Catalyst system for multi-block copolymer formation

Patent metadata

Field	Value
Publication number	US-11897992-B2
Application number	US-201816494136-A
Country	US
Kind code	B2
Filing date	Mar 15, 2018
Priority date	Mar 15, 2017
Publication date	Feb 13, 2024
Grant date	Feb 13, 2024

Abstract

The present disclosure relates to an olefin polymerization catalyst system for use in forming a multi-block copolymer, said copolymer containing therein two or more segments or blocks differing in chemical or physical properties, a polymerization process using the same, and the resulting polymers, wherein the catalyst system comprises: (A) a first olefin polymerization procatalyst, (B) a second olefin polymerization procatalyst capable of preparing polymers differing in chemical or physical properties from the polymer prepared by procatalyst (A) under equivalent polymerization conditions, and (C) a chain shuttling agent.

First claim

What is claimed is:

1. An olefin polymerization catalyst system comprising:
(A) a first olefin polymerization procatalyst,
(B) a second olefin polymerization procatalyst, and
(C) a chain shuttling agent,

wherein the second olefin polymerization procatalyst comprises:

2. The catalyst system of claim 1 , further comprising (D) an activator.

3. The catalyst system of claim 1 , wherein the first olefin polymerization procatalyst (A) and the second olefin polymerization procatalyst (B) have respective reactivity ratios r 1A and r 1B , such that the ratio (r 1A /r 1B ) under polymerization conditions is 0.5 or less.

4. The catalyst system of claim 1 , wherein the first olefin polymerization procatalyst (A) comprises a metal-ligand complex of Formula (III):

wherein:
M is zirconium or hafnium;
R 20 independently at each occurrence is a divalent aromatic or inertly substituted aromatic group containing from 5 to 20 atoms not counting hydrogen;
T 3 is a divalent hydrocarbon or silane group having from 3 to 20 atoms not counting hydrogen, or an inertly substituted derivative thereof; and
R D independently at each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two R D groups together are a divalent ligand group of from 1 to 20 atoms, not counting hydrogen.

5. The catalyst system of claim 4 , wherein said metal-ligand complex of Formula (III) has the following structure:

wherein:
Ar 4 independently at each occurrence is C6-20 aryl or inertly substituted derivatives thereof;
T 4 independently at each occurrence is a propylene-1,3-diyl group, a bis(alkylene)cyclohexan-1,2-diyl group, or an inertly substituted derivative thereof substituted with from 1 to 5 alkyl, aryl or aralkyl substituents having up to 20 carbons each;
R 21 independently at each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen; and
R D , independently at each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R D groups together are a divalent hydrocarbylene, hydrocarbadiyl or trihydrocarbylsilyl group of up to 40 atoms not counting hydrogen.

6. The catalyst system of claim 4 , wherein said metal-ligand complex of Formula (III) has the following structure:

wherein,
Ar 4 independently at each occurrence, is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl,
R 21 independently at each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen;
T 4 is propan-1,3-diyl or bis(methylene)cyclohexan-1,2-diyl; and
R D , independently at each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R D groups together are a hydrocarbylene, hydrocarbadiyl or hydrocarbylsilanediyl group of up to 40 atoms not counting hydrogen.

7. The catalyst system of claim 6 , wherein said metal-ligand complex of Formula (III) has the following structure:

8. The catalyst system of claim 4 , wherein said metal-ligand complex of Formula (III) is selected from the group consisting of:

9. The catalyst system of claim 1 , wherein the chain shuttling agent is an aluminum, zinc, or gallium compound containing at least one hydrocarbyl substituent having from 1 to 12 carbons.

10. The catalyst system of claim 1 , wherein the second olefin polymerization procatalyst requires no activator (cocatalyst) to polymerize olefins.

11. The catalyst system of claim 1 , wherein the chain shuttling agent is a dialkylzinc.

12. The catalyst system of claim 1 , wherein the catalyst system is used in forming a multi-block copolymer.

13. A process for preparing a multi-block copolymer comprising contacting ethylene and at least one copolymerizable comonomer other than ethylene under addition polymerization conditions with a catalyst system according to claim 1 .

14. The process according to claim 13 , wherein the process is a continuous solution process.

15. The process of claim 14 , wherein the process is carried out at a temperature of greater than 125° C. and comprises a combined catalyst efficiency of greater than 30,000 g polymer /g metal .

Assignees

• Dow Global Technologies Llc

Inventors

• Patton Jasson T
• Senecal Todd D
• Arriola Daniel J
• Christianson Matthew D
• Roof Gordon R
• Devore David D
• Davis Anna V

Classifications

• C08F4/64193 Primary

  OOOO · CPC title

• C08F4/52

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

• C08F4/61904

  in combination with another component of C08F4/60 · CPC title

• C08F297/083 Primary

  the monomers being ethylene or propylene · CPC title

• C08F2410/01

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