Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers

Patent metadata

Field	Value
Publication number	US-9975975-B2
Application number	US-201515310553-A
Country	US
Kind code	B2
Filing date	Jul 23, 2015
Priority date	Jul 24, 2014
Publication date	May 22, 2018
Grant date	May 22, 2018

Abstract

The invention provides a process, and transition metal complex, to form an ethylene-based polymer, said process comprising polymerizing ethylene, and optionally at least one comonomer, in the presence of at least one molecular transition metal complex selected from Formula 1, as described herein.

First claim

The invention claimed is:

1. A process to form an ethylene-based polymer, said process comprising polymerizing ethylene, and optionally at least one comonomer, in the presence of at least one molecular transition metal complex selected from Formula 1:

wherein M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4;
n is an integer of from 0 to 3, wherein when n is 0, X is absent;
each X is independently a monodentate ligand that is neutral, monoanionic, or dianionic, or two X are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic;
X and n are selected such that the metal-ligand complex is neutral;
each Z moiety is, independently, —O—, —S—, —N[(C 1 -C 40 )hydrocarbyl]-, or —P[(C 1 -C 40 )hydrocarbyl]-;
R x is selected from the following: a substituted or unsubstituted (C 1 -C 40 )hydrocarbyl; a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbyl: —Si(R C ) 3 , —OSi(R C ) 3 —Ge(R C ) 3 , —P(R C ) 2 , —N(R C ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , —OCF 3 , —S(O)R C , —S(O) 2 R C , —N═C(R C ) 2 , —OC(O)R C , —C(O)OR C , —N(R)C(O)R C , —C(O)N(R C ) 2 , a halogen, or a hydrogen; and wherein each R C is independently a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, or a substituted or unsubstituted (C 1 -C 30 ) heterohydrocarbyl;
R y is selected from the following: a substituted or unsubstituted (C 1 -C 40 )hydrocarbyl; a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbyl; —Si(R C ) 3 , —OSi(R C ) 3 , —Ge(R C ) 3 , —P(R C ) 2 , —N(R C ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , —OCF 3 , —S(O)R C , —S(O) 2 R C , —N═C(R C ) 2 , —OC(O)R C , —C(O)OR C , —N(R)C(O)R C , —C(O)N(R C ) 2 , a halogen, or a hydrogen; and wherein each R C is independently a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, or a substituted or unsubstituted (C 1 -C 30 ) heterohydrocarbyl; and
wherein, when Rx is hydrogen, Ry is not hydrogen, and when Ry is hydrogen, Rx is not hydrogen; and
wherein Rx and Ry optionally form a ring structure; and
wherein R 1a , R 2a , R 3a , R 4a , R 1b , R 2b , R 3b , R 4b , R 5c , R 6c , R 7c , R 8c , R 5d , R 6d , R 7d and R 8d are each, independently, selected from the following: a substituted or unsubstituted (C 1 -C 40 )-hydrocarbyl, a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —OSi(R C ) 3 , —Ge(R C ) 3 , —P(R C ) 2 , —N(R C ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , —OCF 3 , —S(O)R C , —S(O) 2 R C , —N═C(R C ) 2 , —OC(O)R C , —C(O)OR C , —N(R)C(O)R C , —C(O)N(R C ) 2 , a halogen, or a hydrogen; and wherein each R C is independently a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, or a substituted or unsubstituted (C 1 -C 30 ) heterohydrocarbyl; and
wherein, for Formula 1, one or more hydrogen atoms optionally be substituted with deuterium, and
wherein, for Formula 1, two or more of R 1a , R 2a , R 3a , R 4a , R 1b , R 2b , R 3b , R 4b , R 5c , R 6c , R 7c , R 8c , R 5d , R 6d , R 7d and R 8d optionally form one or more ring structures.

2. The process of claim 1 wherein at least one of R 3a or R 3b is a halogen.

3. The process of claim 1 , wherein Rx or Ry is hydrogen, and the other is a substituted or unsubstituted (C1-C40) hydrocarbyl.

4. The process of claim 3 , wherein Rx or Ry is hydrogen, and the other is an unsubstituted (C1-C20) hydrocarbyl.

5. The process of claim 1 , wherein each Z is —O— (oxygen atom).

6. The process of claim 1 , wherein n is 2, and each X is independently an alkyl.

7. The process of claim 1 , wherein R 5c and R 5d are each independently selected from the following: 1,2,3,4-tetrahydronaphthyl; anthracenyl; 1,2,3,4-tetrahydroanthracenyl; 1,2,3,4,5,6,7,8-octahydroanthracenyl; phenanthrenyl; 1,2,3,4,5,6,7,8-octahydrophenanthrenyl; 2,6-dimethylphenyl; 2,6-diisopropylphenyl; 3,5-di(tertiary-butyl)phenyl; 3,5-diphenylphenyl; 1-naphthyl; 2-methyl-1-naphthyl; 2-naphthyl; 1,2,3,4-tetra-hydronaphth-5-yl; 1,2,3,4-tetrahydronaphth-6-yl; anthracen-9-yl; 1,2,3,4-tetrahydro-anthracen-9-yl; 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl; 1,2,3,4,5,6,7,8-octahydrophenanthren-9-yl; indolyl; indolinyl; quinolinyl; 1,2,3,4-tetrahydroquinolinyl; isoquinolinyl; 1,2,3,4-tetrahydro-isoquinolinyl; carbazolyl; 1,2,3,4-tetrahydrocarbazolyl; 1,2,3,4,5,6,7,8-octahydrocarbazolyl; 3,6-di(tertiary-butyl)-carbazol-9-yl; 3,6-di(tertiary-octyl)-carbazol-9-yl; 3,6-diphenylcarbazol-9-yl; 3,6-bis(2,4,6-trimethylphenyl)-carbazol-9-yl; 2,7-di(tertiary-butyl)-carbazol-9-yl; 2,7-di(tertiary-octyl)-carbazol-9-yl; 2,7-diphenylcarbazol-9-yl; or 2,7-bis(2,4,6-trimethylphenyl)-carbazol-9-yl.

8. The process of claim 1 , wherein R 7c and R 7d are each independently an alkyl.

9. The process of claim 1 , wherein R 1a , R 2a , R 4a , R 1b , R 2b , R 4b , R 6c , R 8c , R 6d and R 8d are each hydrogen.

10. The process of claim 1 , wherein the process is run at a polymerization temperature greater than, or equal to, 170° C.

11. The process of claim 1 , wherein the ethylene-based polymer has a melt viscosity, at 177° C., less than, or equal to, 50,000 cP.

12. The process of claim 1 , wherein the ethylene-based polymer is an ethylene/α-olefin copolymer.

13. The process of claim 1 , wherein Formula 1 is selected from the following structures a) through dd):

Assignees

• Dow Global Technologies Llc

Inventors

• Ewart Sean W
• Keaton Richard J
• Klosin Jerzy
• Figueroa Ruth

Classifications

• C08F4/65904

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

• C07F7/00 Primary

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

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/64193

  OOOO · CPC title

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · CPC title