Supported catalyst systems containing a germanium bridged, anthracenyl substituted bis-biphenyl-phenoxy organometallic compound for making polyethylene and polyethylene copolymer resins in a gas phase polymerization reactor

Patent metadata

Field	Value
Publication number	US-2025034292-A1
Application number	US-202218710820-A
Country	US
Kind code	A1
Filing date	Nov 21, 2022
Priority date	Nov 23, 2021
Publication date	Jan 30, 2025
Grant date	—

Abstract

Embodiments of the present application are directed to supported catalyst systems that include a metal-ligand complex having the structure of formula (I).

First claim

1 . A supported catalyst system comprising a metal-ligand complex disposed on one or more support materials, wherein the metal-ligand complex has a structure according to formula (I):

wherein:
M is titanium, zirconium, or hafnium;
n is 1, 2, or 3;
each X is a monodentate ligand independently chosen from (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, halogen, —N(R N ) 2 , N(R N )COR C , —OR, —OPh, —OAr and —H;
the metal-ligand complex is overall charge-neutral;
each Z is independently chosen from —O—, —S—, (C 6 -C 50 )aryl, (C 2 -C 50 )heteroaryl, N(C 1 -C 50 )hydrocarbyl, N(C 1 -C 50 )aryl, P(C 1 -C 50 )aryl, and P(C 1 -C 50 )hydrocarbyl;
R 9 and R 10 are independently chosen from (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl and —H;
R 11 and R 12 are independently chosen from halogen, (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl and —H;
R 1 -R 8 are each independently (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl and —H;
R 13 and R 14 are independently chosen from (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl and —H;
R 15 and R 16 are independently chosen from (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl and —H;
R 17 and R 18 are both: (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl,

 or —H, where R 19-23 are independently chosen from (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl and —H; and
each R, R C and R N are independently chosen from —H, (C 1 -C 50 )hydrocarbyl, and (C 1 -C 50 )heterohydrocarbyl.

2 . The supported catalyst system of claim 1 , wherein Z is —O—; or wherein n is 2 and each X is methyl.

3 . The supported catalyst system of claim 1 , wherein R 9 and R 10 are each 1,1,-dimethyl-3,3,-dimethylbutyl or tert-octyl.

4 . The supported catalyst system of claim 3 , wherein R 11 and R 12 are each 1,1,-dimethyl-3,3,-dimethylbutyl or tert-octyl; or wherein R 11 and R 12 are each —F.

5 . The supported catalyst system of claim 1 , wherein R 1 , R 4 , R 5 and R 8 are each tert-butyl and R 2 , R 3 , R 6 and R 7 are each —H; or wherein R 1 , R 4 , R 5 and R 8 are each —H and R 2 , R 3 , R 6 and R 7 are each tert-butyl; or wherein R 17 and R 18 are both

and R 20 and R 22 are each tert-butyl and R 19 , R 21 and R 23 are each —H; or wherein R 17 and R 18 are both —H; or wherein at least two R groups of R 19-23 are (C 1 -C 20 )hydrocarbyl; or wherein R 11 and R 12 are halogen R 1 , R 4 , R 5 and R 8 are each independently (C 1 -C 20 )hydrocarbyl and R 2 , R 3 , R 6 and R 7 are —H or R 1 , R 4 , R 5 and R 8 are each —H and R 2 , R 3 , R 6 and R 7 are each independently (C 1 -C 20 )hydrocarbyl.

6 . The supported catalyst system of claim 1 , wherein the one or more support materials comprise fumed silica; or wherein the supported catalyst system is a spray-dried supported catalyst system; or further including one or more activators; or further including an activator comprising methylalumoxane (MAO).

