Bis-phenyl-phenoxy polyolefin catalysts having a methylenetrialkylsilicon ligand on the metal for improved solubility

Patent metadata

Field	Value
Publication number	US-11066428-B2
Application number	US-201816646228-A
Country	US
Kind code	B2
Filing date	Sep 20, 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, Formula (I), where X is selected from the group consisting of —(CH2)SiRX3.

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;
X is selected from the group consisting of —(CH 2 )SiR X 3 , where each R X is independently a (C 1 -C 30 )hydrocarbyl or a (C 1 -C 30 )heterohydrocarbyl and at least one of R X is a (C 2 -C 30 )hydrocarbyl, where any two R X or all three R X are optionally covalently linked;
each Z is independently chosen from —O—, —S—, —N(R N )—, or —P(R P )—;
each of R 1 and R 16 is 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 —, (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)—, 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.

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

3. 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.

4. 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.

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

6. 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 ) 2 (n-butyl); and
each Z is oxygen.

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

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

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

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

11. The catalyst system according to claim 1 , 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).

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

where:
M is zirconium or hafnium being in a formal oxidation state of +2, +3, or +4;
X is selected from the group consisting of —(CH 2 )Si(CH 3 )(n-Oct)R X , —(CH 2 )Si(CH 3 ) 2 (n-hexyl), —(CH 2 )Si(CH 3 ) 2 (2-ethylhexyl), —(CH 2 )Si(CH 3 ) 2 (dodecyl), and —CH 2 Si(CH 3 ) 2 CH 2 Si(CH 3 ) 3 , where R X is a (C 1 -C 30 )hydrocarbyl or a (C 1 -C 30 )heterohydrocarbyl;
each Z is —O—;
each of R 1 and R 16 is 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 —, (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)—, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):

 where each 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.

Assignees

• Dow Global Technologies Llc

Inventors

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

Classifications

• C07F7/0812 Primary

  comprising a heterocyclic ring · CPC title

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C08F110/02

  Ethene · CPC title