Multiple catalyst system comprising metallocenes and tridentate nitrogen based ligand complexes for olefin polymerisation

Patent metadata

Field	Value
Publication number	US-9714305-B2
Application number	US-201414775807-A
Country	US
Kind code	B2
Filing date	Feb 21, 2014
Priority date	Mar 15, 2013
Publication date	Jul 25, 2017
Grant date	Jul 25, 2017

Abstract

Catalyst systems and methods for making and using the same are described herein. A catalyst system can include at least three catalysts. The three catalysts include a metallocene catalyst, a first non-metallocene including a ligand complexed to a metal through two or more nitrogen atoms, and a second non-metallocene including a ligand complexed to a metal through one or more nitrogen atoms and an oxygen atom.

First claim

What is claimed is:

1. A polymerization catalyst system, comprising at least three catalysts, comprising:
a metallocene catalyst;
a first non-metallocene comprising a ligand complexed to a metal through two or more nitrogen atoms; and
a second non-metallocene comprising a catalyst of the formula:

or any combinations, wherein X 1 and X 2 are each, independently, phenyl, methyl, chloro, fluoro, or a hydrocarbyl group.

2. The polymerization catalyst system of claim 1 , comprising bis(n-butylcyclopentadienyl) zirconium(X) 2 , wherein each X is, independently, phenyl, methyl, chloro, fluoro, or a hydrocarbyl group.

3. The polymerization catalyst system of claim 1 , comprising bis(n-propylcyclopentadienyl, tetramethylcyclopentadienyl) zirconium(X) 2 , wherein each X is, independently, phenyl, methyl, chloro, fluoro, or a hydrocarbyl group.

4. The polymerization catalyst system of claim 1 , comprising [(pentamethylbenzylNCH 2 ) 2 NH]Zr(X) 2 , wherein each X is, independently, phenyl, methyl, chloro, fluoro, or a hydrocarbyl group.

5. The polymerization catalyst system of claim 1 , comprising a catalyst of the formula:
Cp A Cp B MX n or Cp A (A)Cp B MX n ,

wherein M is a Group 4, 5, or 6 atom; Cp A and Cp B are each bound to M and are independently selected from the group consisting of cyclopentadienyl ligands, substituted cyclopentadienyl ligands, ligands isolobal to cyclopentadienyl and substituted ligands isolobal to cyclopentadienyl; (A) is a divalent bridging group bound to both Cp A and Cp B selected from the group consisting of divalent C 1 to C 20 hydrocarbyls and C 1 to C 20 heteroatom containing hydrocarbonyls, wherein the heteroatom containing hydrocarbonyls comprise from one to three heteroatoms; X is a leaving group selected from the group consisting of chloride ions, bromide ions, C 1 to C 10 alkyls, and C 2 to C 12 alkenyls, carboxylates, acetylacetonates, and alkoxides; and
n is an integer from 1 to 3.

6. The polymerization catalyst system of claim 1 , comprising a catalyst of the formula:

wherein M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal; each X is independently an anionic leaving group; y is 0 or 1; n is the oxidation state of M; m is the formal charge of the ligand represented by YZL or YZL′; L is a Group 15 or 16 element; L′ is a group 15 or 16 element or Group 14 containing group; Y is a Group 15 element; Z is a Group 15 element; le and R 2 are independently a C 1 to C 20 hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus; R 1 and R 2 may be interconnected to each other; R 3 is absent, a hydrocarbon group, hydrogen, a halogen, or a heteroatom containing group; R 4 and R 5 are independently an alky group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group, or a multiple ring system; R 4 and R 5 may be interconnected to each other; R 6 and R 7 are independently absent, hydrogen, an alkyl group, a halogen, a heteroatom, or a hydrocarbyl group; and R* is absent, hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.

7. The polymerization catalyst system of claim 1 , wherein the three catalysts are co-supported on a single support.

8. The polymerization catalyst of claim 1 , wherein the first non metallocene catalyst and the second non metallocene catalyst are co-supported on a single support, and at least a portion of the metallocene catalyst is added as a trim feed to the support.

9. The polymerization catalyst system of claim 1 , comprising a slurry mixture.

Assignees

• Univation Tech Llc

Inventors

• Wagner Juliet B
• Giesbrecht Garth R
• Kao Sun-Chueh
• Jaker Stephen P

Classifications

• C08F4/65908

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

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F210/16 Primary

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