Biaryl phenoxy group iv transition metal catalysts for olefin polymerization

Patent metadata

Field	Value
Publication number	US-11104751-B2
Application number	US-201816624564-A
Country	US
Kind code	B2
Filing date	Jun 19, 2018
Priority date	Jun 20, 2017
Publication date	Aug 31, 2021
Grant date	Aug 31, 2021

Abstract

Embodiments are directed to catalyst systems comprising at least one metal ligand complex and to processes for polyolefin polymerization incorporating the catalyst systems. The metal ligand complexes have the following structures: (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 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 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 Y is independently selected from oxygen or sulfur;
each R 1 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;
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 , and or —Ge(R C ) 3 ;
for each individual ring containing groups z 1 and z 2 , each of z 1 and z 2 is independently selected from the group consisting of sulfur, oxygen, —N(R R )—, ═N—, and —C(R R )—, provided that at least one of z 1 or z 2 is —C(R R )—;
each A is independently chosen from -z 3 -z 4 -z 5 - or —C(R 3 )C(R 4 )C(R 5 )C(R 6 )—, where:
each of z 3 , z 4 , and z 5 is selected from the group consisting of sulfur, oxygen, —N(R R )—, and —C(R R )—, provided that exactly one of z 3 , z 4 , or z 5 is —C(R R )— or that exactly two of z 3 , z 4 , or z 5 are —C(R R )—; and
each R 3 , R 4 , R 5 , and 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)—, halogen, or —H;

each R C , R N , and R P in formula (I) is independently a (C 1 -C 50 )hydrocarbyl; and
each R R 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 R groups bonded to neighboring atoms are optionally linked.

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

3. The catalyst system according to claim 1 , wherein for each individual ring containing groups z 1 and z 2 , one of z 1 and z 2 is sulfur, and the other is C(H).

4. The catalyst system according to claim 1 , wherein each A is —C(R 3 )C(R 4 )C(R 5 )C(R 6 )— each R 3 , R 4 , R 5 , and R 6 is —H.

5. The catalyst system according to claim 1 , wherein each R 1 is carbazolyl and each R 2 is methyl.

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

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

where R 1 , R 2 , z 1 , z 2 , A, Y, and X are as defined in formula (I); and n is 1 or 2.

8. The catalyst system according to claim 7 , 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 Y is oxygen;
each R 1 and 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, halogen, and hydrogen.

9. The catalyst system according to claim 7 , wherein for each individual ring containing groups z 1 and z 2 , one of z 1 and z 2 is sulfur, and the other is —C(H)—.

10. The catalyst system according to claim 7 , wherein each R 1 is carbazolyl and each R 2 is methyl.

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

12. The catalyst system according to claim 7 , wherein each R 1 is 3,5-di-tert-butylphenyl.

13. The catalyst system according to claim 7 , wherein each R 1 is 2,4,6-trimethylphenyl.

14. 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.

15. A polymerization process for producing a propylene-based polymer, the polymerization process comprising:
polymerizing propylene with or without an additional α-olefin in the presence of a catalyst system according to claim 1 and at least one activator to form a polymer.

16. The polymerization process according claim 15 , wherein the activator comprises MMAO, bis(hydrogenated tallow alkyl)methylammonium, tetrakis(pentafluorophenyl)borate, or tris(pentafluorophenyl)borane.

Assignees

• Dow Global Technologies Llc

Inventors

• Camelio Andrew M
• Szuromi Endre
• Devore David D
• Froese Robert D J

Classifications

• C08F4/64196

  OSSO · CPC title

• C08F4/64058

  OO · CPC title

• C08F4/65912 Primary

  in combination with an organoaluminium compound · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C08F4/64024

  OS · CPC title