Polymerization process that include group III and lanthanide bis-phenyl-phenoxy metal-ligand complexes and chain transfer agents

Patent metadata

Field	Value
Publication number	US-12552885-B2
Application number	US-202117796531-A
Country	US
Kind code	B2
Filing date	Jan 29, 2021
Priority date	Jan 31, 2020
Publication date	Feb 17, 2026
Grant date	Feb 17, 2026

Abstract

Embodiments of this disclosure are directed to polymerization process comprising contacting ethylene and optionally one or more α-olefins in solution in the presence of one or more catalyst systems and a chain transfer agent, wherein the catalyst system comprises a metal-ligand complex according to formula (I).

First claim

The invention claimed is:

1 . A polymerization process comprising contacting ethylene and optionally one or more α-olefins in solution in the presence of one or more catalyst systems and a chain transfer agent, wherein the one or more catalyst systems comprise a metal-ligand complex according to formula (I):

where:
M is scandium, yttrium, or a lanthanide metal having an oxidation state of +3;
X is a ligand chosen from (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —CH 2 Si(R C ) 3-Q (OR) Q , —Si(R C ) 3-Q (OR C )Q, —OSi(R C ) 3-Q (OR C )Q, —CH 2 Ge(R C ) 3-Q (OR) Q , —Ge(R C ) 3-Q (OR C ) Q , —P(R C ) 2-W (OR C ) W , —P(O)(R C ) 2-W (OR C ) W , —N(R C ) 2 , —NH(R C ), —N(Si(R C ) 3 ) 2 , —NR C Si(R C ) 3 , —NHSi(R C ) 3 , —OR C , —SR C , —NO 2 , CN, —CF 3 , —OCF 3 , —S(O)R C , —S(O) 2 R C , —OS(O) 2 R C , —N═C(R C ) 2 , —N═CH(R C ), —N═CH 2 , —N═P(R C ) 3 , —OC(O)R C , —C(O)OR C , —N(R C )C(O)R C , —N(R C )C(O)H, —NHC(O)R C , —C(O)N(R C ) 2 , —C(O)NHR C , —C(O)NH 2 , a halogen, or a hydrogen, wherein each R C is independently a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, or a substituted or unsubstituted (C 1 -C 30 )heterohydrocarbyl, and each Q is 0, 1, 2 or 3 and each W is 0, 1, or 2; B(R Y ) 4 , Al(R Y ) 4 , or Ga(R Y ) 4 , wherein each R Y is —H, (C 1 -C 30 )hydrocarbyl, or halogen atom;
each M-Z bond is a dative bond;
each T is a Lewis Base;
n is 0, 1, or 2, when n is 1, X and T are optionally linked, when n is 2, X and one of T are optionally linked;
the metal-ligand complex is overall charge-neutral;
each Z is independently chosen from —O—, —S—, —N(R N )—, or —P(R P )—, wherein the dotted line optionally defines a davtive bond;
R 1 and R 16 are independently selected from the group consisting of (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)—, or 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 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 ) 2 P═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, and halogen;
provided that when M is yttrium or a lanthanide metal, R 1 is not phenyl or tert-butyl; and R 16 is not phenyl or tert-butyl;
L is (C 1 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene; and
each R C , R P , and R N in formula (I) is independently a (C 1 -C 30 )hydrocarbyl, (C 1 -C 30 )heterohydrocarbyl, or —H.

2 . The polymerization process of claim 1 , wherein the chain transfer agent is chosen from (C 1 -C 40 )hydrocarbyl) 2 Zn, ((C 1 -C 40 )hydrocarbyl) 3 Al, alkylaluminum halide, or modified alkyl aluminoxane.

3 . The polymerization process of claim 1 , wherein a co-catalyst is absent from the one or more catalyst systems.

4 . The polymerization process of claim 1 , wherein the chain transfer agent is modified methylaluminoxane.

