Polymerization of ethylene in solution processes using a Ziegler-Natta catalyst and a hydrogenation procatalyst
Processes of polymerizing olefin monomers and catalyst systems. The catalyst systems include a non-hydrogen-generating post-metallocene procatalyst; a co-catalyst; and a hydrogenation procatalyst having the formula Cp 2 TiX n TiCp 2 or Cp 2 TiX n , in which each Cp is cyclopentadienyl substituted with at least one (C 1 -C 10 )alkyl; each X is independently monoanionic or neutral, wherein each X is independently (C 1 -C 40 )hydrocarbon, (C 1 -C 40 )heterohydrocarbon, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, or a halogen atom; and n is 1 or 2.
1 . A catalyst system comprising:
a non-hydrogen-generating post-metallocene procatalyst;
a co-catalyst; and
a hydrogenation procatalyst having the formula Cp 2 TiX 2 TiCp 2 or Cp 2 TiX n , where:
each Cp is cyclopentadienyl optionally substituted with at least one (C 1 -C 10 ) alkyl;
each X is independently (C 1 -C 40 )hydrocarbon, (C 1 -C 40 )heterohydrocarbon, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, or a halide; and
n is 1 or 2;
wherein the non-hydrogen-generating post-metallocene procatalyst is a metal-ligand complex according to formula (I):
where:
M is a metal selected from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4;
n is 0, 1, or 2;
when n is 1, X 1 is a monodentate ligand or a bidentate ligand;
when n is 2, each X 1 is independently a monodentate ligand;
each X 1 that is a monodentate ligand is independently halide, unsubstituted (C 1 -C 20 )hydrocarbyl, unsubstituted (C 1 -C 20 )hydrocarbyl, C(O)O—, or R K R L N—, where each of R K and R L is independently an unsubstituted (C 1 -C 20 )hydrocarbyl;
L is a diradical selected from the group consisting of (C 1 -C 40 )hydrocarbylene, (C 1 -C 40 )heterohydrocarbylene, —Si(R C ) 2 -, —Si(R C ) 2 OSi(R C ) 2 -, —Si(R C ) 2 C(R C ) 2 -, —Si(R C ) 2 Si(R C ) 2 -, —Si(R C ) 2 C(R C ) 2 Si(R C ) 2 -, —C(R C ) 2 Si(R C ) 2 C(R C ) 2 -, —N(R N )C(R C ) 2 -, —N(R N )N(R N )-, and —C(R C ) 2 N(R N )C(R C ) 2 -,
each Z is independently selected from —O—, —S—, —N(R N )-, or —P (R P )-;
R 1 , 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 , R 15 , and R 16 are 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 —, —N═C(R C ) 2 , R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, halide, radicals having formula (XI), radicals having formula (XII), and radicals having formula (XIII):
where:
each of R 31 -R 35 , R 41 -R 48 , and R 51 -R 59 is independently selected from —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 N )-, (R C ) 2 NC(O)—, or halide; and
wherein the non-hydrogen-generating post-metallocene procatalyst is unsupported and the hydrogenation procatalyst is unsupported.
2 . A catalyst system comprising:
a non-hydrogen-generating post-metallocene procatalyst; and
Cp 2 TiX 2 treated with an aluminum alkyl species, where:
each Cp is cyclopentadienyl substituted with at least one (C 1 -C 10 ) alkyl;
each X is independently (C 1 -C 40 )hydrocarbon, (C 1 -C 40 )heterohydrocarbon, (C 1 -C 40 )hydrocarbon anion, (C 1 -C 40 )heterohydrocarbon anion, or a halide;
wherein the non-hydrogen-generating post-metallocene procatalyst is a metal-ligand complex according to formula (I):
where:
M is a metal selected from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4;
n is 0, 1, or 2;
when n is 1, X 1 is a monodentate ligand or a bidentate ligand;
when n is 2, each X 1 is independently a monodentate ligand;
each X 1 that is a monodentate ligand is independently halide, unsubstituted (C 1 -C 20 )hydrocarbyl, unsubstituted (C 1 -C 20 )hydrocarbyl, C(O)O—, or R K R L N—, where each of R K and R L is independently an unsubstituted (C 1 -C 20 )hydrocarbyl;
L is a diradical selected from the group consisting of (C 1 -C 40 )hydrocarbylene, (C 1 -C 40 )heterohydrocarbylene, —Si(R C ) 2 -, —Si(R C ) 2 OSi(R C ) 2 -, —Si(R C ) 2 C(R C ) 2 -, —Si(R C ) 2 Si(R C ) 2 -, —Si(R C ) 2 C(R C ) 2 Si(R C ) 2 -, —C(R C ) 2 Si(R C ) 2 C(R C ) 2 -, —N(R N )C(R C ) 2 -, —N(R N )N(R N )-, and —C(R C ) 2 N(R N )C(R C ) 2 -,
each Z is independently selected from —O—, —S—, —N(R N )-, or —P (R P )-;
R 1 , 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 , R 15 , and R 16 are 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 —, —N═C(R C ) 2 , R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, halide, radicals having formula (XI), radicals having formula (XII), and radicals having formula (XIII):
where:
each of R 31 -R 35 , R 41 -R 48 , and R 51 -R 59 is independently selected from —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 N )-, (R C ) 2 NC(O)—, or halide; and
wherein the non-hydrogen-generating post-metallocene procatalyst is unsupported and the Cp 2 TiX 2 treated with an aluminum alkyl species is unsupported.
3 . The catalyst system of claim 2 , wherein the aluminum alkyl species comprises alkylaluminoxane, modified alkylaluminoxane, or an aluminum alkyl having the formula AlR 3 wherein each R is independently (C 1 -C 40 )hydrocarbon (C 1 -C 40 )heterohydrocarbon, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, or a halide.
4 . The catalyst system of claim 2 , wherein the aluminum alkyl species is the reaction product of AlR 3 and water, alcohol, silanol, or a Lewis base.
5 . The catalyst system of claim 4 , wherein the Lewis base is pyridine or mono-substituted alkylamine, disubstituted alkylamine, or tri-substituted alkylamine.
6 . The catalyst system of claim 2 , wherein the aluminum alkyl species is diisobutylaluminum oxide (DIBAO or DIBAL-O) or Isobutylaluminoxane (IBAO).
7 . The catalyst system of claim 1 , wherein the catalyst system further comprises an impurity scavenger.
8 . The catalyst system of claim 1 , wherein each X is a substituted benzyl or substituted heteroarylbenzyl.
9 . The catalyst system of claim 1 , wherein X is selected from the group consisting of:
10 . The catalyst system of claim 1 , wherein the non-hydrogen-generating post-metallocene procatalyst produces less than or equal to 1 ppm of hydrogen under polymerization conditions.
11 . The catalyst system of claim 2 , wherein the catalyst system further comprises an impurity scavenger.
12 . The catalyst system of claim 2 , wherein each X is a substituted benzyl or substituted heteroarylbenzyl.
13 . The catalyst system of claim 2 , wherein X is selected from the group consisting of:
14 . The catalyst system of claim 2 , wherein the non-hydrogen-generating post-metallocene procatalyst produces less than or equal to 1 ppm of hydrogen under polymerization conditions.