Polymerizations for olefin-based polymers

Patent metadata

Field	Value
Publication number	US-10519260-B2
Application number	US-201515311299-A
Country	US
Kind code	B2
Filing date	Jun 29, 2015
Priority date	Jun 30, 2014
Publication date	Dec 31, 2019
Grant date	Dec 31, 2019

Abstract

The invention provides a process to form an olefin-based polymer, said process comprising polymerizing at least one olefin in the presence of at least one catalyst system comprising the reaction product of the following: A) at least one cocatalyst; and B) a procatalyst comprising a metal-ligand complex of Formula (I), as described herein: (Formula I).

First claim

The invention claimed is:

1. A process to form an olefin-based polymer, said process comprising polymerizing, in a solution polymerization, at least one olefin, in the presence of at least one catalyst system comprising the reaction product of the following:
A) at least one cocatalyst; and
B) a procatalyst comprising a metal-ligand complex of Formula (I):

wherein:
M is zirconium in a formal oxidation state of +2, +3, or +4; and n is an integer of from 0 to 3, and wherein when n is 0, X is absent; and
each X, independently, is a (C 1 -C 40 )hydrocarbyl, a (C 1 -C 40 )heterohydrocarbyl, or a halide, and wherein each X, independently, is a monodentate ligand that is neutral, monoanionic, or dianionic; or
wherein two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; and
wherein X and n are chosen, in such a way, that the metal-ligand complex of Formula (I) is, overall, neutral; and
each Z independently is an oxygen atom, a sulfur atom, —N[(C 1 -C 40 )hydrocarbyl]-, or —P[(C 1 -C 40 )hydrocarbyl]-; and
L is a substituted or unsubstituted (C 1 -C 40 )hydrocarbylene, or a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbylene, and
wherein, for L, the (C 1 -C 40 )hydrocarbylene has a portion that comprises a 1-carbon atom to 10-carbon atom linker backbone linking R 21 and R 22 in Formula (I), or
wherein, for L, the (C 1 -C 40 )heterohydrocarbylene has a portion that comprises a 1-atom to 10-atom linker backbone linking R 21 and R 22 in Formula (I), wherein each of the 1 to 10 atoms of the 1-atom to 10-atom linker backbone of the (C 1 -C 40 )heterohydrocarbylene, independently, is one of the following: i) a carbon atom, ii) a heteroatom, wherein each heteroatom independently is —O— or —S—, or iii) a substituent selected from —S(O)—, —S(O) 2 —, —Si(R C ) 2 —, —Ge(R C ) 2 —, —P(R C )—, or —N(R C )—, 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
R 21 and R 22 are each, independently, C or Si;
R 6 and R 11 are chosen from (C 1 -C 20 )hydrocarbyl or halogen atom;
R 1 , R 3 , R 7 , R 10 , R 14 , R 16 , R 17 , R 18 , R 19 , R 20 are each, independently, selected from the group consisting of a substituted or unsubstituted (C 1 -C 40 )hydrocarbyl, a substituted or unsubstituted (C 1 -C 40 )hetero-hydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R C ) 2 , —N(R C ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 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 atom, and a hydrogen atom; 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 R 17 is a hydrogen atom, then R 18 is a substituted or unsubstituted (C 1 -C 40 )hydrocarbyl, a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R C ) 2 , —N(R C ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 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 atom; 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; or
wherein, when R 18 is a hydrogen atom, then R 17 is a substituted or unsubstituted (C 1 -C 40 )hydrocarbyl, a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R C ) 2 , —N(R C ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 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 atom; 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/or
wherein, when R 19 is a hydrogen atom, then R 20 is a substituted or unsubstituted (C 1 -C 40 )hydrocarbyl, a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R C ) 2 , —N(R C ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 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 atom; 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; or
wherein, when R 20 is a hydrogen atom, then R 19 is a substituted or unsubstituted (C 1 -C 40 )hydrocarbyl, a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R C ) 2 , —N(R C ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 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 atom; 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
provided that when R 1 and R 16 are both 3,6-(di-tert-butyl)carbozyl, and R 3 and R 14 are tert-octyl, and R 6 and R 11 are fluorine, then R 17 and R 19 are not methyl;
wherein, for Formula (I), two or more of R 1 through R 22 , optionally, may form one or more ring structures, and wherein each ring structure has from 3 to 50 atoms in the ring, excluding any hydrogen atoms; and
wherein, for Formula (I), one or more hydrogen atoms may optionally be substituted with one or more deuterium atoms; and
wherein the polymerization takes place at a temperature greater than, or equal to, 140° C.

2. The process of claim 1 , wherein the cocatalyst is selected from a borate, an alkyl aluminum, or an aluminoxane.

3. The process of claim 1 , wherein the solution polymerization takes place at a pressure from 10 psi to 2000 psi.

4. The process of claim 1 , wherein the olefin-based polymer is an ethylene-based polymer.

5. The process of claim 1 , wherein the olefin-based polymer is a propylene-based polymer.

6. The process of claim 1 , wherein for Formula (I), each Z is an oxygen atom.

7. The process of claim 1 , wherein for Formula (I), R 21 and R 22 are each C (carbon).

8. The process of claim 1 , wherein for Formula (I), L is selected from the following: CH 2 CH 2 CH 2 , —CH 2 CH 2 — or —CH 2 —.

9. The process of claim 1 , wherein for Formula (I), each (C 1 -C 40 )hydrocarbyl, and each (C 1 -C 40 )heterohydrocarbyl is not substituted.

10. The process of claim 1 , wherein for Formula (I), n is 2; and each X, independently, is a (C 1 -C 40 )hydrocarbyl, a (C 1 -C 40 )hetero-hydrocarbyl, or a halide.

11. The process of claim 1 , wherein R 3 and R 14 are chosen from (C 1 -C 20 )hydrocarbyl.

12. The process of claim 1 , wherein for Formula (I), R 1 and R 16 are each independently selected from the following i) through v):

13. A process to form an olefin-based polymer, said process comprising polymerizing at least one olefin, in a solution polymerization, at a temperature greater than, or equal to, 140° C., and in the presence of at least one catalyst system comprising the reaction product of the following:
A) at least one cocatalyst; and
B) a procatalyst comprising a metal-ligand complex, and wherein the procatalyst is selected from the group consisting of the following I1 through I76:

Assignees

• Dow Global Technologies Llc

Inventors

• Fontaine Philip P
• Klosin Jerzy
• Szuromi Endre
• Iverson Carl N
• Rickaway Zach T
• Young Andrew J
• Brown Susan G
• Figueroa Ruth
• Demirors Mehmet
• Kapur Mridula

Classifications

• C08F4/659

  Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F210/16 Primary

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

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title