5 . The polymerization process of claim 1 , wherein the chain transfer agent is an allylaluminum, a dialkyl zinc or a combination thereof.

6 . The polymerization process according to claim 1 , where R 1 and R 16 are chosen from radicals having formula (II), radicals having formula (III), or radicals having formula (IV):

where each of R 31-35 , R 41-48 , and R 51-59 is independently chosen 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 halogen.

7 . The polymerization process according to claim 6 , wherein at least one of R 1 and R 16 is a radical having formula (III).

8 . The polymerization process according to claim 7 , wherein R 42 and R 47 are (C 1 -C 20 )hydrocarbyl, —Si[(C 1 -C 20 )hydrocarbyl] 3 , or —Ge[(C 1 -C 20 )hydrocarbyl] 3 ; or R 43 and R 46 are (C 1 -C 20 )hydrocarbyl, —Si[(C 1 -C 20 )hydrocarbyl] 3 , or —Ge[(C 1 -C 20 )hydrocarbyl] 3 .

9 . The polymerization process according to claim 7 , wherein optionally R 42 and R 43 are linked to form a cyclic structure, and optionally R 46 and R 47 are linked to form a cyclic structure.

10 . The polymerization process according to claim 6 , wherein at least one of R 1 and R 16 is a radical having formula (II) and R 32 and R 34 are (C 1 -C 20 )hydrocarbyl, —Si[(C 1 -C 20 )hydrocarbyl] 3 , or —Ge[(C 1 -C 20 )hydrocarbyl] 3 .

11 . The polymerization process according to claim 6 , wherein at least one of R 1 and R 16 is a radical having formula (IV) and at least two of R 52 , R 53 , R 55 , R 57 , and R 58 are (C 1 -C 20 )hydrocarbyl, —Si[(C 1 -C 20 )hydrocarbyl] 3 , or —Ge[(C 1 -C 20 )hydrocarbyl] 3 .

12 . The polymerization process according to claim 1 , wherein R 8 and R 9 are methyl.

13 . The polymerization process according to claim 1 , wherein R 6 and R 11 are not —H.

14 . The polymerization process according to claim 1 , where L is chosen from —CH 2 —, —CH 2 (CH 2 ) m CH 2 — where m is from 0 to 3, —CH 2 Si(R C ) 2 CH 2 —, —CH 2 Ge(R C ) 2 CH 2 —, —CH(CH 3 )CH 2 CH(CH 3 ), and —CH 2 (phen-1,2-di-yl)CH 2 —, where each R C in L is (C 1 -C 20 )hydrocarbyl.

15 . The polymerization process according to claim 1 , wherein X is —CH 2 Si[(C 1 -C 20 )alkyl] 3 .

16 . The polymerization process according to claim 1 , wherein n is 1 or 2; and at least one T is (C 1 -C 20 )heterohydrocarbon, wherein a hetero atom of the heterohydrocarbon is oxygen.

17 . The polymerization process according to claim 1 , wherein n is 1 or 2; and at least one T is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

18 . The polymerization process according to claim 1 , wherein when M is yttrium or a lanthanide metal, at least one of R 5-8 is not —H and at least one of R 9-12 is not —H.

19 . The polymerization process according to claim 1 , wherein the one or more catalyst systems further comprise an additive.

Assignees

• Dow Global Technologies Llc

Inventors

• Baillie Rhett A
• Fontaine Philip P
• Delorbe Johnathan E
• Huacuja Rafael
• Auyeung Evelyn
• Klosin Jerzy
• Grigg Robert David
• Pal Sudipta
• Bailey Brad C

Classifications

• C08F4/52

  selected from boron, aluminium, gallium, indium, thallium or rare earths (C08F4/14 takes precedence) · CPC title

• C08F4/545

  rare earths being present, e.g. triethylaluminium + neodymium octanoate · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C08F4/63912

  in combination with an organoaluminium compound · CPC title