Bidentate biarylphenoxy group IV transition metal catalysts for olefin polymerization with chain transfer agents

Patent metadata

Field	Value
Publication number	US-12552879-B2
Application number	US-202017764369-A
Country	US
Kind code	B2
Filing date	Sep 28, 2020
Priority date	Sep 30, 2019
Publication date	Feb 17, 2026
Grant date	Feb 17, 2026

Abstract

Processes of polymerizing olefins include contacting ethylene, a (C3-C40)alpha-olefin comonomer, and a solvent in the presence of a chain transfer agent and a catalyst system, the catalyst system comprising a metal-ligand complex according to formula (I).

First claim

The invention claimed is:

1 . A process of polymerizing olefins, the process comprising contacting ethylene, a (C 3 -C 40 ) alpha-olefin comonomer, and a solvent in the presence of a chain transfer agent and a catalyst system, wherein the chain transfer agent comprises dialkyl zinc, and wherein the catalyst system comprises a metal-ligand complex according to formula (Ia) or formula (Ic):

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 50 ) 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 ;
n is 1 or 2;
m is 2;
the metal-ligand complex has 6 or fewer metal-ligand bonds;
each Y is oxygen;
each R 1 is independently selected from carbazolyl or substituted carbazolyl;
each R 2 is independently chosen from (C 1 -C 10 )alkyl;
z 3 , z 4 , and z 5 are selected from the group consisting of sulfur, oxygen, —N(R A )—, and —C(R A )—, provided that exactly one of z 3 , z 4 , or z 5 is —C(R A )— or that exactly two of z 3 , z 4 , or z 5 are —C(R A )—;
R 3 , R 4 , R 5 , and R 6 are independently chosen from (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, halogen, or —H;
R 7 , R 8 , and R 9 are 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, wherein in formula (Ia), R 8 is methyl;
each R A 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, wherein any two R A groups bonded to neighboring atoms are optionally linked; and
each R C , R N , and R P is independently a (C 1 -C 50 )hydrocarbyl.

2 . The polymerization process according to claim 1 , wherein:
M is zirconium or hafnium; and each X is independently chosen from (C 6 -C 20 )aryl, (C 4 -C 20 )heteroaryl, (C 4 -C 12 ) diene, or a halogen.

3 . The polymerization process according to claim 1 , wherein the metal-ligand complex has a structure according to formula (Ia), and wherein R 3 , R 4 , R 5 and R 6 are —C(H)—.

4 . The polymerization process according to claim 1 , wherein each R 2 is methyl.

5 . The polymerization process according to claim 1 , wherein in formula (Ic), R 7 and R 9 are —C(H)— and R 8 is (C 1 -C 20 )alkyl.

6 . The polymerization process according to claim 1 , wherein each R 1 is carbazolyl.

7 . The polymerization process according to claim 1 , wherein each R 1 is independently 3,6-di-tert-butylcarbazol-9-yl or 2,7-di-tert-butylcarbazol-9-yl.

8 . The polymerization process of claim 1 , wherein the chain transfer agent is diethyl zinc.

9 . The polymerization process according to claim 1 , wherein the polymerization process occurs in a reactor.

10 . The polymerization process according to claim 1 , wherein the polymerization process occurs at a reaction temperature from 120° C. to 190° C.

11 . The polymerization process according to claim 1 , wherein the catalyst system further comprises a co-catalyst.

12 . The polymerization process according to claim 1 , wherein each X is independently benzyl, phenyl, or chloro.

13 . The polymerization process according to claim 1 , wherein the metal-ligand complex has a structure according to formula (Ia).

14 . The polymerization process according to claim 1 , wherein the metal-ligand complex has a structure according to formula (Ic).

15 . The polymerization process according to claim 1 , wherein the metal-ligand complex is one of the following structures:

Assignees

• Dow Global Technologies Llc

Inventors

• Szuromi Endre
• Camelio Andrew M
• Devore David D
• Milbrandt Kara A
• Christianson Matthew D

Classifications

• C08F2410/04

  Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene · CPC title

• C08F210/16 Primary

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

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F4/65904

  in combination with another component of C08F4/64 · CPC title

• C08F4/6496

  containing sulfur · CPC title