# US 7,410,926 B2 · Polymerization process using a supported, treated catalyst system

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- Number: US 7,410,926 B2
- Document ID: US7410926B2
- Status: Granted
- Kind: B2
- Application number: 10/748,014
- Filed: 2003-12-30
- Published: 2005-07-07
- Granted: 2008-08-12
- Earliest claimed: 2003-12-30
- Assignees: Univation Technologies, LLC
- Inventors: Sun-Chueh Kao
- Web page: https://patentgrep.com/patent/US7410926B2

## CPC

- B01J 31/1805: {the ligands containing nitrogen}
- B01J 31/128: {Mixtures of organometallic compounds}
- B01J 31/143: {of aluminium}
- B01J 31/1616: {Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts (catalysts comprising molecular sieves B01J29/00)}
- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- B01J 31/38: of titanium, zirconium or hafnium
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- B01J 31/0214: {Aryloxylates, e.g. phenolates}
- B01J 2531/0238: Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J 2531/46: Titanium
- B01J 2531/48: Zirconium
- B01J 2531/49: Hafnium
- C08F 4/659: Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged}
- C08F 110/02: Ethene
- Y02P 20/50: Improvements relating to the production of bulk chemicals
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention relates to a supported, treated catalyst system and its use in a process for polymerizing olefin(s). More particularly, it provides a supported, treated catalyst system produced by a process comprising the steps of: (a) forming a supported bimetallic catalyst system comprising a first catalyst component and a metallocene catalyst compound; and (b) contacting the supported bimetallic catalyst system of (a) with at least one methylalumoxane-activatable compound.

## Claims

### Claim 1

A supported, treated catalyst system produced by a process comprising the steps of:
(a) forming a supported bimetallic catalyst system comprising a first catalyst compound and a second catalyst compound, wherein the first and second catalyst compounds are supported on a common support and comprise Group 4 or 5 metals; wherein the common support is an inorganic oxide; and
(b) contacting the supported bimetallic catalyst system of (a) with at least one compound that can be activated by methylalumoxane, wherein said compound is different from the first catalyst compound and the second catalyst compound.

### Claim 2 (depends on 1)

The supported, treated catalyst system of claim 1 wherein the supported bimetallic catalyst system further comprises an activator.

### Claim 3 (depends on 2)

The supported, treated catalyst system of claim 2 wherein the support is selected from the group consisting of silica, alumina, silica-alumina, and mixtures thereof.

### Claim 4 (depends on 2)

The supported, treated catalyst system of claim 2 wherein the activator is selected from the group consisting of: a Lewis acid, an alkylaluminum compound, and an ionic activator.

### Claim 5 (depends on 4)

The supported, treated catalyst system of claim 4 wherein the Lewis acid is methylalumoxane.

### Claim 6 (depends on 4)

The supported, treated catalyst system of claim 4 wherein the alkylaluminum compound is trimethylaluminum.

### Claim 7 (depends on 1)

The supported, treated catalyst system of claim 1 wherein the supported bimetallic catalyst system comprises a first and a second transition metal.

### Claim 8 (depends on 7)

The supported, treated catalyst system of claim 7 wherein the at least one compound that can be activated by methylalumoxane comprises a transition metal that is the same as the first transition metal.

### Claim 9 (depends on 7)

The supported, treated catalyst system of claim 7 wherein the at least one compound that can be activated by methylalumoxane comprises a transition metal that is the same as the second transition metal.

### Claim 10 (depends on 7)

The supported, treated catalyst system of claim 7 wherein the at least one compound that can be activated by methylalumoxane comprises a transition metal that is different from both the first and second transition metals.

### Claim 11 (depends on 1)

The supported, treated catalyst system of claim 1 wherein the second catalyst compound comprises a metallocene catalyst compound.