7 . A method for producing a supported activated metal-ligand catalyst, the method comprising:
contacting one or more support materials and one or more activators with a metal-ligand complex in an inert hydrocarbon solvent to produce the supported activated metal-ligand catalyst, wherein the metal-ligand complex has a structure according to formula (Ib):

wherein:
A − is an anion;
M is titanium, zirconium, or hafnium;
n is 1, 2, or 3;
each X is a monodentate ligand independently chosen from (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, halogen, —N(R N ) 2 , —N(R N )COR C , —OR, —OPh, —OAr and —H;
each Z is independently chosen from —O—, —S—, (C 6 -C 50 )aryl, (C 2 -C 50 )heteroaryl, N(C 1 -C 50 )hydrocarbyl, N(C 1 -C 50 )aryl, P(C 1 -C 50 )aryl, and P(C 1 -C 50 )hydrocarbyl;
R 9 and R 10 are independently chosen from (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl and —H;
R 11 and R 12 are independently chosen from halogen, (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl and —H;
R 1 -R 8 are each independently (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl and —H;
R 13 and R 14 are independently chosen from (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl and —H;
R 15 and R 16 are independently chosen from (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl and —H;
R 17 and R 18 are both: (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl,

 or —H, where R 19-23 are independently chosen from (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl and —H; and
each R, R C and R N are independently chosen from —H, (C 1 -C 50 )hydrocarbyl, and (C 1 -C 50 )heterohydrocarbyl.

8 . The method of claim 7 , wherein the activator comprises methylalumoxane (MAO); or further including drying the supported activated metal-ligand catalyst, wherein drying includes spray drying the supported activated metal-ligand catalyst to produce particles of a spray-dried supported activated metal-ligand catalyst.

9 . The method of claim 7 , wherein the method further comprises:
disposing the one or more activators on the one or more support materials to produce a supported activator; and contacting the supported activator with a solution of the metal-ligand complex in the inert hydrocarbon solvent; or wherein disposing the one or more activators on the one or more support materials comprises spray drying to produce a spray-dried supported activator.

10 . The method of claim 7 , wherein at least two R groups of R 19-23 are (C 1 -C 20 )hydrocarbyl; or wherein R 11 and R 12 are halogen R 1 , R 4 , R 5 and R 8 are each independently (C 1 -C 20 )hydrocarbyl and R 2 , R 3 , R 6 and R 7 are —H or R 1 , R 4 , R 5 and R 8 are each —H and R 2 , R 3 , R 6 and R 7 are each independently (C 1 -C 20 )hydrocarbyl.

11 . A process for producing a polyethylene or polyethylene copolymer resin in a gas phase polymerization reactor comprising:
contacting ethylene and, optionally, one or more (C 3 -C 12 )α-olefin comonomers with a supported activated metal-ligand catalyst in a gas-phase polymerization reactor, wherein the supported activated metal-ligand catalyst comprises a metal-ligand complex disposed on one or more support materials and one or more activators; wherein the metal-ligand complex has a structure according to formula (Ib):

wherein:
A − is an anion;
M is titanium, zirconium, or hafnium;
n is 1, 2, or 3;
each X is a monodentate ligand independently chosen from (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, halogen, —N(R N ) 2 , —N(R N )COR C , —OR, —OPh, —OAr and —H;
each Z is independently chosen from —O—, —S—, (C 6 -C 50 )aryl, (C 2 -C 50 )heteroaryl, N(C 1 -C 50 )hydrocarbyl, N(C 1 -C 50 )aryl, P(C 1 -C 50 )aryl, and P(C 1 -C 50 )hydrocarbyl;
R 9 and R 10 are independently chosen from (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl and —H;
R 11 and R 12 are inde

Assignees

• Dow Global Technologies Llc

Inventors

• Camelio Andrew M
• Baillie Rhett A
• Bailey Brad C
• Delorbe Johnathan E
• Do Hien Q
• Pearson David M
• Fontaine Philip P

Classifications

• C08F10/02 Primary

  Ethene · CPC title

• C08F2/34

  Polymerisation in gaseous state · CPC title

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/64193

  OOOO · CPC title