Bidentate biarylphenoxy group IV transition metal catalysts for olefin polymerization with chain transfer agents
Processes of polymerizing olefins include contacting ethylene, a (C 3 -C 40 )alpha-olefin comonomer, and a solvent in the presence of a chain transfer agent and a catalyst system, the catalyst system comprising a metal-ligand complex according to formula (I).
1 . A process of polymerizing olefins, the process comprising contacting ethylene, a (C 3 -C 40 ) alpha-olefin comonomer, and a solvent in the presence of a chain transfer agent and a catalyst system, wherein the chain transfer agent comprises dialkyl zinc, and wherein the catalyst system comprises a metal-ligand complex according to formula (Ia) or formula (Ic):
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 , and —NCOR C ;
n is 1 or 2;
m is 2;
the metal-ligand complex has 6 or fewer metal-ligand bonds;
each Y is oxygen;
each R 1 is independently selected from carbazolyl or substituted carbazolyl;
each R 2 is independently chosen from (C 1 -C 10 )alkyl;
z 3 , z 4 , and z 5 are selected from the group consisting of sulfur, oxygen, —N(R A )—, and —C(R A )—, provided that exactly one of z 3 , z 4 , or z 5 is —C(R A )— or that exactly two of z 3 , z 4 , or z 5 are —C(R A )—;
R 3 , R 4 , R 5 , and R 6 are independently chosen from (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, halogen, or —H;
R 7 , R 8 , and R 9 are independently chosen from (C 1 -C 50 ) hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, halogen, or —H, wherein in formula (Ia), R 8 is methyl;
each R A is independently chosen from (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, halogen, or —H, wherein any two R A groups bonded to neighboring atoms are optionally linked; and
each R C , R N , and R P is independently a (C 1 -C 50 )hydrocarbyl.
2 . The polymerization process according to claim 1 , wherein:
M is zirconium or hafnium; and
each X is independently chosen from (C 6 -C 20 )aryl, (C 4 -C 20 )heteroaryl, (C 4 -C 12 ) diene, or a halogen.
3 . The polymerization process according to claim 1 , wherein the metal-ligand complex has a structure according to formula (Ia), and wherein R 3 , R 4 , R 5 and R 6 are —C(H)—.
4 . The polymerization process according to claim 1 , wherein each R 2 is methyl.
5 . The polymerization process according to claim 1 , wherein in formula (Ic), R 7 and R 9 are —C(H)— and R 8 is (C 1 -C 20 )alkyl.
6 . The polymerization process according to claim 1 , wherein each R 1 is carbazolyl.
7 . The polymerization process according to claim 1 , wherein each R 1 is independently 3,6-di-tert-butylcarbazol-9-yl or 2,7-di-tert-butylcarbazol-9-yl.
8 . The polymerization process of claim 1 , wherein the chain transfer agent is diethyl zinc.
9 . The polymerization process according to claim 1 , wherein the polymerization process occurs in a reactor.
10 . The polymerization process according to claim 1 , wherein the polymerization process occurs at a reaction temperature from 120° C. to 190° C.
11 . The polymerization process according to claim 1 , wherein the catalyst system further comprises a co-catalyst.
12 . The polymerization process according to claim 1 , wherein each X is independently benzyl, phenyl, or chloro.
13 . The polymerization process according to claim 1 , wherein the metal-ligand complex has a structure according to formula (Ia).
14 . The polymerization process according to claim 1 , wherein the metal-ligand complex has a structure according to formula (Ic).
15 . The polymerization process according to claim 1 , wherein the metal-ligand complex is one of the following structures: