Non-cyclopentadienyl-based chromium catalysts for olefin polymerization

Patent metadata

Field	Value
Publication number	US-9422375-B2
Application number	US-201514931258-A
Country	US
Kind code	B2
Filing date	Nov 3, 2015
Priority date	May 12, 2011
Publication date	Aug 23, 2016
Grant date	Aug 23, 2016

Abstract

Provided is a non-cyclopentadienyl-based chromium-ligand complex, preferably a chromium-ligand complex of formula (J): LCr(R A ) m (D) k (J), wherein L is a non-Cp monoanionic ligand; Cr (chromium) is in a formal oxidation state of +3 or +2; when Cr formally is Cr +3 , either m is 1 and R A is hydrocarbylene (a hydrocarbylene chromium-ligand complex of formula (J)) or m is 2 and each R A independently is hydrocarbyl (a dihydrocarbyl chromium-ligand complex of formula (J)), wherein each hydrocarbyl or hydrocarbylene of R A independently is unsubstituted or substituted by from 1 to 5 R AS ; each R AS independently is a neutral aprotic heteroalkyl, neutral aprotic heterocycloalkyl, neutral aprotic heteroaryl, or neutral aprotic aryl; when Cr formally is Cr +2 , m is 1 and R A is hydrocarbyl (a hydrocarbyl chromium-ligand complex of formula (J)); k is an integer of 0 or 1; D is absent when k is 0 or D is a neutral ligand when k is 1; wherein the chromium-ligand complex of formula (J) is overall neutral and lacks a cyclopentadienyl-based (Cp-based) moiety. Also provided is a chromium catalyst comprising or prepared from the complex. Also provided is a process of making the catalyst and a process employing the chromium catalyst for polymerizing the olefin monomer, especially a straight chain 1-alkene, to prepare the polyolefin, especially a partially chain-straightened poly(1-alkene) or olefin block copolymer. Further provided is the partially chain-straightened poly(1-alkene) or olefin block copolymer prepared thereby. Also provided is a high throughput workflow.

First claim

What is claimed is:

