Biaryl hydroxythiophene group IV transition metal polymerization with chain transfer capability
Embodiments of this disclosure include polymerization processes that include contacting propylene and/or one or more (C4-C12)α-olefins in a reactor including a catalyst system. The catalyst system comprises a metal-ligand complex according to formula (I).
1. A polymerization process comprising:
contacting propylene and one or more (C 4 -C 12 )α-olefins in a reactor including a catalyst system, the catalyst system comprising a chain transfer or chain shuttling agent and 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;
each Y is —O—;
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 , —OR C , 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, or (C 1 -C 12 )heteroalkylene;
each z 1 is sulfur, oxygen, —N(R Z )—, and each z 2 is —C(R Z )—, where R Z is (C 1 -C 8 )alkyl or —H;
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 , —OR C , —CN, —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 76 may be covalently connected to form an aromatic ring or a non-aromatic ring;
each R C , R N , R Z 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.
2. The polymerization process of claim 1 , wherein the catalyst system further comprises one or more cocatalysts.
3. The polymerization process 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, (C 6 -C 40 )aryl, (C 5 -C 40 )heteroaryl, —Si(R C ) 3 , —CF 3 , or halogen, and R 42 and R 47 are —H.
4. The polymerization process 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.
5. The polymerization process of claim 1 wherein each R 1 is a radical having formula (IV), in which at least one of R 53 , R 55 , and R 57 is (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.
6. The polymerization process of claim 1 , wherein each R 1 is a radical having formula (II).
7. The polymerization process of claim 1 , wherein each R 1 is a radical having formula (II), and wherein R 32 and R 34 are independently (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.
8. The polymerization process of claim 1 , wherein each R 1 is a radical having formula (II), and wherein R 32 and R 34 are independently (C 1 -C 20 )alkyl, substituted (C 6 -C 20 )aryl, or unsubstituted (C 6 -C 20 )aryl.
9. The polymerization process of claim 1 , wherein each R 1 is a radical having formula (II), and wherein R 32 and R 34 are independently tert-butyl, phenyl, 3,5-di(tert-butyl)phenyl, 2,4,6-trimethylphenyl, or 2,4,6-tri(iso-propyl)phenyl.
10. The polymerization process of claim 1 , wherein the reactor has a reactor temperature of 140° C. or greater.
11. The polymerization process of claim 1 , wherein the polymer process further comprises a solution polymerization, and the solution polymerization takes place at a pressure from 10 psi to 2000 psi.
12. The polymerization process of claim 1 , wherein the chain transfer or chain shuttling agent is diethyl zinc.