Catalyst systems and processes for producing polyethylene using the same
Embodiments of the present application are directed to procatalysts, and catalyst systems including procatalysts including a metal-ligand complex having the structure of formula (1): [Formula I].
1 . A procatalyst comprising a metal-ligand complex disposed on one or more support materials, wherein the metal-ligand complex has a structure according to formula (I):
wherein:
M is titanium, zirconium, or hafnium;
N is 1, 2, or 3;
each X is a monodentate ligand independently chosen from unsaturated (C 2 -C 50 )hydrocarbon, unsaturated (C 2 -C 50 )heterohydrocarbon, (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, halogen, —N(R N ) 2 , and —N(R N )COR C ;
the metal-ligand complex is overall charge-neutral;
each Z is independently chosen from —O—, —S—, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, N(C 1 -C 50 )hydrocarbyl, and P(C 1 -C 50 )hydrocarbyl;
R 1 and R 16 are independently chosen from (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, (C 1 -C 50 )alkyl, (C 3 -C 40 )heteroalkyl, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):
wherein R 31-35 , R 41-48 , and R 51-59 are independently chosen from —H, (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )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 N )—, (R C ) 2 NC(O)—, and halogen;
R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 are independently chosen from —H, (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )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)—, and halogen;
R 23 and R 24 are independently chosen from —(CR C 2 ) m —, wherein subscript m is from 1 to 10;
R 17 and R 18 are independently chosen from linear or branched (C 1 -C 20 )alkyl; and
each R C , R P , and R N are independently chosen from —H, (C 1 -C 50 )hydrocarbyl, and (C 1 -C 50 )heterohydrocarbyl.
2 . The procatalyst of claim 1 , wherein R 1 and R 16 are the same.
3 . The procatalyst of claim 1 , wherein at least one of R 1 and R 16 is a radical having formula (II) and at least one of R 32 and R 34 is tert-butyl.
4 . The procatalyst of claim 1 , wherein at least one of R 1 and R 16 is a radical having formula (III).
5 . The procatalyst of claim 4 , wherein at least one of R 42 , R 43 , R 46 , and R 47 is tert-butyl.
6 . The procatalyst of claim 4 , wherein R 41-48 are —H.
7 . The procatalyst of claim 1 , wherein the one or more support materials comprise fumed silica.
8 . A catalyst system comprising the procatalyst of claim 1 and one or more activators.
9 . The catalyst system of claim 8 , wherein the activator comprises methylalumoxane (MAO).
10 . A method for producing a catalyst system, the method comprising:
contacting one or more support materials, one or more activators, and a metal-ligand complex in an inert hydrocarbon solvent to produce the catalyst system, wherein the metal-ligand complex has a structure according to formula (Ia):
wherein:
A − is an anion;
M is titanium, zirconium, or
hafnium; n is 1, 2, or 3;
each X is a monodentate ligand independently chosen from unsaturated (C 2 -C 50 )hydrocarbon, unsaturated (C 2 -C 50 )heterohydrocarbon, (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, halogen, —N(R N ) 2 , and —N(R N )COR C ;
each Z is independently chosen from —O—, —S—, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, N(C 1 -C 40 )hydrocarbyl, and P(C 1 -C 40 )hydrocarbyl;
R 1 and R 16 are independently chosen from (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, (C 1 -C 40 )alkyl, (C 3 -C 40 )heteroalkyl, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):
wherein R 31-35 , R 41-48 , and R 51-59 are independently chosen from —H, (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )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 N )—, (R C ) 2 NC(O)—, and halogen;
R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 are independently chosen from —H, (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )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)—, and halogen;
R 23 and R 24 are independently chosen from —(CR C 2 ) m —, wherein subscript m is from 1 to 10;
R 17 and R 18 are independently chosen from linear or branched (C 1 -C 20 )alkyl; and
each R C , R P , and R N are independently chosen from —H, (C 1 -C 50 )hydrocarbyl, and (C 1 -C 50 )heterohydrocarbyl.
11 . The method of claim 10 , wherein the activator comprises methylalumoxane (MAO).
12 . The method of claim 10 , wherein the method further comprises:
mixing the one or more support materials, the one or more activators, and the metal-ligand complex in the inert hydrocarbon solvent to produce a catalyst system precursor; and
drying the catalyst system precursor to produce the catalyst system.
13 . The method of claim 12 , wherein the catalyst system precursor is spray dried to produce the catalyst system; and the catalyst system comprises spray-dried particles.
14 . The method of claim 10 , wherein the method further comprises:
disposing the one or more activators on the one or more support materials to produce a supported activator; and
contacting the supported activator with a solution of the metal-ligand complex in the inert hydrocarbon solvent.
15 . The method of claim 14 , wherein disposing the one or more activators on the one or more support materials comprises spray drying to produce a spray-dried supported activator.
16 . A process for producing polyethylene, the process comprising contacting ethylene and, optionally, one or more (C 3 -C 12 )α-olefin comonomers with a catalyst system in a gas-phase polymerization reactor, wherein the catalyst system comprises a metal-ligand complex disposed on one or more support materials; and the metal-ligand complex has a structure according to formula (Ia):
wherein:
A − is an anion;
M is titanium, zirconium, or
hafnium; subscript n of (X) n is 1, 2, or 3;
each X is a monodentate ligand independently chosen from unsaturated (C 2 -C 50 )hydrocarbon, unsaturated (C 2 -C 50 )heterohydrocarbon, (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, halogen, —N(R N ) 2 , and —N(R N )COR C ;
each Z is independently chosen from —O—, —S—, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, N(C 1 -C 40 )hydrocarbyl, and P(C 1 -C 40 )hydrocarbyl;
R 1 and R 16 are independently chosen from (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, (C 1 -C 40 )alkyl, (C 3 -C 40 )heteroalkyl, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):
wherein R 31-35 , R 41-48 , and R 51-59 are independently chosen from —H, (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )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 N )—, (R C ) 2 NC(O)—, and halogen;
R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 are independently chosen from —H, (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )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)—, and halogen;
R 23 and R 24 are independently chosen from —(CR C 2 ) m —, wherein subscript m is from 1 to 10;
R 17 and R 18 are independently chosen from linear or branched (C 1 -C 20 )alkyl; and
each R C , R P , and R N are independently chosen from —H, (C 1 -C 50 )hydrocarbyl, and (C 1 -C 50 )heterohydrocarbyl.
17 . The process of claim 16 , wherein the catalyst system further comprises an activator.
18 . The process of claim 17 , wherein the activator comprises methylalumoxane (MAO).
19 . The process of claim 16 , wherein the catalyst system is fed to the gas-phase polymerization reactor in neat form, as a solution, or as a slurry.
20 . The process of claim 16 , wherein the catalyst system comprises spray-dried particles.