Biaryl phenoxy group IV transition metal catalysts for olefin polymerization
Catalyst systems for olefin polymerization include a metal-ligand complex of a general formula (I). The metal-ligand complex of formula (I) is a transition metal complex of titanium, zirconium, or hafnium, in which the transition metal is coordinated with a biaryl phenoxy ligand structure. Olefin polymerization processes include contacting ethylene and optionally one or more (C 3 -C 12 ) alpha-olefins in the presence of the catalyst system to produce an ethylene-based polymer or copolymer.
1. A 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 20 )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, —OR C , —N(R N ) 2 , and —NCOR C ;
n is 1 or 2;
Y is oxygen, sulfur, or —N(R N )—;
each R 1 is independently selected from the group consisting of —H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —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, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):
where each of R 31-35 , R 41-48 and R 51-59 is independently chosen from (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —N═CHR C , —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 N )—, (R C ) 2 NC(O)—, halogen, or —H, provided at least one R 1 in formula (I) is a radical having formula (II), a radical having formula (III), or a radical having formula (IV);
Q is (C 1 -C 12 )alkylene, (C 1 -C 12 )heteroalkylene, (—CH 2 Si(R Q ) 2 CH 2 —), (—CH 2 CH 2 Si(R Q ) 2 CH 2 CH 2 —), (—CH 2 Ge(R Q ) 2 CH 2 —), or (—CH 2 CH 2 Ge(R Q ) 2 CH 2 CH 2 —), where each R Q is (C 1 -C 20 )hydrocarbyl;
each z 1 and z 2 is independently selected from the group consisting of sulfur, oxygen, —N(R C )—, and —C(R C )—, provided at least one of z 1 and z 2 in each individual ring containing groups z 1 and z 2 is sulfur;
R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b , and R 7b 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)—, —P(O)(R P ) 2 , 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, and —H, in which optionally R 4a and R 5a , or R 5a and R 6a , or R 6a and R 7a , or R 4b and R 5b , or R 5b and R 6b , or R 6b and R 7b are covalently connected to form an aromatic ring or a non-aromatic ring;
each R C , R N , and R P in formula (I) is independently selected from the group consisting of (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl, and —H; and
provided that when Q is —CH 2 CH 2 CH 2 CH 2 —:
(1) when each R 1 is 3,6-di-tert-butylcarbazol-9-yl and z 2 is sulfur and each X is benzyl, R 5a and R 5b are not —OMe, fluorine, or tert-octyl; or
(2) at least one of R 4a , R 5a , R 6a , and R 7a is halogen, and at least one of R 4b , R 5b , R 6b , and R 7b is halogen; or
(3) at least one of R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b , and R 7b is 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 , —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)—, —P(O)(R P ) 2 , 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)—, and (R C ) 2 NC(O)—.
2. The catalyst system of claim 1 , wherein each z 1 is sulfur.
3. The catalyst system of claim 1 , wherein each z 2 is sulfur.
4. The catalyst system of claim 1 , wherein each Y is oxygen.
5. The catalyst system of claim 1 , further comprising one or more cocatalysts.
6. The catalyst system of claim 1 , wherein each R 1 is a radical having formula (III), in which at least one of R 41-48 is chosen from (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , OR C —SR C , —NO 2 , —CN, —CF 3 , or halogen.
7. The catalyst system of claim 1 , wherein each R 1 is a radical having formula (III), in which:
(1) R 42 and R 47 are independently chosen from (C 1 -C 20 )alkyl, —Si(R C ) 3 , —CF 3 , or halogen and R 43 and R 46 are —H; or
(2) R 43 and R 46 are independently chosen from (C 1 -C 20 )alkyl, —Si(R C ) 3 , —CF 3 , or halogen and R 42 and R 47 are —H.
8. The catalyst system of claim 1 , wherein each R 1 is a radical having formula (IV), in which at least one of R 51-59 is chosen from (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , or halogen.
