Olefin polymerization catalysts bearing a thiazole or imidazole
Processes of polymerizing olefin monomers using catalyst systems comprising a procatalyst having a structure according to Formula (I).
1. A catalyst system comprising a metal-ligand complex having a structure according to formula (I):
where:
M is a metal chosen from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4;
each X is a monodentate or bidentate ligand independently chosen from unsaturated (C 2 -C 50 ) hydrocarbon, unsaturated (C 2 -C 50 ) heterohydrocarbon, (C 1 -C 50 ) hydrocarbyl, (C 6 -C 50 ) aryl, (C 6 -C 50 ) heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C 4 -C 12 ) diene, halogen, —N(R N ) 2, or —NCOR C ;
m is 1 or 2;
n is 2 or 3, provided m+n=4;
each Z is NR N or S, wherein R N is (C 1 -C 40 ) hydrocarbyl or (C 1 -C 40 ) heterohydrocarbyl;
each R 1 is (C 1 -C 40 ) hydrocarbyl, (C 1 -C 40 ) heterohydrocarbyl, or trimethylsilyl methyl;
each R 2 and R 3 is independently selected from the group consisting of (C 1 -C 50 ) hydrocarbyl, (C 1 -C 50 ) heterohydrocarbyl, (C 6 -C 50 ) aryl, (C 4 -C 50 ) heteroaryl, —Si(R C ) 3 , halogen, and —H, wherein R C is independently selected from the group consisting of (C 1 -C 20 ) hydrocarbyl, (C 1 -C 20 ) heterohydrocarbyl, and —H; and
optionally, R 2 and R 3 are covalently linked to form a ring.
2. The catalyst system of claim 1 , wherein R 3 is (2,4,6-triisopropyl) phenyl, 2,4,6-trimethylphenyl, 3,5-di-tert butylphenyl, naphthyl, carbazolyl, or cyclopropyl.
3. The catalyst system of claim 1 , wherein R 2 and R 3 are covalently linked to form an aromatic ring, and the metal-ligand complex has a structure according to formula (II):
where each R 1 , Z, X, n, m, and M are defined as in formula (I); and
each R 4 , R 5 , R 6 , and R 7 are independently (C 1 -C 40 ) hydrocarbyl or (C 1 -C 40 ) heterohydrocarbyl.
4. The catalyst system of claim 3 , wherein each R 7 is (C 6 -C 40 ) aryl or (C 6 -C 40 ) heteroaryl.
5. The catalyst system of claim 3 , wherein each R 7 is phenyl, (2,4,6-triisopropyl) phenyl, 2,4,6-trimethylphenyl, 3,5-di-tert-butylphenyl, naphthyl, carbazolyl, or cyclopropyl.
6. The catalyst system of claim 1 , wherein each Z is NR N , where R N is (C 1 -C 8 ) alkyl.
7. The catalyst system of claim 1 , wherein each Z is S.
8. The catalyst system of claim 1 , wherein m is 2.
9. The catalyst system of claim 1 , wherein m is 1.
10. The catalyst system of claim 1 , wherein the metal-ligand complex has a structure according to formula (Ia), formula (Ib), formula (Ic), or formula (Id):
where each R 1 , R 2 , R 3 , R N , X, and M are as defined in formula (I).
11. The catalyst system of claim 3 , wherein the metal-ligand complex has a structure according to formula (IIa), formula (IIb), formula (IIc), or formula (IId):
where each R 1 , R 4 , R 5 , R 6 , R 7 , R N , X, and M are as defined in formula (II).
12. The catalyst system of claim 1 , wherein each R 1 is chosen from a linear (C 1 -C 12 ) alkyl, branched (C 1 -C 12 ) alkyl, (C 1 -C 12 ) cycloalkyl, trimethylsilyl methyl, benzyl, or 1-adamantyl.
13. The catalyst system of claim 1 , wherein each X is independently benzyl, phenyl, or chloro.
14. The catalyst system of claim 1 , further comprising a chain transfer agent and an activator mixed in solution with one or more metal-ligand complexes according to formula (I).
15. A polymerization process comprising:
polymerizing ethylene and one or more olefins in the presence of a catalyst system under olefin polymerization conditions to form an ethylene-based polymer, the catalyst system comprising a metal-ligand complex according to formula (I):
where:
M is a metal chosen from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4;
each X is a monodentate or bidentate ligand independently chosen from unsaturated (C 2 -C 50 ) hydrocarbon, unsaturated (C 2 -C 50 ) heterohydrocarbon, (C 1 -C 50 ) hydrocarbyl, (C 6 -C 50 ) aryl, (C 6 -C 50 ) heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C 4 -C 12 ) diene, halogen, —N(R N ) 2 , or —NCOR C ;
m is 1 or 2;
n is 2 or 3, provided m+n=4;
each Z is NR N or S, wherein R N is (C 1 -C 40 ) hydrocarbyl or (C 1 -C 40 ) heterohydrocarbyl;
each R 1 is a (C 1 -C 40 ) hydrocarbyl or (C 1 -C 40 ) heterohydrocarbyl;
each R 2 and R 3 is independently selected from the group consisting of (C 1 -C 50 ) hydrocarbyl, (C 1 -C 50 ) heterohydrocarbyl, (C 6 -C 50 ) aryl, (C 4 -C 50 ) heteroaryl, —Si(R C ) 3 , halogen, and —H, wherein R C is independently selected from the group consisting of (C 1 -C 20 ) hydrocarbyl, (C 1 -C 20 ) heterohydrocarbyl, and —H; and
optionally, R 2 and R 3 are covalently linked to form a ring.
16. The polymerization process of claim 15 , wherein Z is NR N , where R N is (C 1 -C 8 ) alkyl.
17. The polymerization process of claim 15 , wherein Z is S.
18. The polymerization process of claim 15 , wherein the catalyst system further comprises a chain transfer agent and an activator, and wherein the process further comprises mixing the chain transfer agent and the activator in solution with the one or more metal-ligand complexes according to formula (I).