Catalyst system for multi-block coploymer formation

Patent metadata

Field	Value
Publication number	US-11208502-B2
Application number	US-201816494150-A
Country	US
Kind code	B2
Filing date	Mar 15, 2018
Priority date	Mar 15, 2017
Publication date	Dec 28, 2021
Grant date	Dec 28, 2021

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 composition comprises the admixture or reaction product resulting from combining: (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

The invention 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 (B) comprises a metal-ligand complex of Formula (I):

wherein:
each Z1 independently is (C 1 -C 40 )hydrocarbon, (C 1 -C 40 )heterohydrocarbon, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, Si(R C1 ) 3 , Ge(R C1 ) 3 , P(R C1 ) 2 , N(R C1 ) 2 , OR C1 , SR C1 , CN, CF 3 , R C1 S(O)—, R C1 S(O) 2 —, (R C1 ) 2 C═N—, R C1 C(O)O—, R C1 OC(O)—, R C1 C(O)N(R)—, (R C1 ) 2 NC(O)—, halogen atom, or hydrogen atom;
each R C1 independently is (C 1 -C 30 )hydrocarbyl or (C 1 -C 30 )heterohydrocarbyl;
each M A independently is a metal of Group 3 of a Periodic Table of the Elements, the metal being in a formal oxidation state of +2 or +3;
nn is an integer of 1 or 2;
each Q 1 independently is hydrogen, (C 1 -C 40 )hydrocarbyl, or (C 1 -C 40 )heterohydrocarbyl;
each of Q 2 , Q 3 , and Q 4 independently is hydrogen, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )hydrocarbylO—, (C 1 -C 40 )hydrocarbylS—, (C 1 -C 40 )hydrocarbylS(O)—, (C 1 -C 40 )hydrocarbylS(O) 2 —, ((C 1 -C 40 )hydrocarbyl) 2 N—, ((C 1 -C 40 )hydrocarbyl) 2 P—, or (C 1 -C 40 )heterohydrocarbyl;
each Q 5 independently is (C 1 -C 40 )hydrocarbyl or (C 1 -C 40 )heterohydrocarbyl;
wherein Q 1 and Q 2 , Q 2 and Q 3 , Q 3 and Q 4 , and Q 4 and Q 5 optionally are taken together to form a (C 1 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene, or any three or four of Q 1 to Q 5 optionally are taken together to form a respective trivalent or tetravalent analog of (C 1 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene, and the remainder of Q 1 to Q 5 , are as defined above;
each of the (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, Si(R C1 ) 3 , Ge(R C1 ) 3 , P(R C1 ) 2 , N(R C1 ) 2 , OR C1 , SR C1 , R C1 S(O)—, R C1 S(O) 2 —, (R C1 ) 2 C═N—, R C1 C(O)O—, R C1 OC(O)—, R C1 C(O)N(R)—, (R C1 ) 2 NC(O)—, (C 1 -C 40 )hydrocarbylene, and (C 1 -C 40 )heterohydrocarbylene groups independently is unsubstituted or substituted with one or more R S substituents; and
each R S independently is a halogen atom, polyfluoroalkyl, perfluoroalkyl, polyfluoroaryl, perfluoroaryl, unsubstituted (C 1 -C 18 )alkyl, F 3 C—, FCH 2 O—, F 2 HCO—, F 3 CO—, oxo (═O), R 3 Si—, R 3 Ge—, RO—, RS—, RS(O)—, RS(O) 2 —, R 2 P—, R 2 N—, R 2 C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R 2 NC(O)—, and two R S are optionally taken together to form an unsubstituted (C 1 -C 18 )alkylene, wherein each R independently is an unsubstituted (C 1 -C 18 )alkyl; and
optionally, R C1 or R S may have an additional interaction with M A .

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

3. The olefin polymerization catalyst system of claim 1 , wherein M is a metal of any of Groups 3 to 6.

4. The olefin polymerization catalyst system of claim 1 , wherein M A is a metal of Group 3.

5. The olefin polymerization catalyst system of claim 1 , wherein M A is scandium.

6. The olefin polymerization catalyst system of claim 1 , wherein Z1 is (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, Si(R C1 ) 3 , or a hydrogen atom.

7. The olefin polymerization catalyst system of claim 1 , wherein Z1 is substituted benzyl or substituted heteroarylbenzyl.

8. The olefin polymerization catalyst system of claim 1 , wherein Z1 is selected from the group consisting of:

9. The olefin polymerization catalyst system of claim 1 , wherein the metal-ligand complex of Formula (I) has the following structure:

10. The olefin polymerization 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 a ratio (r 1A /r 1B ) under polymerization conditions is 0.5 or less.

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

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.

12. The olefin polymerization catalyst system of claim 11 , wherein said metal-ligand complex of Formula (II) has the following structure:

wherein:
Ar 4 independently at each occurrence is C 6-20 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.

13. The olefin polymerization catalyst system of claim 11 , wherein said metal-ligand complex of Formula (II) 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.

14. The olefin polymerization catalyst system of claim 11 , wherein said metal-ligand complex of Formula (ID is selected from the group consisting of:

15. The olefin polymerization catalyst system of claim 1 , wherein the first olefin polymerization procatalyst (A) has the following structure:

wherein X 1 at eac

Assignees

• Dow Global Technologies Llc

Inventors

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

Classifications

• C08F4/545 Primary

  rare earths being present, e.g. triethylaluminium + neodymium octanoate · CPC title

• C08F2500/03

  Narrow molecular weight distribution, i.e. Mw/Mn < 3 · CPC title

• C08F4/52

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

• C08F4/64044

  NN · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title