9. The catalyst system of claim 1 , wherein each R 1 is a radical having formula (IV), in which R 51-59 are —H.
10. The catalyst system of claim 1 , wherein when Q is (C 3 -C 4 )alkylene, at least two of R 4a , R 1a , R 6a , R 7a , R 4b , R 5b , R 6b , and R 7b are selected from the group consisting of (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)—, —P(O)(R P ) 2 , 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 N )—, (R C ) 2 NC(O)—, and halogen.
11. The catalyst system of claim 1 , wherein at least one of R 4a , R 5a , R 6a , R 7a is halogen and at least one of R 4b , R 5b , R 6b , and R 7b is halogen.
12. The catalyst system of claim 1 , wherein at least two of R 4a , R 5a , R 6a , R 7a are halogen and at least two of R 4b , R 5b , R 6b , and R 7b are halogen.
13. The catalyst system of claim 1 , wherein Q is (—CH 2 Si(R Q ) 2 CH 2 —), (—CH 2 CH 2 Si(R Q ) 2 CH 2 CH 2 —), (—CH 2 Ge(R Q ) 2 CH 2 —), or (—CH 2 CH 2 Ge(R Q ) 2 CH 2 CH 2 —), where R Q is (C 1 -C 5 )alkyl.
14. The catalyst system of claim 1 , wherein Q is benzene-1,2-diyl or cyclohexane-1,2-diyl.
15. The catalyst system of claim 1 , wherein Q is (—CH 2 Si(R Q ) 2 CH 2 —) or (—CH 2 Si(R Q ) 2 CH 2 —), where R Q is ethyl or 2-propyl.
16. The catalyst system of claim 1 , wherein Q is benzene-1,2-diyldimethyl.
17. The catalyst system of claim 1 , wherein the catalyst system further comprises a chain transfer agent.
18. A process for polymerizing olefins, the process comprising: contacting ethylene, or a combination of ethylene and one or more (C 3 -C 12 )α-olefins with a catalyst system according to claim 1 .
19. The process of claim 18 , wherein the catalyst system further comprises a chain transfer agent.
20. A catalyst system comprising:
a metal-ligand complex according to formula (I):
where:
M is a metal chosen from 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 (C 1 -C 50 )hydrocarbyl;
n is 1 or 2;
Y is oxygen or sulfur;
each R 1 is independently selected from the group consisting of radicals having formula (II), radicals having formula (III), and radicals having formula (IV):
where each of R 31-35 , R 41-48 and R 51-59 is independently chosen from (C 1 -C 2 M) hydrocarbyl, (C 1 -C 20 ) heterohydrocarbyl, —CN, —CF 3 , halogen, or —H, provided at least one R 1 in formula (I) is a radical having formula (II), a radical having formula (III), or a radical having formula (IV);
Q is —CH 2 CH 2 CH 2 CH 2 —, benzene-1,2-diyl, benzene-1,2-diyldimethyl, cyclohexane-1,2-diyl, or cyclohexane-1,2-diyldimethyl;
each z 1 and z 2 is independently selected from the group consisting of sulfur and —C(R C )—, provided at least one of z 1 and z 2 in each individual ring containing groups z 1 and z 2 is sulfur;
R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b , and R 7b are independently chosen from (C 1 -C 50 )hydrocarbyl, —CF 3 , halogen, and —H, in which optionally R 4a and R 5a , or R 5a and R 6a , or R 6a and R 7a , or R 4b and R 5b , or R 5b and R 6b , or R 6b and R 7b are covalently connected to form an aromatic ring or a non-aromatic ring;
each R C in formula (I) is independently selected from the group consisting of (C 1 -C 20 )hydrocarbyl and —H; and
provided that when Q is —CH 2 CH 2 CH 2 CH 2 —:
(1) when each R 1 is 3,6-di-tert-butylcarbazol-9-yl and z 2 is sulfur and each X is benzyl, R 5a and R 5b are not —OMe, fluorine, or tert-octyl; or
(2) at least one of R 4a , R 5a , R 6a , and R 7a is halogen, and at least one of R 4b , R 5b , R 6b , and R 7b is halogen; or
(3) at least one of R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b , and R 7b is 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 , —CN, and —CF 3 .