 2 is N.

12. The polymerization process of claim 1 , wherein when z 2 is N and z 1 is CR 1 , R 1 and R 11 are not covalently connected to form an aromatic or non-aromatic ring.

13. The polymerization process of claim 1 , wherein the metal-ligand complex is selected from:

Assignees

• Dow Global Technologies Llc

Inventors

• Koenigs David
• Devore David D
• Bailey Brad C
• Szuromi Endre
• Grigg Robert D
• Pearson David M
• Mcdougal Nolan T
• Etienne John B
• Mukhopadhyay Sukrit

Classifications

• C07F7/00

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

• C07F9/5728

  condensed with carbocyclic rings or carbocyclic ring systems · CPC title

• C08F210/16 Primary

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

• C08F4/64044

  NN · CPC title

• C08F4/65908 Primary

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title