Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts

Patent metadata

Field	Value
Publication number	US-9605098-B2
Application number	US-201414781419-A
Country	US
Kind code	B2
Filing date	Jun 26, 2014
Priority date	Jun 28, 2013
Publication date	Mar 28, 2017
Grant date	Mar 28, 2017

Abstract

A process for preparing an olefin homopolymer or copolymer comprises contacting ethylene, an alpha-olefin, or a combination, and a catalytic amount of a metal-ligand complex catalyst of a particular formula that requires at least one halogen atom that is ortho to a bridging moiety. The strategic location of the halogen atom(s) ensures a product having a molecular weight that is predictably and significantly reduced in comparison with that of copolymers produced using otherwise identical metal-ligand complex catalysts that lack halogen atoms at the specified sites.

First claim

The invention claimed is:

1. A process for preparing an olefin homopolymer or copolymer, comprising contacting ethylene, an alpha-olefin, or a combination thereof, and a catalytic amount of a metal-ligand complex catalyst of the formula:

wherein M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4;
n is an integer of from 0 to 3, wherein when n is 0, X is absent;
each X is independently a monodentate ligand that is neutral, monoanionic, or dianionic, or two X are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic;
X and n are selected such that the metal-ligand complex is neutral;
each Z moiety independently is O, S, N(C 1 -C 40 ) hydrocarbyl, or P(C 1 -C 40 ) hydrocarbyl;
L is (C 1 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene, provided such has a portion that comprises a 2- to 8-carbon atom linker backbone linking the Z moieties, each atom of such 2- to 8-atom linker being independently a carbon atom or a heteroatom, wherein each heteroatom independently is O, S, S(O), S(O) 2 , Si(R C ) 2 , Ge(R C ) 2 , P(R P ), or N(R N ), wherein independently each R C is unsubstituted (C 1 -C 18 )hydrocarbyl or the two R C are taken together to form a (C 2 -C 9 )alkylene, each R P is unsubstituted (C 1 -C 18 )hydrocarbyl; and each R N is unsubstituted (C 1 -C 18 )hydrocarbyl, a hydrogen atom or absent;
R 1a , R 1b , or both is a halogen atom;
R 2a , R 3a , R 4a , R 2b , R 3b , R 4b , R 6c , R 7c , R 8c , R 6d , R 7d , and R 8d independently is a hydrogen atom; (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, F 3 C, F 3 CO, RCS(O)—, RCS(O) 2 —, (RC) 2 C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC) 2 NC(O)—or halogen atom;
and R 5c and R 5d is independently selected from 1,2,3,4-tetrahydronaphthyl; anthracenyl; 1,2,3,4-tetrahydroanthracenyl; 1,2,3,4,5,6,7,8-octahydroanthracenyl; phenanthrenyl; 1,2,3,4,5,6,7,8-octahydrophenanthrenyl; 2,6-dimethylphenyl; 2,6-diisopropylphenyl; 3,5-di(tertiary-butyl)phenyl; 3,5-diphenylphenyl; 1-naphthyl; 2-methyl-l-naphthyl; 2-naphthyl; 1,2,3,4-tetra-hydronaphth-5-yl; 1,2,3,4-tetrahydronaphth-6-yl; anthracen-9-yl; 1,2,3,4-tetrahydroanthracen-9-yl; 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl; 1,2,3,4,5,6,7,8-octahydrophenanthren-9-yl; indolyl; indolinyl; quinolinyl; 1,2,3,4-tetrahydroquinolinyl; isoquinolinyl; 1,2,3,4-tetrahydroisoquinolinyl; carbazolyl; 1,2,3,4-tetrahydrocarbazolyl; 1,2,3,4,5,6,7,8-octahydrocarbazolyl; 2,7-di(tertiary-butyl)-carbazol-9-yl; 2,7-di(tertiary-octyl)-carbazol-9-yl; 2,7-diphenylcarbazol-9-yl; or 2,7-bis(2,4,6-trimethylphenyl)-carbazol-9-yl;
under conditions such that an ethylene homopolymer, an alpha-olefin homopolymer, or an ethylene/alpha-olefin copolymer is formed, such having a weight average molecular weight that is reduced by at least 20 percent when compared with an otherwise identical ethylene homopolymer, alpha- olefin homopolymer or ethylene/alpha-olefin copolymer prepared under identical conditions with a catalyst that is otherwise identical but wherein neither R 1a nor R 1b is a halogen atom.

2. The process of claim 1 wherein R 1a , R 1b , or both is a halogen atom selected from fluorine, chlorine, iodine, or combinations thereof.

3. The process of claim 1 wherein the alpha-olefin is selected from the group consisting of linear alpha-olefins having from 3 to 12 carbons, branched alpha-olefins having from 5 to 16 carbons, and combinations thereof.

Assignees

• Dow Global Technologies Llc

Inventors

• Klosin Jerzy
• Figueroa Ruth
• Froese Robert D J

Classifications

• C08F210/16 Primary

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

• C08F4/65908

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

• C08F4/659

  Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F2500/03

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