Ethylene/alpha-olefin/nonconjugated polyene interpolymers and processes to form the same

Patent metadata

Field	Value
Publication number	US-9422383-B2
Application number	US-201214367478-A
Country	US
Kind code	B2
Filing date	Dec 20, 2012
Priority date	Dec 20, 2011
Publication date	Aug 23, 2016
Grant date	Aug 23, 2016

Abstract

The invention provides a solution polymerization process to form an ethylene/α-olefin/nonconjugated polyene interpolymer, said process comprising polymerizing ethylene, an α-olefin, and a nonconjugated polyene in at least one reactor in the presence of a catalyst selected from Formula I, as described herein; and wherein the polymerization is conducted in a continuous process; and wherein the interpolymer has a rheology ratio (V0.1/V100 at 19° C.) greater than, or equal to, 20.

First claim

The invention claimed is:

1. A solution polymerization process to form an ethylene/α-olefin/nonconjugated polyene interpolymer, said process comprising polymerizing ethylene, an α-olefin, and a nonconjugated polyene in at least one reactor in the presence of a metal-ligand complex selected from Formula I:

wherein:
M is a metal of any one of Groups 3 to 6 of the Periodic Table of the Elements (e.g., Group 4), the metal M being in a formal oxidation state of +2, +3, +4, +5, or +6; n is an integer of from 0 to 5, wherein when n is 0, X is absent (i.e., (X)n is absent);
each X, independently, is a monodentate ligand that is neutral, monoanionic, dianionic, trianionic, or tetraionic; or two X are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral;
each Z, independently, is O, S, N(C1-C40)hydrocarbyl, or P(C1-C40)hydrocarbyl;
L is (C1-C40)hydrocarbylene or (C1-C40)heterohydrocarbylene, wherein the (C1-C40)hydrocarbylene has a portion that comprises a 1-carbon atom to 18-carbon atom linker backbone, linking the Z atoms in formula (I) (to which Z atoms L is bonded) and the (C1-C40)heterohydrocarbylene has a portion that comprises a 1-atom to 18-atom linker backbone, linking the Z atoms in formula (I), wherein each of the from 1 to 18 atoms of the 1-atom to 18-atom linker backbone of the (C1-C40)heterohydrocarbylene independently is a carbon atom or heteroatom, wherein each heteroatom independently is O, S, S(O), S(O) 2 , Si( R C) 2 , P( R P), or N( R N), wherein independently each R C independently is substituted or unsubstituted (C1-C18)hydrocarbyl; (C1-C18)heterohydrocarbyl; each R P independently is substituted or unsubstituted (C1-C18)hydrocarbyl; (C1-C18)heterohydrocarbyl; and each R N independently is substituted or unsubstituted (C1-C18)hydrocarbyl; (C1-C18)heterohydrocarbyl or absent (e.g., when the N to which R N is bonded as —N═);
each of R 3a , R 4a , R 3b and R 4b , independently, is a hydrogen atom; (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl; Si( R C) 3 ; O( R C); S( R C); N( R N) 2 ; P( R P) 2 or halogen atom; wherein R C, R N and R P are defined above;
at least one of R 6c , R 7c , and R 8c , and at least one of R 6d , R 7d , and R 8d , independently, are (C2-C40)hydrocarbyl; Si(Rc) 3 , and each of the others of R 6c , R 7c , R 8c , R 6d , R 7d , and R 8d , independently, is a hydrogen atom; (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl; Si( R C) 3 ; O( R C); S( R C); N( R N) 2 ; P( R P) 2 ; or halogen atom; wherein R C, R N and R P are defined above; and;
optionally two or more R groups (from R 3a to R 8d ) can combine together into one or more ring structures, with such ring structures having from 3 to 50 atoms in the ring not counting hydrogen atoms;
at least one of R 5c and R 5f , independently, is a (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl; Si( R C) 3 ; O( R C); S( R C); N( R N) 2 ; P( R P) 2 ; or halogen atom; and the other of R 5c and R 5f , independently, is a hydrogen atom; (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl; Si( R C) 3 ; O( R C); S( R C); N( R N) 2 ; P( R P) 2 or halogen atom; wherein R C, R N and R P are defined above;
at least one of R 5cc and R 5ff independently is a (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl; Si( R C) 3 ; O( R C); S( R C); N( R N) 2 ; P( R P) 2 or halogen atom; and the other of R 5cc and R 5ff independently is a hydrogen atom; (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl; Si( R C) 3 ; O( R C); S( R C); N( R N) 2 ; P( R P) 2 ; or halogen atom; wherein R C, R N and R P are defined above;
each of R 9a , R 10a , R 11a , R 9b , R 10b , R 11b , R 9aa , R 10aa , R 11aa , R 9bb , R 10bb and R 11bb , independently, is a hydrogen atom; (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl; Si( R C) 3 ; O( R C); S( R C); N( R N) 2 ; P( R P) 2 ; or halogen atom; wherein R C, R N and R P are defined above; and
optionally two or more carbazole R groups (e.g. R 9a , R 10a , R 5a , R 11a , R 9b , R 10b , R 5f , R 11b ) can combine together into one or more ring structures, with such ring structures having from 3 to 50 atoms in the ring not counting hydrogen atoms;
each of the aforementioned hydrocarbyl (e.g., R C, R N, R P, (C1-C40)hydrocarbyl), heterohydrocarbyl (e.g., (C1-C40)heterohydrocarbyl), hydrocarbylene (e.g., (C1-C40) hydrocarbylene), and heterohydrocarbylene (e.g., (C1-C40)heterohydrocarbylene) groups, independently, is unsubstituted or substituted with at least one substituent R S (up to and including persubstitution by R S );
the sum of carbon atoms in R 5c +R 5f +R 7c is greater than 5 carbon atoms or the sum of carbon atoms in R 5cc +R 5ff +R 7d is greater than 5 carbon atoms; and
each R S , independently, is a halogen atom, polyfluoro substitution (that is one of the at least one substituent R S stands for at least two fluoro substituents, which formally replace at least two hydrogen atoms of an unsubstituted version of the substituted group), perfluoro substitution (that is the one R S stands for as many fluoro substituents as hydrogen atoms of an unsubstituted version of the substituted group that is substituted thereby), unsubstituted (C1-C18)alkyl, F 3 C—, FCH 2 O—, F 2 HCO—, F 3 CO—, R 3 Si—, RO—, RS—, RS(O)—, RS(O) 2 —, R 2 P—, R 2 N—, R2C═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 (C1-C18)alkylene, wherein each R independently is an unsubstituted (C1-C18)alkyl; and
wherein the polymerization is conducted in a continuous process; and

