Olefin polymerization activators

Patent metadata

Field	Value
Publication number	US-11447586-B2
Application number	US-201917043304-A
Country	US
Kind code	B2
Filing date	Mar 26, 2019
Priority date	Mar 30, 2018
Publication date	Sep 20, 2022
Grant date	Sep 20, 2022

Abstract

Embodiments of this disclosure include processes of polymerizing olefins, the process comprising contacting ethylene and a (C3-C40)alpha-olefin comonomer in the presence of a catalyst system, the catalyst system comprising a Group IV metal-ligand complex and an ionic metallic activator complex, the ionic metallic activator complex comprising an anion and a countercation, the anion having a structure according to formula (I):formula (I)

First claim

The invention claimed is:

1. A process of polymerizing olefins, the process comprising contacting ethylene and a (C 3 -C 40 )alpha-olefin comonomer in the presence of a catalyst system to produce an ethylene-based polymer, the catalyst system comprising a procatalyst and an ionic metallic activator complex, the ionic metallic activator complex comprising an anion and a countercation, the anion having a structure according to formula (I):

where:
M is aluminum, boron, or gallium;
n is 3 or 4;
each R is independently selected from the group consisting of radicals having formula (II) and radicals having formula (III):

each Y is independently carbon or silicon;
each R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , and R 25 is independently chosen from (C 1 -C 40 )alkyl, (C 6 -C 40 )aryl, —OR C , —SR C , —H, or —F, wherein when R is a radical according to formula (III), at least one of R 21 , R 22 , R 23 , R 24 , or R 25 is a halogen-substituted (C 1 -C 40 )alkyl , a halogen-substituted (C 6 -C 40 )aryl, or —F; and
provided that:
when each R is a radical according to formula (II) and Y is carbon, at least one of R 11 , R 12 , or R 13 is a halogen-substituted (C 1 -C 40 )alkyl , a halogen-substituted (C 6 -C 40 )aryl, or —F; and
when M is aluminum and n is 4 and each R is a radical according to formula (II), and each Y is carbon:
each R 11 , R 12 , and R 13 of each R is a halogen-substituted (C 1 -C 40 )alkyl, a halogen-substituted (C 6 -C 40 )aryl, or —F; or
at least one of R 11 , R 12 , or R 13 is —H and a total number of halogen atoms in R 11 , R 12 , and R 13 of each R is at least six;

each X is a monodentate ligand independently chosen from halogen-substituted (C 1 -C 20 )alkyl, (C 1 -C 20 )alkyl, halogen-substituted (C 6 -C 40 )aryl, (C 6 -C 40 )aryl, triflate, or —S(O) 3 R C ;
optionally, two groups R in formula (I) are covalently connected;
each R C is independently (C 1 -C 30 )hydrocarbyl or —H;
wherein
when n is 4, no more than one R is a radical having formula (III); and
the countercation is + N(H)R N 3 , where each R N is chosen from (C 1 -C 20 )alkyl or (C 6 -C 20 )aryl, + C(C 6 H 5 ) 3 ; or + C(C 6 H 4 R C ) 3 , where R C is (C 1 -C 20 )alkyl;
the procatalyst is selected from the group consisting of Group IV metal-ligand complexes (Group IVB according to CAS or Group 4 according to IUPAC naming conventions.

2. The process according to claim 1 , wherein the procatalyst is a bis(phenylphenoxy) metal-ligand complex.

3. The process according to claim 1 , wherein n is 4 and each R is independently —C(H)(CF 3 ) 2 , —C 6 F 5 , or —C(CF 3 ) 3 .

4. The process according to claim 1 , wherein n is 3 and X is chosen from, triflate (—OTf), methyl, or halogen.

5. The process according to claim 1 , wherein n is 4, and three of four groups R are —C(CF 3 ) 3 and one of four groups R is —C 6 F 5 .

6. The process according to claim 1 , wherein the countercation is + N(H)R N 3 , where each R N is chosen from (C 1 -C 20 )alkyl or (C 6 -C 20 )aryl.

7. The process according to claim 1 , wherein the countercation is + N(H)R N 3 , where each where at least two R N are chosen from (C 10 -C 20 )alkyl.

8. The process according to claim 1 , wherein the countercation is + C(C 6 H 5 ) 3 .

9. The process according to claim 1 , wherein the countercation is + C(C 6 H 4 R C ) 3 , where R C is (C 1 -C 20 )alkyl.

10. The process according to claim 1 , wherein two groups R are covalently connected and the anion has a structure according to formula (IV):

where:
M and X are as defined in formula (I);
n is 2;
L represents the two groups R that are covalently connected;
each L is independently chosen from (C 2 -C 40 )alkylene, (C 2 -C 40 )heteroalkylene or or —(Si(R C ) 2 —O) z —Si(R C ) 2 —, where z is 0, 1, 2, or 3; and wherein R C is independently (C 1 -C 30 )hydrocarbyl or —H; and
when n is 1, X is a monodentate ligand independently chosen from halogen, halogenated-(C 1 -C 20 )alkyl, or triflate.

11. The process according to claim 1 , wherein the ionic metallic activator complex in a high-boiling-point fully saturated hydrocarbon solution having a concentration of 200 micromoles of ionic metallic activator complex and 20 millimoles of water in a high-boiling-point fully saturated hydrocarbon solution has a percent dissipation factor of less than or equal to 0.1 as measured by the Hydrocarbon Conductivity Test.

Assignees

• Dow Global Technologies Llc

Inventors

• Keaton Richard J
• Huacuja Rafael
• Wilson David R
• Klosin Jerzy
• Pearson David M
• Senecal Todd D
• Mukhopadhyay Sukrit
• Woodward William H H

Classifications

• C08F4/6437

  containing aluminium · CPC title

• C08F4/659

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

• C08F4/52

  selected from boron, aluminium, gallium, indium, thallium or rare earths (C08F4/14 takes precedence) · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F4/65908

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