Catalyst system for multi-block copolymer formation

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, 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.

17. 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 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.

18. The catalyst system of claim 15 , wherein said metal-ligand complex of Formula (III) is selected from the group consisting of:

19. 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 14 , wherein the process is a continuous solution process carried out at a temperature of greater than 125° C.

20. The process of claim 19 , 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 .