Monobidentate, bis-bidentate, and tetrabidentate guanidine Group IV transition metal olefin copolymerization catalysts

Patent metadata

Field	Value
Publication number	US-12221507-B2
Application number	US-202017615440-A
Country	US
Kind code	B2
Filing date	May 28, 2020
Priority date	May 31, 2019
Publication date	Feb 11, 2025
Grant date	Feb 11, 2025

Abstract

Processes for polymerizing polyolefins include contacting ethylene and optionally one or more (C 3 -C 12 )α-olefin in the presence of a catalyst system, wherein the catalyst system comprises a metal-ligand complex having a structure according to formula (I).

First claim

The invention claimed is:

1. A process for polymerizing polyolefin, the process comprising contacting ethylene and optionally one or more (C 3 -C 12 ) α-olefin in the presence of a catalyst system, wherein the catalyst system comprises a metal-ligand structure 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;
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, (C 4 -C 12 )diene, halogen, —OR X , —N(R X ) 2 , or —NCOR X , wherein each R X is (C 1 -C 30 ) hydrocarbyl or —H;
n is 1, 2, or 3;
m is 1 or 2;
m+n=3 or 4;
each R 1 is R 1a or R 1b ;
each R 4 is R 4a or R 4b ;
R 1a , R 1b , R 4a , and R 4b are independently chosen from −H, (C 1 -C 40 ) hydrocarbyl, (C 1 -C 40 ) heterohydrocarbyl, (C 1 -C 40 ) aryl, (C 1 -C 40 ) heteroaryl, −P(R P ) 2 , —N(R N ) 2 , R C S(O)—, R C S(O) 2 —, or (R C ) 2 C═N—, where each R C and each R P is unsubstituted (C 1 -C 18 ) hydrocarbyl or —H, and where each R N is unsubstituted (C 1 -C 18 ) hydrocarbyl;
each A is selected from the group consisting of:

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

where:
R 1a , R 1b , R 4a , R 4b , M and X are as defined in formula (I), and A 1 and A 2 are independently A as defined in formula (I).

3. The process according to claim 2 , wherein m is 2, n is 2, and R 4a and R 4b are covalently linked, whereby the metal-ligand complex comprises a divalent radical Q consisting of the two covalently linked groups R 4a and R 4b and the metal-ligand complex has a structure according to formula (III):

where:
Q is (C 2 -C 12 )alkylene, (C 2 -C 12 ) heteroalkylene, (C 6 -C 50 ) arylene, (C 4 -C 50 ) heteroarylene, (—CH 2 Si(R C ) 2 CH 2 —), (—CH 2 CH 2 Si(R C ) 2 CH 2 CH 2 —), (—CH 2 Ge(R C ) 2 CH 2 —), or (—CH 2 CH 2 Ge(R C ) 2 CH 2 CH 2 —), where each R C is unsubstituted (C 1 -C 18 ) hydrocarbyl or —H; and
R 1a , R 1b , R 4a , R 4b , M, and X are as defined in formula (I) and A 1 and A 2 are as defined in formula (II).

4. The process of claim 1 , wherein each X is identical when n is 2 or 3.

5. The process of claim 1 , wherein each X is benzyl, chloro, —CH 2 SiMe 3 , or phenyl.

6. The process of claim 1 , wherein each R 1 , R 1a , or R 1a and each R 4 , R 4a , or R 4b are independently (C 1 -C 20 )alkyl or (C 1 -C 20 ) aryl.

7. The process of claim 1 , wherein each R 1 and each R 4 are independently benzyl, cyclohexyl, 2,6-dimethylphenyl, tert-butyl, or ethyl.

8. The process of claim 3 , wherein R 1a and R 1b are 2-propyl.

9. The process of claim 1 , wherein each A has one of the following structures:

10. The process of claim 1 , wherein R 1a , R 1b , R 4a , and R 4b are independently chosen from 3,5-di-tert-butylphenyl; 2,4,6-trimethylphenyl; 2,6-dimethylphenyl; 2,4,6-triisopropylphenyl; 2,6-di-iso-propylphenyl; benzyl, cyclohexyl, or 2-propyl.

11. The process according to claim 3 , wherein Q is chosen from —(CH 2 ) x —, where x is from 2 to 5.

12. The process according to claim 3 , wherein Q is —(CH 2 ) 4 —.

13. The process of claim 1 , wherein the catalyst system further comprises a chain transfer agent.

14. The process according to claim 13 , wherein the chain transfer agent is diethylzinc.

Assignees

• Dow Global Technologies Llc

Inventors

• Camelio Andrew M
• Bailey Brad C
• Froese Robert D J
• Mukhopadhyay Sukrit

Classifications

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title

• C08F210/16 Primary

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

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F4/65904

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

• C08F4/65912

  in combination with an organoaluminium compound · CPC title