Catalyst system for multi-block copolymer formation

Patent metadata

Field	Value
Publication number	US-11459409-B2
Application number	US-201816494085-A
Country	US
Kind code	B2
Filing date	Mar 14, 2018
Priority date	Mar 15, 2017
Publication date	Oct 4, 2022
Grant date	Oct 4, 2022

Abstract

The present disclosure relates to a 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, (C) an activator, and (D) 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 a metal-ligand complex of Formula (I):

wherein M is titanium, zirconium, or hafnium;
wherein each Z1 is independently a monodentate or polydentate ligand that is neutral, monoanionic, or dianionic, wherein nn is an integer, and wherein Z1 and nn are chosen in such a way that the metal-ligand complex of Formula (I) is overall neutral;
wherein each Q 1 and Q 10 independently is selected from the group consisting of (C 6 -C 40 )aryl, substituted (C 6 -C 40 )aryl, (C 3 -C 40 )heteroaryl, and substituted (C 3 -C 40 )heteroaryl;
wherein each Q 2 , Q 3 , Q 4 , Q 7 , Q 8 , and Q 9 independently is selected from a group consisting of hydrogen, (C 1 -C 40 )hydrocarbyl, substituted (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, substituted (C 1 -C 40 )heterohydrocarbyl, halogen, and nitro (NO 2 );
wherein each Q 5 and Q 6 independently is selected from the group consisting of a (C 1 -C 40 )alkyl, substituted (C 1 -C 40 )alkyl, and [(Si) 1 —(C+Si) 40 ] substituted organosilyl;
wherein each N independently is nitrogen;
optionally, two or more of the Q 1-5 groups can combine together to form a ring structure, with such ring structure having from 5 to 16 atoms in the ring excluding any hydrogen atoms; and
optionally, two or more of the Q 6-10 groups can combine together to form a ring structure, with such ring structure having from 5 to 16 atoms in the ring excluding any hydrogen atoms.

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

3. The catalyst system of claim 1 , wherein each Z1 independently is Me, Bn, or Cl.

4. The catalyst system of claim 1 , wherein Q 1 and Q 10 are substituted phenyl groups, as shown in Formula (II):

wherein J 1 -J 10 are each independently selected from the group consisting of R s substituents and hydrogen; and wherein each R S independently is a halogen atom, polyfluoro substitution, perfluoro substitution, unsubstituted (C 1 -C 18 )alkyl, (C 6 -C 18 )aryl, F 3 C, FCH 2 O, F 2 HCO, F 3 CO, (R C1 ) 3 Si, (R C1 ) 3 Ge, (R C1 )O, (R C1 )S, (R C1 )S(O), (R C1 )S(O) 2 , (R C1 ) 2 P, (R C1 ) 2 N, (R C1 ) 2 C═N, NC, NO 2 , (R C1 )C(O)O, (R C1 )OC(O), (R C1 )C(O)N(R C1 ), or (R C1 ) 2 NC(O), or two of the R S are taken together to form an unsubstituted (C 1 -C 18 )alkylene where each R S independently is an unsubstituted (C 1 -C 18 )alkyl, and
wherein independently each R C1 is hydrogen, unsubstituted (C 1 -C 18 )hydrocarbyl or an unsubstituted (C 1 -C 18 )heterohydrocarbyl, or absent (e.g., absent when N comprises —N═).

5. The catalyst system of claim 4 , wherein J 1 , J 5 , J 6 and J 10 are each independently selected from the group consisting of halogen atoms, (C 1 -C 8 )alkyl groups, and (C 1 -C 8 )alkoxyl groups.

6. The catalyst system of claim 1 , wherein Q 5 and Q 6 are each independently (C 1 -C 40 ) primary or secondary alkyl groups.

7. The catalyst system of claim 1 , wherein Q 5 and Q 6 are each independently propyl, isopropyl, neopentyl, hexyl, and benzyl.

8. The catalyst system of claim 1 , wherein said metal-ligand complex of Formula (I) is selected from the group consisting of:

9. The catalyst system of claim 1 , wherein M is zirconium or hafnium.

10. 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 IB ) under polymerization conditions is 0.5 or less.

11. A process for preparing a multi-block copolymer comprising contacting one or more addition polymerizable monomers under addition polymerization conditions with a catalyst system according to claim 1 , wherein the process is a continuous solution process carried out at a temperature of greater than 125° C.

12. The process of claim 11 , wherein the process is carried out at a temperature of about 150° C. and comprises a combined catalyst efficiency of above 400 kg polymer /g metal .

13. The process of claim 11 , wherein the process is carried out at a temperature from about 150° C. to about 170° C. and comprises a combined catalyst efficiency of above 200 kg polymer /g metal .

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

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.

15. The catalyst system of claim 14 , wherein the first olefin polymerization procatalyst (A) comprises a metal-ligand complex of Formula (III):

wherein:
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.

16. The catalyst system of claim 15 , wherein said metal-ligand complex of Formula (III) has the following structure:

wherein:
Ar 4 independently at each occurrence is C 6-20 aryl or inertly substituted derivatives thereof, especially 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrole-1-yl, naphthyl, anthracen-5-yl, 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl;
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

Assignees

• Dow Global Technologies Llc

Inventors

• Young Andrew J
• Do Hien Q
• Bailey Brad C
• Christianson Matthew D
• Munro Jeffrey C
• Carnahan Edmund M

Classifications

• C08F4/64172 Primary

  Neutral ligand · CPC title

• C08F2410/01

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

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title

• C08F297/083 Primary

  the monomers being ethylene or propylene · CPC title

• C08F4/64044

  NN · CPC title