1. A non-cyclopentadienyl-based chromium-ligand complex of formula (J): LCr(R A ) m (D) k (J), wherein L is a non-Cp monoanionic ligand; Cr (chromium) is in a formal oxidation state of +3 or +2; when Cr formally is Cr +3 , either m is 1 and R A is hydrocarbylene (a hydrocarbylene chromium-ligand complex of formula (J)) or m is 2 and each R A independently is hydrocarbyl (a dihydrocarbyl chromium-ligand complex of formula (J)), wherein each hydrocarbyl or hydrocarbylene of R A independently is unsubstituted or substituted by from 1 to 5 R AS ; each R AS independently is a neutral aprotic heteroalkyl, neutral aprotic heterocycloalkyl, neutral aprotic heteroaryl, or neutral aprotic aryl; when Cr formally is Cr +2 , m is 1 and R A is hydrocarbyl (a hydrocarbyl chromium-ligand complex of formula (J)); k is an integer of 0 or 1; D is absent when k is 0 or D is a neutral ligand when k is 1; wherein the chromium-ligand complex of formula (J) is overall neutral and lacks a cyclopentadienyl-based (Cp-based) moiety, wherein k is 0; D is absent; and, wherein L is a conjugate base form of any one of the following compounds:
N 1 -((1H-pyrrol-2-yl)methylene)-N 2 ,N 2 -dimethylethane-1,2-diamine; diphenyl(pyridin-2-yl)methanol; N-(2-((benzylimino)methyl)phenyl)methanesulfonamide; N-((1H-pyrrol-2-yl)methylene)-2-methoxyethanamine; N-((1H-pyrrol-2-yl)methylene)-2-(methylthio)ethanamine; N-((1H-pyrrol-2-yl)methylene)-2-(benzylthio)ethanamine; N 1 -((1H-indol-2-yl)methylene)-N 2 ,N 2 -dimethylethane-1,2-diamine; N-((1H-pyrrol-2-yl)methylene)-2-(diphenylphosphino)ethanamine; N-((1H-pyrrol-2-yl)methylene)-2-(di(propan-2-yl)phosphino)ethanamine; N-((1H-pyrrol-2-yl)methylene)-2-(pyrrolidin-1-yl)ethanamine; N-((1H-pyrrol-2-yl)methylene)-2-(piperidin-1-yl)ethanamine; N-methylisoquinolin-1-amine; 2,6-di(propan-2-yl)-N-((6-(naphthalen-1-yl)pyridin-2-yl)methylene)aniline; 4-chloro-N-((6-(4-chlorophenyl)pyridin-2-yl)methylene)-2,6-di(propan-2-yl)aniline; 3-((pyridin-2-ylmethyl)amino)butan-2-one oxime; 4-methyl-N-(2-0(4-methylphenyl)imino)methyl)phenyl)-benzenesulfonamide; N-(2-((butylimino)methyl)phenyl)-4-methylbenzenesulfonamide; N-(2-((benzylimino)methyl)phenyl)-4-methylbenzenesulfonamide; N-(2-((benzylimino)methyl)phenyl)-2,4,6-tri(propan-2-yl)benzenesulfonamide; 9-(4-methoxypyrimidin-5-yl)-9H-xanthen-9-ol; bis(4-methoxypyrimidin-5-yl)(phenyl)methanol; bis(4-ethoxypyrimidin-5-yl)(phenyl)methanol; 1-(2-ethoxy-6-methoxyphenyl)-2-methyl-1-phenylpropan-1-ol; N-([1,1′-biphenyl]-2-yl(6-naphthalen-1-yl)pyridin-2-yl)methyl-2,6-di(propan-2-yl)aniline; N-benzyl-6-methylpyridin-2-amine; N 1 -(isoquinolin-1-yl)-N 2 ,N 2 -dimethylethane-1,2-diamine; N-(2-methoxyethyl)isoquinolin-1-amine; N 1 -(isoquinolin-1-yl)-N 3 ,N 3 -dimethylpropane-1,3-diamine; N-((tetrahydrofuran-2-yl)methyl)isoquinolin-1-amine; N 1 -(isoquinolin-1-yl)-N 3 ,N 3 ,2,2-tetramethylpropane-1,3-diamine; 2,3-dihydro-1H-pyrrolo[2,3-b]pyridine; N-(furan-2-ylmethyl)isoquinolin-1-amine; 1,2-dihydropyrrolo[4,3,2-ij]isoquinoline; 2,3-dihydro-1H-benzo[de][1,8]naphthyridine; and N,N′-diphenylbenzamidine.

2. The complex as in claim 1 , wherein m is 2 and each R A is methyl or benzyl.

3. A non-cyclopentadienyl-based chromium-ligand complex, wherein the complex is any one of complexes (1) to (7):

4. A chromium catalyst useful for polymerizing an olefin monomer, the chromium catalyst comprising a mixture or reaction product of the complex of any one of complexes (1) to (7) as in claim 3 and an activating cocatalyst, wherein the ratio of total number of moles of the complex of any one of complexes (1) to (7) to total number of moles of the activating cocatalyst is from 1:10,000 to 100:1.

Assignees

• Dow Global Technologies Llc

Inventors

• Christianson Matthew D
• De Vries Timothy S
• Froese Robert D J
• Ober Matthias S
• Patton Jasson T
• Romer Duane R
• Roof Gordon R
• Sun Lixin
• Szuromi Endre
• Theriault Curt N
• Welsh Dean M
• Wenzel Timothy T
• Moran Paul H

Classifications

• C08F110/02

  Ethene · CPC title

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F210/06

  Propene · CPC title

• C08F110/06

  Propene · CPC title

• C08F4/78 Primary

  selected from chromium, molybdenum or tungsten · CPC title