Transition metal catalysts for olefin polymerization

Patent metadata

Field	Value
Publication number	US-12473383-B2
Application number	US-202017772910-A
Country	US
Kind code	B2
Filing date	Oct 20, 2020
Priority date	Oct 30, 2019
Publication date	Nov 18, 2025
Grant date	Nov 18, 2025

Abstract

Processes of polymerizing olefin monomers using catalyst systems and catalysts systems that include a procatalyst having a structure according to formula (I):

First claim

The invention claimed is:

1 . A catalyst system comprising a metal-ligand complex according to formula (I):

where
M is a metal chosen from 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 50 )hydrocarbon, unsaturated (C 2 -C 50 )heterohydrocarbon, (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C 4 -C 12 )diene, halogen, —N(R N ) 2 , or —NCOR C ;
n is 1, 2, or 3;
m is 1 or 2;
the metal-ligand complex has 6 or fewer metal-ligand bonds;
each T is nitrogen or CR 4 , wherein each R 4 is independently chosen from (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 , halogen, or —H;
each R 1 is independently selected from the group consisting of an aliphatic (C 1 -C 50 )hydrocarbyl, an aliphatic (C 1 -C 50 )heterohydrocarbyl, -halogen, or —H, and, when m is 2, two R 1 are optionally covalently connected to each other;
each R 2 is independently chosen from (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, —Si(R C ) 3 , or —Ge(R C ) 3 ;
R 1 and R 2 are optionally covalently connected to form a ring structure;
each R 3 and each R 5 is independently chosen from (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)—, 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, or —H;
each R 6 is independently chosen from (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)—, 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)—, or halogen;
R 5 and R 6 are optionally covalently connected to form a ring structure; and
each R C , R P , and R N in formula (I) is independently a (C 1 -C 50 )hydrocarbyl.

2 . The catalyst system according to claim 1 , wherein:
each X is independently chosen from (C 6 -C 20 )aryl, (C 4 -C 20 )heteroaryl, (C 4 -C 12 )diene, or a halogen; and each R 6 is independently chosen from (C 6 -C 50 )aryl or (C 4 -C 50 )heteroaryl.

3 . The catalyst system according to claim 1 , wherein R 5 and R 6 are covalently connected to form a six-member aromatic ring.

4 . The catalyst system according to claim 1 , wherein R 5 and R 6 are covalently connected to form a six-member aromatic ring; R 3 is —H; and R 2 is methyl.

5 . The catalyst system according to claim 1 , wherein each R 6 is anthracenyl, di-substituted anthracenyl, or tri-substituted anthracenyl.

6 . The catalyst system according to claim 1 , wherein each R 6 is phenyl or a substituted phenyl.

7 . The catalyst system according to claim 1 , wherein each R 6 is a substituted phenyl chosen from 2,4,6-trimethylphenyl; 2,6-di(iso-propyl)phenyl; 3,5-di-tert-butylphenyl, or 3,5-diphenylphenyl.

8 . The catalyst system according to claim 1 , wherein m is 2 and the metal-ligand complex has a structure according to formula (II):

where M, T, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and X are as defined in formula (I); n is 1 or 2; and the dotted lines indicate optional covalent connections.

9 . The catalyst system according to claim 8 , wherein:
M is zirconium or hafnium; each X is independently chosen from (C 6 -C 50 )aryl, (C 6 -C 50 )heteroaryl, (C 4 -C 12 )diene, or halogen; each R 1 is independently chosen from (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, or halogen, and each R 2 is independently chosen from (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, or (C 4 -C 50 )heteroaryl.

10 . The catalyst system according to claim 8 , wherein the two R 1 are covalently connected to each other; and each R 2 is independently (C 1 -C 10 )alkyl.

11 . The catalyst system according to claim 8 , wherein the two R 1 are covalently connected as an alkylene chosen from —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, or —CH 2 CH 2 CH 2 CH 2 —.

12 . The catalyst system according to claim 1 , wherein m is 2 and the metal-ligand complex has a structure according to formula (III):

where M, T, R 3 , R 4 , R 5 , R 6 , and X are as defined in formula (I); n is 1 or 2; and the dotted lines indicate optional covalent connections.

13 . The catalyst system according to claim 12 , wherein each R 6 is independently chosen from carbazolyl, 3,5-di-tert-butylphenyl; 2,4,6-trimethylphenyl; 2,6-di-iso-propylphenyl; or 3,5-di-iso-propylphenyl.

14 . The catalyst system according to claim 12 , wherein each R 6 is 2,6-di-iso-propylphenyl.

15 . The catalyst system according to claim 12 , wherein each R 6 is 2,4,6-trimethylphenyl.

16 . The catalyst system according to claim 1 , wherein T is N.

17 . The catalyst system according to claim 1 , wherein T is CR 4 , and R 4 is —H.

18 . A polymerization process for producing an ethylene-based polymer, the polymerization process comprising:
polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system according to claim 1 and at least one activator to form a polymer.

19 . The polymerization process according claim 18 , wherein the activator comprises MMAO, bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate, or tris(pentafluorophenyl)borane.

Assignees

• Dow Global Technologies Llc

Inventors

• Senecal Todd D
• Pearson David M
• Jenkins Roxanne M

Classifications

• C08F4/64044

  NN · CPC title

• C08F210/16 Primary

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

• C07F7/00

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

• C08F4/64186 Primary

  Dianionic ligand · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title