Procatalyst and polymerization process using the same

Patent metadata

Field	Value
Publication number	US-10870713-B2
Application number	US-201615763945-A
Country	US
Kind code	B2
Filing date	Sep 29, 2016
Priority date	Sep 30, 2015
Publication date	Dec 22, 2020
Grant date	Dec 22, 2020

Abstract

A procatalyst for the polymerization of ethylene and optionally one or more alpha-olefins having the structure shown in formula (I) below. Formula (I) is provided. Also provided is a polymerization process using the inventive procatalyst.

First claim

We claim:

1. A procatalyst for the polymerization of ethylene and optionally one or more alpha-olefins having the structure shown in formula (I) below:

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 2 -C 40 )hydrocarbylene or (C 2 -C 40 )heterohydrocarbylene, wherein the (C 2 -C 40 )hydrocarbylene has a portion that comprises a 2-carbon atom to 10-carbon atom linker backbone linking the Z atoms in formula (I) (to which L is bonded) and the (C 2 -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 2 -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 selected from the group consisting of (C 1 -C 40 )hydrocarbyl, each R P is (C 1 -C 40 )hydrocarbyl; and each R N is (C 1 -C 40 )hydrocarbyl or absent; and
R 1-16 are each independently 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 any combination thereof, provided that
at least one of the R 1 -R 16 is —Si(Y 1 )(Y 2 )(Y 3 ) or (C 1 -C 40 )heterohydrocarbyl substituted with —Si(Y 1 )(Y 2 )(Y 3 ); Y 1 is a (C 3 -C 40 )hydrocarbyl; Y 2 is a (C 1 -C 40 )hydrocarbyl; Y 3 is a (C 1 -C 40 )hydrocarbyl, with the further proviso that Y 1 , Y 2 and Y 3 are not all isopropyl groups; and
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 )hydrocarbylene wherein each R independently is an unsubstituted (C 1 -C 18 )hydrocarbyl; and

optionally two or more R groups of the R 1-16 groups (for example, from R 1-8 , R 9-16 ) can combine together into ring structures with such ring structures having from 2 to 50 atoms in the ring excluding any hydrogen atoms.

2. The procatalyst according to claim 1 , having the structure shown below:

3. The procatalyst according to claim 1 , having the structure shown below:

4. The procatalyst according to claim 1 , having the structure shown below:

5. The procatalyst according to claim 1 , having the structure shown below:

6. The procatalyst according to claim 1 , having the structure shown below:

7. The procatalyst according to claim 1 , having the structure shown below:

8. The procatalyst according to claim 1 , having the structure shown below:

9. A polymerization process for producing ethylene based polymers comprising polymerizing ethylene and optionally one or more a-olefins in the presence of a catalyst system in a reactor system having one or more reactors, wherein the catalyst system comprises
one or more procatalysts comprising a metal-ligand complex of formula (I) below:

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 2 -C 40 )hydrocarbylene or (C 2 -C 40 )heterohydrocarbylene, wherein the (C 2 -C 40 )hydrocarbylene has a portion that comprises a 2-carbon atom to 10-carbon atom linker backbone linking the Z atoms in formula (I) (to which L is bonded) and the (C 2 -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 2 -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 selected from the group consisting of (C 1 -C 40 )hydrocarbyl, each R P is (C 1 -C 40 )hydrocarbyl; and each R N is (C 1 -C 40 )hydrocarbyl or absent; and
R 1-16 are each independently 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 any combination thereof, provided that at least one of the R 1 -R 16 is —Si(Y 1 )(Y 2 )(Y 3 ) or (C 1 -C 40 )heterohydrocarbyl substituted with —Si(Y 1 )(Y 2 )(Y 3 ); Y 1 is a (C 3 -C 40 )hydrocarbyl; Y 2 is a (C 1 -C 40 )hydrocarbyl; Y 3 is a (C 1 -C 40 )hydrocarbyl, with the further proviso that Y 1 , Y 2 and Y 3 are not all isopropyl groups; and
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 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—,

Assignees

• Dow Global Technologies Llc

Inventors

• Figueroa Ruth
• Delorbe Johnathan
• Fontaine Phillip P
• Klosin Jerzy
• Shankar Ravi
• Yonkey Matthew

Classifications

• C08F2500/08

  Low density, i.e. < 0.91 g/cm3 · 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

• C08F4/65908

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

• C08F4/64193 Primary

  OOOO · CPC title