### Claim 12 (depends on 11)

The supported, treated catalyst system of claim 11 wherein the metallocene catalyst compound is represented by a formula selected from the group consisting of:
CpACpBMXn;
CpA(A)CpBMXn;
CpA(A)QMXr;
CpAMQqXw;
CpAM(W2GZ)Xy; and
T(CpAM(W2GZ)Xy)m
wherein M is a metal atom selected from the group consisting of: Group 4 or 5 metal atoms;
Cp is a ligand selected from the group consisting of: substituted or unsubstituted cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl;
X is selected from the group consisting of: halogen ions, hydrides, C1 to C12 alkyls, C2 to C12 alkenyls, C6 to C12 aryls, C7 to C20 alkylaryls, C1 to C12 alkoxys, C6 to C16 aryloxys, C7 to C18 alkylaryloxys, C1 to C12 fluoroalkyls, C6 to C12 fluoroaryls, C1 to C12 heteroatom-containing hydrocarbons and substituted derivatives thereof; amines, phosphines, ethers, carboxylates, dienes, and hydrocarbon radicals having from 1 to 20 carbon atoms;
(A) is a bridging group;
Q is a heteroatom-containing ligand;
T is a bridging group selected from the group consisting of C1 to C10 alkylenes, C6 to C12 arylenes and C1 to C10 heteroatom containing groups, and C6 to C12 heterocyclic groups;
G is selected from the group consisting of carbon and silicon;
W is selected from the group consisting of —O—; —NR—; —CR2— and —S—;
R is selected from the group consisting of C1 to C10 heteroatom containing groups, C1 to C10 alkyls, C6 to C12 aryls, C6 to C12 alkylaryls, C1 to C10 alkoxys, and C6 to C12 aryloxys;
Z is selected from the group consisting of R, —OR, —NR2, —CR3, —SR, —SiR3, —PR2, and hydride;
each X is chemically bonded to M;
each Cp group is chemically bonded to M;
m is an integer in the range of from 1 to 7;
n is 0 or an integer from 1 to 4;
q is in the range of from 0 to 3;
r is 0, 1 or 2;
w is in the range of from 0 to 3; and
y is 1 or 2.

### Claim 13 (depends on 11)

The supported, treated catalyst system of claim 11 wherein the metallocene catalyst compound is represented by a formula selected from the group consisting of:
wherein M is a metal atom selected from the group consisting of: Group 4 or 5 metal atoms;
Q is selected from the group consisting of halogen ions, alkyls, alkylenes, aryls, arylenes, alkoxys, aryloxys, amines, alkylamines, phosphines, alkylphosphines, substituted alkyls, substituted aryls, substituted alkoxys, substituted aryloxys, substituted amines, substituted alkylamines, substituted phosphines, substituted alkylphosphines, carbamates, heteroallyls, carboxylates, fluorinated alkyls, fluorinated aryls, and fluorinated alkylcarboxylates;
q is an integer ranging from 1 to 3; each R* is independently selected from the group consisting of hydrocarbyls and heteroatom-containing hydrocarbyls;
A is a bridging group;
X is selected from the group consisting of: halogen ions, hydrides, C1 to C12 alkyls, C2 to C12 alkenyls, C6 to C12 aryls, C7 to C20 alkylaryls, C1 to C12 alkoxys, C6 to C16 aryloxys, C7 to C18 alkylaryloxys, C1 to C12 fluoroalkyls, C6 to C12 fluoroaryls, C1 to C12 heteroatom-containing hydrocarbons and substituted derivatives thereof; amines, phosphines, ethers, carboxylates, dienes, and hydrocarbon radicals having from 1 to 20 carbon atoms;
n is 0 or an integer from 1 to 4; and
R1 through R12 are independently: selected from the group consisting of hydrogen radical, halogen radicals, C1 to C12 alkyls, C2 to C12 alkenyls, C6 to C12 aryls, C7 to C20 alkylaryls, C1 to C12 alkoxys, C1 to C12 fluoroalkyls, C6 to C12 fluoroaryls, and C1 to C12 heteroatom-containing hydrocarbons and substituted derivatives thereof.

### Claim 14

A supported, treated catalyst system produced by a process comprising the steps of:
(a) forming a supported bimetallic catalyst system comprising a first catalyst compound and a second catalyst compound, wherein the second catalyst compound comprises a metallocene catalyst compound, and wherein the first and second catalyst compounds are supported on a common support; wherein the common support is an inorganic oxide; and
(b) contacting the supported bimetallic catalyst system of (a) with at least one compound that can be activated by methylalumoxane, wherein said compound is different from the first catalyst compound and the second catalyst compound;
wherein the metallocene catalyst compound is selected from the group consisting of:
bis(n-butylcyclopentadienyl)zirconium dichloride; bis(n-butylcyclopentadienyl)zirconium difluoride; (tetramethylcyclopentadienyl) (n-propylcyclopentadienyl)zirconium dichloride; (pentamethylcyclopentadienyl) (n-propylcyclopentadienyl)zirconium dichloride; bis(1,3-methylbutylcyclopentadienyl)zirconium dichloride; and bis(n-propylcyclopentadienyl)hafnium difluoride.

### Claim 15 (depends on 1)

The supported, treated catalyst system of claim 1 wherein the supported, treated catalyst system and the supported bimetallic catalyst system each have a transition metal concentration, and wherein the supported, treated catalyst system has a higher transition metal concentration than does the supported bimetallic catalyst system.

### Claim 16 (depends on 1)

The supported, treated catalyst system of claim 1 wherein the first catalyst compound is a Ziegler-Natta catalyst.

### Claim 17 (depends on 16)

The supported, treated catalyst system of claim 16 wherein the Ziegler-Natta catalyst comprises a compound selected from the group consisting of Group 4 and Group 5 halides, oxides, oxyhalides, alkoxides, and mixtures thereof.

