Mixed catalysts with 2,6-bis(imino)pyridyl iron complexes and bridged hafnocenes

Patent metadata

Field	Value
Publication number	US-10844150-B2
Application number	US-201816016161-A
Country	US
Kind code	B2
Filing date	Jun 22, 2018
Priority date	Aug 4, 2017
Publication date	Nov 24, 2020
Grant date	Nov 24, 2020

Abstract

The present invention provides a supported catalyst system comprising: a bridged group 4 metallocene compound, an iron compound, specifically a 2,6-bis(imino)pyridyl iron complex, a support material and an activator. The present invention further provides a process for polymerization of monomers (such as olefin monomers) comprising contacting one or more monomers with the above supported catalyst systems.

First claim

What is claimed is:

1. A supported catalyst system comprising:
a bridged group 4 metallocene catalyst;
an iron catalyst;
a support material; and
an activator; wherein the bridged group 4 metallocene compound is represented by the formula (A):

where
M* is a group 4 metal;
each of R 1a , R 2a , and R 4a is independently hydrogen, alkoxide or C 1 to C 40 substituted or unsubstituted hydrocarbyl;
R 3a is independently hydrogen, alkoxide, C 1 to C 40 substituted or unsubstituted hydrocarbyl, or
—R 9a —SiR′ 3 or —R 9a —CR′ 3 where R 9a is C 1 to C 4 hydrocarbyl, and each R′ is independently C 1 to C 20 substituted or unsubstituted hydrocarbyl and at least one R′ is C 1 to C 20 substituted or unsubstituted hydrocarbyl;
each of R 5a , R 6a , and R 8a is independently hydrogen, halide, alkoxide or C 1 to C 40 substituted or unsubstituted hydrocarbyl;
R 7a is —R 9a —SiR′ 3 or —R 9a —CR′ 3 where R 9a is C 1 to C 4 hydrocarbyl, and each R′ is independently C 1 to C 20 substituted or unsubstituted hydrocarbyl, and at least one R′ is H;
T is a bridging group; and
each X is independently a univalent anionic ligand, a diene ligand, an alkylidene ligand, or two Xs are joined to form a metallocyclic ring;
and the iron complex is represented by formula (B):

wherein:
A is chlorine, bromine, iodine, —CF 3 or —OR 11 ;
each of R 1 and R 2 is independently hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from the group consisting of N, P, O and S;
wherein each of R 1 and R 2 is optionally substituted by halogen, —NR 11 2 , —OR 11 or —SiR 12 3 ; wherein R 1 optionally bonds with R 3 , and R 2 optionally bonds with R 5 , in each case to independently form a five-, six- or seven-membered ring;
R 7 is a C 1 -C 20 alkyl;
each of R 3 u , R 4 u , R 5 u , R 8 , R 9 , R 10 , R 15 , R 16 , and R 17 is independently hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, —NR 11 2 , —OR 11 , halogen, —SiR 12 3 or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from the group consisting of N, P, O, and S;
wherein R 3 u , R 4 u , R 5 u , R 7 , R 8 , R 9 , R 10 , R 15 , R 16 , and R 17 are optionally substituted by halogen,
—NR 11 2 , —OR 11 or —SiR 12 3 ;
wherein R 3 optionally bonds with R 4 , R 4 optionally bonds with R 5 , R 7 optionally bonds with R 10 , R 10 optionally bonds with R 9 , R 9 optionally bonds with R 8 , R 17 optionally bonds with R 16 and R 16 optionally bonds with R 15 , in each case to independently form a five-, six- or seven-membered carbocyclic or heterocyclic ring, the heterocyclic ring comprising at least one atom from the group consisting of N, P, O and S;
R 13 is C 1 -C 20 -alkyl bonded with the aryl ring via a primary or secondary carbon atom;
R 14 is chlorine, bromine, iodine, —CF 3 or —OR 11 , or C 1 -C 20 -alkyl bonded with the aryl ring;
each R 11 is independently hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or —SiR 12 3 , wherein R 11 is optionally substituted by halogen, or two R 11 radicals optionally bond to form a five- or six-membered ring;
each R 12 is independently hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or two R 12 radicals optionally bond to form a five- or six-membered ring;
each of E 1 , E 2 , and E 3 is independently carbon, nitrogen or phosphorus;
each u is independently 0 if E 1 , E 2 , and/or E 3 is nitrogen or phosphorus and is 1 if E 1 , E 2 , and/or E 3 is carbon;
each X is independently fluorine, chlorine, bromine, iodine, hydrogen, C 1 -C 20 -alkyl, C 2 -C 10 -alkenyl, C 6 -C 20 -aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, —NR 18 2 , —OR 18 , —SR 18 , —SO 3 R 18 , —OC(O)R 18 , —CN, —SCN, β-diketonate, —CO, —BF 4 —, —PF 6 — or bulky non-coordinating anions, and the radicals X can be bonded with one another;
each R 18 is independently hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or —SiR 193 , wherein R 18 can be substituted by halogen or nitrogen- or oxygen-containing groups and two R 18 radicals optionally bond to form a five- or six-membered ring;
each R 19 is independently hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl or arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, wherein R 19 can be substituted by halogen or nitrogen- or oxygen-containing groups or two R 19 radicals optionally bond to form a five- or six-membered ring;
s is 1, 2, or 3;
D is a neutral donor; and
t is 0 to 2.

