Catalyst systems for olefin polymerization

Patent metadata

Field	Value
Publication number	US-9751998-B2
Application number	US-201314437543-A
Country	US
Kind code	B2
Filing date	Dec 10, 2013
Priority date	Dec 27, 2012
Publication date	Sep 5, 2017
Grant date	Sep 5, 2017

Abstract

The instant invention provides procatalysts and catalyst systems for olefin polymerization, olefin based polymers polymerized therewith, and process for producing the same. In one embodiment, the instant invention provides a procatalyst comprising a metal-ligand complex of formula (I).

First claim

We claim:

1. A catalyst system comprising the reaction product of a metal-ligand complex of formula (I):

wherein:
M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; and n is an integer of from 0 to 3, and wherein when n is 0, X is absent; and each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic; or two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; and X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral; and each Z independently is O, S, N(C 1 -C 40 )hydrocarbyl, or P(C 1 -C 40 )hydrocarbyl; and L is (C 3 -C 40 )hydrocarbylene or (C 3 -C 40 )heterohydrocarbylene, wherein the (C 3 -C 40 )hydrocarbylene has a portion that comprises a 3-carbon atom to 10-carbon atom linker backbone linking the Z atoms in formula (I) (to which L is bonded) and the (C 3 -C 40 )heterohydrocarbylene has a portion that comprises a 3-atom to 10-atom linker backbone linking the Z atoms in formula (I), wherein each of the 3 to 10 atoms of the 3-atom to 10-atom linker backbone of the (C 3 -C 40 )heterohydrocarbylene independently is a carbon atom or 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 (C 1 -C 30 )hydrocarbyl, each R P is (C 1 -C 30 )hydrocarbyl; and each R N is (C 1 -C 30 )hydrocarbyl or absent; and
R 1-24 are selected from the group consisting of a (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 atom, hydrogen atom, and combination thereof; and, wherein at least R 1 , R 16 , or both comprise of formula (II),

wherein at least one of R 22 or R 19 is H, and when R 22 is H, then R 19 is a (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)— or halogen atom; and when R 19 is H, then R 22 is a (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)— or halogen atom; and
wherein at least one of R 8 or R 9 is H, and when R 8 is H, then R 9 is a (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)— or halogen atom; and when R 9 is H, then R 8 is a (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)— or halogen atom; and
optionally two or more R groups from R 9-15 , R 9-13 , R 9-12 , R 2-8 , R 4-8 , R 5-8 can combine together into ring structures, with such ring structures having from 3 to 50 atoms in the ring excluding any hydrogen atoms;
each of the hydrocarbyl, heterohydrocarbyl, Si(R C ) 3 , Ge(R C ) 3 , P(R P ) 2 , N(R N ) 2 , OR C , SR C , 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)—, hydrocarbylene, and heterohydrocarbylene groups independently is unsubstituted or substituted with one or more R S substituents;
each R S independently is a halogen atom, polyfluoro substitution, perfluoro substitution, unsubstituted (C 1 -C 18 )alkyl, F 3 C—, FCH 2 O—, F 2 HCO—, F 3 CO—, R 3 Si—, R 3 Ge—, RO—, RS—, RS(O)—, RS(O) 2 —, R 2 P—, R 2 N—, R 2 C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R 2 NC(O)—, or two of the R S are taken together to form an unsubstituted (C 1 -C 18 )alkylene, wherein each R independently is an unsubstituted (C 1 -C 18 )alkyl; and
one or more cocatalysts; wherein the ratio of total number of moles of the one or more metal-ligand complexes of formula (I) to total number of moles of the one or more cocatalysts is from 1:10,000 to 100:1; and
wherein said catalyst system has a reactivity ratio r 1 in the range of greater than 100.

2. The procatalyst according to claim 1 wherein Z is O.

3. A polymerization process comprising the steps of:
polymerizing one or more α-olefins in the presence of one or more catalyst systems of claim 1 under olefin polymerizing conditions; and thereby forming an olefin based polymer.

4. An olefin based polymer comprising the polymerization reaction product of:
one or more α-olefins polymerized in the presence of one or more catalyst systems of claim 1 under olefin polymerizing conditions.

5. The procatalyst of claim 1 wherein and R 1 and R 16 are the same.

Assignees

• Dow Global Technologies Llc

Inventors

• Klosin Jerzy
• Figueroa Ruth
• Thomas Pulikkottil J
• Demirors Mehmet
• Desjardins Sylvie
• Kapur Mridula
• Fontaine Philip P

Classifications

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• C08L2205/02

  containing two or more polymers of the same C08L -group · CPC title

• C08L23/0815

  with aliphatic 1-olefins containing one carbon-to-carbon double bond · CPC title

• C08L23/08

  Copolymers of ethene (C08L23/16 takes precedence) · CPC title

• C08L23/06

  Polyethylene · CPC title