Bis-phenyl-phenoxy polyolefin catalysts having two methylenetrialkylsilicon ligands on the metal for improved solubility

Patent metadata

Field	Value
Publication number	US-11066489-B2
Application number	US-201816646237-A
Country	US
Kind code	B2
Filing date	Sep 19, 2018
Priority date	Sep 29, 2017
Publication date	Jul 20, 2021
Grant date	Jul 20, 2021

Abstract

Embodiments are directed to a catalyst system comprising metal ligand complexes and processes for polyolefin polymerization using the metal ligand complex having the following structure: where each X is selected from the group consisting of —(CH 2 )SiR X 3 .

First claim

The invention claimed is:

1. A catalyst system comprising a metal-ligand complex according to formula (I):

where:
M is a metal chosen from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4;
each X is selected from the group consisting of —(CH 2 )SiR X 3 , each R X is independently a (C 1 -C 30 )hydrocarbyl or a (C 1 -C 30 )heterohydrocarbyl, and at least one R X is (C 2 -C 30 )hydrocarbyl, and any two R X or all three R X are optionally covalently linked;
n is 1 or 2;
each Z is independently chosen from —O—, —S—, —N(R N )—, or —P(R P )—;
R 1 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)—, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):

where each of R 31 —R 35 , R 41 —R 48 , and R 51 —R 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,

provided that at least one of R 1 or R 16 is a radical having formula (II), a radical having formula (III), or a radical having formula (IV);
each of R 2 —R 4 , R 5 —R 8 , R 9 —R 12 , and R 13 —R 15 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)—, (R C ) 2 NC(O)—, and halogen;
L is (C 2 -C 40 )hydrocarbylene or (C 2 -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,

wherein the metal-ligand complex according to formula (I) has a wt % solubility ratio W/Y of at least 1.5, wherein W is the wt % solubility of the metal-ligand complex of formula (I) in methylcyclohexane (MCH) at standard temperature and pressure (STP); wherein Y is the wt % of a corresponding comparative metal-ligand complex of formula (Ia) in MCH at STP; and
wherein the corresponding comparative complex has a structure according to formula (Ia):

 in which M, each Z, each R 1 —R 16 , and L all are identical to corresponding groups of the metal-ligand complex according to formula (I).

2. The catalyst system according to claim 1 , wherein:
M is zirconium or hafnium;
each X is —(CH 2 )Si(CH 2 CH 3 ) 3 ; and
each Z is oxygen.

3. The catalyst system according to claim 1 , wherein:
M is zirconium or hafnium;
each X is selected from the group consisting of —(CH 2 )Si(CH 3 )(n-Oct)R X ; and
each Z is oxygen.

4. The catalyst system according to claim 1 , wherein exactly two R X are covalently linked or exactly three R X are covalently linked.

5. A catalyst system comprising a metal-ligand complex according to formula (I):

where:
M is a metal chosen from zirconium or hafnium, the metal being in a formal oxidation state of +2, +3, or +4;
each X is selected from the group consisting of —(CH 2 )Si(n-Oct)R X 2 , where each R X is independently a (C 1 -C 30 )hydrocarbyl or a (C 1 -C 30 )heterohydrocarbyl and any two R X are optionally covalently linked;
n is 1 or 2;
each Z is —O—;
R 1 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)—, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):

where each of R 31 —R 35 , R 41 —R 48 , and R 51 —R 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,

provided that at least one of R 1 or R 16 is a radical having formula (II), a radical having formula (III), or a radical having formula (IV);
each of R 2 —R 4 , R 5 —R 8 , R 9 —R 12 , and R 13 —R 15 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)—, (R C ) 2 NC(O)—, and halogen;
L is (C 2 -C 40 )hydrocarbylene or (C 2 -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,

wherein the metal-ligand complex according to formula (I) has a wt % solubility ratio W/Y of at least 1.5, wherein W is the wt % solubility of the metal-ligand complex of formula (I) in methylcyclohexane (MCH) at standard temperature and pressure (STP); wherein Y is the wt % of a corresponding comparative metal-ligand complex of formula (Ia) in MCH at STP; and
wherein the corresponding comparative complex has a structure according to formula (Ia):

in which M, each Z, each R 1 —R 16 , and L all are identical to corresponding groups of the metal-ligand complex according to formula (I).

Assignees

• Dow Global Technologies Llc

Inventors

• Krasovskiy Arkady L
• Wilson David R
• Stubbert Bryan D
• Vaidya Tulaza
• Klosin Jerzy
• Carnahan Edmund M
• Fontaine Philip P
• Rosen Mari S

Classifications

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F2500/03

  Narrow molecular weight distribution, i.e. Mw/Mn < 3 · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title