IP Library Granted Patent US 9,234,060
Granted Patent B2
US 9,234,060 · App. 14/356,419 · Granted Jan 12, 2016

Methods of preparing a catalyst system

Inventors: Sun-Chueh Kao (Pearland, TX); Phuong A. Cao (Old Bridge, NJ); C. Jeff Harlan (Houston, TX); Parul A. Khokhani (Manalapan, NJ); George Rodriguez (Houston, TX); Francis C. Rix (Houston, TX); Garth R. Giesbrecht (The Woodlands, TX)
Assignee: Univation Technologies, LLC
C08F210/16B01J31/14B01J31/143C08F4/642C08F4/64079C08F4/6592C08F4/65912C08F4/65916C08F4/64141C08F4/64148C08F4/64189C08F4/64193C08F4/65925C08F4/65927
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 9,234,060
App. No.
14/356,419
Granted
Jan 12, 2016
Kind
B2
Abstract

Disclosed herein are methods of preparing a catalyst system comprising a spray-dried activator and polymerization processes employing these catalyst systems.

Claims (42)

1. A method of preparing a catalyst system comprising:

forming a spray-dried activator;

combining the spray-dried activator and one or more catalyst components with a diluent to produce a slurry for the catalyst system, where the diluent is a mixture of mineral oil and an aliphatic hydrocarbon.

2. The method of claim 1 , further comprising:

combining an activator, a filler material, and a diluent; and

spray drying the suspension to produce the spray-dried activator.

3. The method of claim 1 , wherein the spray-dried activator comprises at least one activator selected from the group consisting of a Lewis acid activator, a non-coordinating ionic activator, an ionizing activator, an organoaluminum compound, an aluminoxane, a modified aluminoxane, and any combination thereof.

4. The method of claim 1 , wherein the spray-dried activator comprises at least one activator selected from the group consisting of methylaluminoxane, modified methylaluminoxane, and combinations thereof.

5. The method of claim 1 , wherein the spray-dried activator comprises an aluminoxane, the aluminoxane being present in the catalyst system in an amount of about 10 mmol or less per gram of the catalyst system.

6. The method of claim 1 , wherein the spray-dried activator has an average particle size ranging from about 1 micron to about 500 microns.

7. The method of claim 1 , wherein the catalyst system further comprises a filler material and the filler material comprises fumed silica having an average particle size of less than about 150 microns.

8. The method of claim 1 , wherein the catalyst system comprises at least one catalyst selected from the group consisting of a metallocene catalyst, a transition metal-containing catalyst, a Group 15-containing catalyst, a catalyst comprising an oxadiazole compound, a biphenyl phenol catalyst, a mixed catalyst, and any combination thereof.

9. The method of claim 1 , wherein the catalyst system comprises a metallocene catalyst represented by the following structure:

Cp A Cp B MX n

wherein

M is selected from a Group 3 atom, a Group 4 atom, a Group 5 atom, a Group 6 atom, a Group 7 atom, a Group 8 atom, a Group 9 atom, a Group 10 atom, a Group 11 atom, a Group 12 atom, and a lanthanide Group atom;

Cp A and Cp B are each individually selected from cycloalkadienyl ligand, a substituted cyclopentadienyl ligand, a ligand isolobal to cyclopentadienyl, and a substituted isolobal to cyclopentadienyl, wherein Cp A and Cp B are each chemically bonded to M;

X is a leaving group, wherein X is chemically bonded to M; and

n is 0 or an integer from 1 to 4.

10. The method of claim 1 , wherein the catalyst system comprises a metallocene catalyst represented by the following structure:

Cp A (A)Cp B MX n

wherein

M is selected from a Group 3 atom, a Group 4 atom, a Group 5 atom, a Group 6 atom, a Group 7 atom, a Group 8 atom, a Group 9 atom, a Group 10 atom, a Group 11 atom, a Group 12 atom, and a lanthanide Group atom;

Cp A and Cp B are each individually selected from a cycloalkadienyl, ligand, a substituted cyclopentadienyl ligand, a ligand isolobal to cyclopentadienyl, and a substituted isolobal to cyclopentadienyl;

A is a divalent bridging group bound to both Cp A and Cp B ;

X is a leaving group; and

n is 0 or an integer from 1 to 4.

11. The method of claim 1 , wherein the catalyst system comprises an oxadiazole compound represented by the following structure (I):

wherein:

M is selected from the group consisting of Ti, Zr, and Hf;

at least one group selected from R 1 through R 9 is substituted with a moiety having the following structure (II):

where the structure is attached at any one of R 1 through R 9 at the R 10 or R 11 position;

at least one nitrogen selected from N 1 and N 2 of the structure (II) forms a dative bond with M;

each of R 1 through R 11 are independently selected from hydride, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkyl thio, aiylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino, phosphine, amino, and amine; and

X is a leaving group.

12. The method of claim 1 , wherein the catalyst system comprises a Group-15 containing catalyst, wherein the Group-15 containing catalyst comprises a metal complex comprising a Group 3 to Group 12 metal that is 2 to 6 coordinate with a coordinating moiety comprising at least two Group 15 atoms.

13. The method of claim 1 , wherein the catalyst system comprises a biphenyl phenol catalyst represented by the following structure:

wherein:

M is selected from the group consisting of Ti, Zr, and Hf;

R 1 is selected from the group consisting of hydride, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkyl thio, arylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino, phosphine, amino, and amine;

each of R 2 through R 9 are independently selected from hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkyl thio, arylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino, phosphine, amino, and amine; and

X is a leaving group.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 23, 2015
From: KAO, SUN-CHUEH; CAO, PHUONG A.; HARLAN, C. JEFF; KHOKHANI, PARUL A.; RODRIGUEZ, GEORGE; RIX, FRANCIS C.; GIESBRECHT, GARTH R.
To: UNIVATION TECHNOLOGIES, LLC
Reel/Frame 037116/0276 →
Continuity (2)
Provisional Application 61556925 · Nov 8, 2011
Related Publication 20150166699A1 · Jun 18, 2015