wherein interpolymer has a rheology ratio (V0.1/V100 at 190° C.) greater than, or equal to, 20.

2. The process of claim 1 , wherein each Z is O.

3. The process of claim 2 , wherein the metal-ligand complex of formula (I) is a metal-ligand complex of formula (Ia):

and wherein R 7c and R 7d are each independently a (C 4 -C 40 )hydrocarbyl; and
wherein M is a metal of any one of Groups 3 to 6 of the Periodic Table of the Elements (e.g., Group 4), the metal M being in a formal oxidation state of +2, +3, +4, +5, or +6; n is an integer of from 0 to 5, wherein when n is 0, X is absent (i.e., (X)n is absent);
each X, independently, is a monodentate ligand that is neutral, monoanionic, dianionic, trianionic, or tetraionic; or two X are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral;
L is (C1-C40)hydrocarbylene or (C1-C40)heterohydrocarbylene, wherein the (C1-C40)hydrocarbylene has a portion that comprises a 1-carbon atom to 18-carbon atom linker backbone, linking the Z atoms in formula (I) (to which Z atoms L is bonded) and the (C1-C40)heterohydrocarbylene has a portion that comprises a 1-atom to 18-atom linker backbone, linking the Z atoms in formula (I), wherein each of the from 1 to 18 atoms of the 1-atom to 18-atom linker backbone of the (C1-C40)heterohydrocarbylene independently is a carbon atom or heteroatom, wherein each heteroatom independently is O, S, S(O), S(O) 2 , Si( R C) 2 , P( R P), or N( R N), wherein independently each R C independently is substituted or unsubstituted (C1-C18)hydrocarbyl; (C1-C18)heterohydrocarbyl; each R P independently is substituted or unsubstituted (C1-C18)hydrocarbyl; (C1-C18)heterohydrocarbyl; and each R N independently is substituted or unsubstituted (C1-C18)hydrocarbyl; (C1-C18)heterohydrocarbyl or absent (e.g., when the N to which R N is bonded as —N═);
each of R 3a , R 4a , R 3b and R 4b , independently, is a hydrog

Assignees

• Dow Global Technologies Llc

Inventors

• Lipishan Colin
• Karjala Thomas W
• Smith Michael L
• Spencer Liam P
• Klosin Jerzy

Classifications

• C08F210/18 Primary

  with non-conjugated dienes, e.g. EPT 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

  OOOO · CPC title

• C08F236/20

  unconjugated · CPC title