2. The supported catalyst system according to claim 1 , wherein M* of formula (A) is Hf or Zr, each R 1a , R 2a , R 3a , and R 4a is a C 1 to C 20 alkyl group and R 7a is —CH 2 SiR′ 3 or —CH 2 CR′ 3 where R′ is C 1 to C 20 alkyl or aryl.

3. The supported catalyst system according to claim 1 , wherein for the catalyst represented by formula (B):
each of A and R 14 is chlorine;
each of R 1 and R 2 is methyl;
each of R 3 -R 5 is hydrogen;
each of R 7 and R 9 is methyl;
each of R 8 and R 10 , and R 15 , R 16 , R 17 is independently hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, —NR 11 2 , —OR 11 , halogen, —SiR 12 3 or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from the group consisting of N, P, O, and S;
wherein R 7 , R 8 , R 9 , R 10 , R 15 , R 16 , and R 17 are optionally substituted by halogen, —NR 11 2 , —OR 11 or —SiR 12 3 ; and
wherein R 7 optionally bonds with R 10 , R 10 optionally bonds with R 9 , R 9 optionally bonds with R 8 , R 17 optionally bonds with R 16 , and R 16 optionally bonds with R 15 , in each case to independently form a five-, six- or seven-membered carbocyclic or heterocyclic ring, the heterocyclic ring comprising at least one atom selected from the group consisting of N, P, O, and S;
R 13 is independently a C 1 -C 3 -alkyl bonded with the aryl ring via a primary or secondary carbon atom;
each R 11 is independently hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or —SiR 12 3 , wherein R 11 is optionally substituted by halogen, or two R 11 radicals optionally bond to form a five- or six-membered ring;
each R 12 is independently hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl or arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or two R 12 radicals optionally bond to form a five- or six-membered ring;
each of E 1 , E 2 , and E 3 is carbon; and
each u is 1.

4. A supported catalyst system comprising:
a bridged group 4 metallocene catalyst;
an iron catalyst;
a support material; and
an activator; wherein the iron complex is represented by formula (B):

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Holtcamp Matthew W
• Ye Xuan
• Harlan Charles J
• Titone Michelle E
• Bedoya Matthew S
• Kuppuswamy Subramaniam
• Rangwalla Hasnain

Classifications

• C08F210/16 Primary

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

• C08F2500/05

  Bimodal or multimodal molecular weight distribution · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title