### Claim 18 (depends on 17)

The supported, treated catalyst system of claim 17 wherein the Ziegler-Natta catalyst is titanium tetrachloride.

### Claim 19 (depends on 1)

The supported, treated catalyst system of claim 1 wherein the at least one compound that can be activated by methylalumoxane is selected from the group consisting of: a metallocene catalyst compound; a Group-15-component-containing compound; a phenoxide catalyst compound; or a conventional transition metal catalyst compound.

### Claim 20 (depends on 19)

The supported, treated catalyst system of claim 19 wherein the Group-15-component-containing compound is represented by a formula selected from the group consisting of:
wherein M is selected from the group consisting of: Group 3 to 12 transition metals and Group 13 to 14 main group metals;
each X is a leaving group;
y is 0 or 1;
n is the oxidation state of M and is selected from the group consisting of: +3, +4, and +5;
m is the formal charge of the YZL or the YZL′ ligand and is selected from the group consisting of 0, −1, −2 and −3;
L is a Group 15 or 16 element;
L′ is selected from the group consisting of: a Group 15 element, a Group 16 element, and a Group 14-containing group;
Y is a Group 15 element;
Z is a Group 15 element;
R1 and R2 are each selected from the group consisting of: a C1 to C20 hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, halogen and phosphorus;
R3 is absent or is selected from the group consisting of: a hydrocarbon group, hydrogen, a halogen, and a heteroatom containing group;
R4 and R5 are each selected from the group consisting of: an alkyl 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 multiple ring system having up to 20 carbon atoms, a C1 to C20 hydrocarbon group, a C1 to C20 aryl group, a C1 to C20 aralkyl group, and a heteroatom containing group;
R6 and R7 are each absent, or are selected from the group consisting of: hydrogen, an alkyl group, a halogen, a heteroatom or a hydrocarbyl group; and
R* is absent or is selected from the group consisting of: hydrogen, a Group 14 atom containing group, a halogen, and a heteroatom containing group.

### Claim 21 (depends on 20)

The supported, treated catalyst system of claim 20 wherein the Group-15-component-containing compound is
wherein Ph represents a phenyl group.

### Claim 22 (depends on 19)

The supported, treated catalyst system of claim 19 wherein the phenoxide catalyst compound is represented by a formula selected from the group consisting of:
wherein R1 is selected from the group consisting of: hydrogen and a C4 to C100 group;
at least one of R2 to R5 is a heteroatom-containing group;
each of R2 to R5 that is not a heteroatom-containing group is selected from the group consisting of: hydrogen and a C1 to C100 group;
O is oxygen;
M is selected from the group consisting of: Group 3 to Group 10 transition metals and lanthanide metals;
n is the valence state of the metal M and is selected from the group consisting of 2, 3, 4, and 5; and
Q is an alkyl, halogen, benzyl, amide, carboxylate, carbamate, thiolate, hydride or alkoxide group.

### Claim 23 (depends on 1)

The supported, treated catalyst system of claim 1 wherein the at least one compound that can be activated by methylalumoxane is selected from the group consisting of: complexes of nickel; complexes of nickel and palladium; Group 8 to 10 metal catalyst compounds containing diimine-based ligands; Group 5 and 6 metal imido complexes; bridged bi-aromatic ligand compounds; and compounds represented by the formula
((Z)XAt(YJ))qMQn
where M is a metal selected from Group 3 to 13 or lanthanide and actinide series of the Periodic Table of Elements;
Q is bonded to M and each Q is a monovalent, bivalent, or trivalent anion;
X and Y are bonded to M;
X and Y are heteroatoms;
Y is contained in a heterocyclic ring J, where J comprises from 2 to 50 non-hydrogen atoms,
Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms;
t is 0 or 1;
A is a bridging group joined to at least one of X, Y or J;
q is 1 or 2;
n is an integer from 1 to 4.

### Claim 24 (depends on 19)

The supported, treated catalyst system of claim 19 wherein the conventional transition metal catalyst is selected from the group consisting of: a Ziegler-Natta catalyst; a vanadium catalyst; and a Phillips catalyst.

### Claim 25 (depends on 1)

The supported, treated catalyst system of claim 1 wherein an antistatic agent is present in an amount less than 2% by weight of the supported, treated catalyst system.

### Claim 26 (depends on 1)

The supported, treated catalyst system of claim 1 wherein an antistatic agent is present in an amount in the range of from 0% to 1% by weight of the supported, treated catalyst system.

### Claim 27 (depends on 1)

The supported, treated catalyst system of claim 1 wherein each different catalyst compound that comprises the bimetallic catalyst is supported on a single type of support such that, on average, each particle of support material includes both the first and second catalyst component.