Polymerization of ethylene in solution processes using a Ziegler-Natta catalyst and a hydrogenation procatalyst

Patent metadata

Field	Value
Publication number	US-12466901-B2
Application number	US-202017630802-A
Country	US
Kind code	B2
Filing date	Jul 30, 2020
Priority date	Jul 31, 2019
Publication date	Nov 11, 2025
Grant date	Nov 11, 2025

Abstract

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.

First claim

The invention claimed is:

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.

Assignees

• Dow Global Technologies Llc

Inventors

• Chen Linfeng
• Pearson David M

Classifications

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C08F10/02 Primary

  Ethene · CPC title

• C08F4/61912

  in combination with an organoaluminium compound · CPC title

• C08F2500/02

  Low molecular weight, e.g. <100,000 Da. · CPC title

• C08F2420/07

  Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom · CPC title