# US 9,040,642 B2 · Catalyst systems containing a bridged metallocene

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- Number: US 9,040,642 B2
- Document ID: US9040642B2
- Status: Granted
- Kind: B2
- Application number: 14/070,650
- Filed: 2013-11-04
- Published: 2014-02-27
- Granted: 2015-05-26
- Earliest claimed: 2010-10-07
- Assignees: Chevron Phillips Chemical Company LP
- Applicants: Chevron Phillips Chemical Company LP
- Inventors: Richard M. Buck; Qing Yang; Albert P. Masino; Christopher E. Wittner
- Web page: https://patentgrep.com/patent/US9040642B2

## CPC

- C08F 4/76: selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
- C08F 4/642: Component covered by group C08F4/64 with an organo-aluminium compound {(C08F4/64003 - C08F4/64196 take precedence)}
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 4/63912: {in combination with an organoaluminium compound}
- C08F 4/63916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 110/02: Ethene
- C08F 2410/07: Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

The present invention provides polymerization processes utilizing a catalyst system containing an ansa-metallocene and a second metallocene compound for the production of olefin polymers.

## Claims

### Claim 1

A catalyst composition capable of producing an ethylene polymer having a narrower molecular weight distribution as hydrogen addition during polymerization is increased, the catalyst composition comprising:
(i) an ansa-metallocene compound having formula (I):
E(CpARAm)(CpBRBn)MXq (I),
wherein:
M is Ti, Zr, Hf, Cr, Sc, Y, La, or a lanthanide;
CpA and CpB independently are a cyclopentadienyl, indenyl, or fluorenyl group;
each RA and RB independently is H or a hydrocarbyl, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxide group having up to 18 carbon atoms;
E is a bridging chain of 3 to 8 carbon atoms or 2 to 8 silicon, germanium, or tin atoms, wherein any substituents on atoms of the bridging chain independently are H or a hydrocarbyl group having up to 18 carbon atoms;
each X independently is F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;
m is 0, 1, 2, 3, or 4;
n is 0, 1, 2, 3, or 4;
q is 2 when M is Ti, Zr, or Hf; and
q is 1 when M is Cr, Sc, Y, La, or a lanthanide;
(ii) a second metallocene compound; and
(iii) an activator.

### Claim 2 (depends on 1)

The composition of claim 1, wherein E is a bridging chain of 2 to 8 silicon, germanium, or tin atoms, wherein any substituents on atoms of the bridging chain independently are H or a hydrocarbyl group having up to 12 carbon atoms.

### Claim 3 (depends on 1)

The composition of claim 1, wherein:
M is Ti, Zr, or Hf;
each RA and RB independently is H or a hydrocarbyl group having up to 12 carbon atoms;
E is a bridging chain of 3 to 6 carbon atoms or 2 to 4 silicon atoms, wherein any substituents on atoms of the bridging chain independently are H or a hydrocarbyl group having up to 12 carbon atoms;
each X independently is F, Cl, Br, I, methyl, benzyl, or phenyl;
m is 0, 1, or 2;
n is 0, 1, or 2; and
q is 2.

### Claim 4 (depends on 3)

The composition of claim 3, wherein:
M is Zr or Hf;
CpA and CpB independently are a cyclopentadienyl or indenyl group;
each RA and RB independently is H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl; and
E is —SiMe2-SiMe2-.

### Claim 5 (depends on 1)

The composition of claim 1, wherein the ansa-metallocene compound having formula (I) comprises:
or a combination thereof.

### Claim 6 (depends on 1)

The composition of claim 1, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

### Claim 7 (depends on 1)

The composition of claim 1, wherein the activator comprises an activator-support comprising a solid oxide treated with an electron-withdrawing anion.

### Claim 8 (depends on 7)

The composition of claim 7, wherein the activator-support comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.

### Claim 9 (depends on 8)

The composition of claim 8, wherein the catalyst composition further comprises an organoaluminum compound, and wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof.

### Claim 10 (depends on 1)

The composition of claim 1, wherein the second metallocene compound comprises an unbridged metallocene compound.

### Claim 11 (depends on 1)

The composition of claim 1, wherein the second metallocene compound comprises a bridged metallocene compound.

### Claim 12

A catalyst composition comprising:
(i) an ansa-metallocene compound having formula (I):
E(CpARAm)(CpBRBn)MXq (I),
wherein:
M is Ti, Zr, or Hf;
CpA and CpB independently are a cyclopentadienyl, indenyl, or fluorenyl group;
each RA and RB independently is a hydrocarbyl group having up to 12 carbon atoms;
E is —SiMe2-SiMe2-;
each X independently is F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;
m is 0, 1, 2, 3, or 4;
n is 0, 1, 2, 3, or 4; and
q is 2;
(ii) a second metallocene compound; and
(iii) an activator.

### Claim 13 (depends on 12)

The composition of claim 12, wherein:
M is Zr or Hf;
CpA and CpB independently are a cyclopentadienyl or indenyl group;
each X independently is F, Cl, Br, I, methyl, benzyl, or phenyl;
m is 0, 1, or 2; and
n is 0, 1, or 2.

### Claim 14 (depends on 12)

The composition of claim 12, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

### Claim 15 (depends on 12)

The composition of claim 12, wherein the activator comprises an activator-support comprising a solid oxide treated with an electron-withdrawing anion.

### Claim 16 (depends on 15)

The composition of claim 15, wherein the catalyst composition further comprises an organoaluminum compound.

### Claim 17 (depends on 12)

The composition of claim 12, wherein the second metallocene compound comprises a bridged metallocene compound having formula (C2):
wherein:
M3 is Ti, Zr, or Hf;
X4 and X5 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;
E3 is a bridging group having the formula >E3AR7AR8A, wherein E3A is C or Si, and R7A and R8A are independently H or a hydrocarbyl group having up to 18 carbon atoms;
R9 and R10 are independently H or a hydrocarbyl group having up to 18 carbon atoms; and
Cp1 is a cyclopentadienyl or indenyl group, any substituent on Cp1 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms.

### Claim 18 (depends on 17)

The composition of claim 17, wherein:
M3 is Zr or Hf;
X4 and X5 are independently F, Cl, Br, I, methyl, benzyl, or phenyl;
E3A is C, and at least one of R7A and R8A is phenyl or a terminal alkenyl group having up to 6 carbon atoms;
R9 and R10 are independently H or an alkyl group having up to 8 carbon atoms; and
Cp1 is a cyclopentadienyl group.

### Claim 19 (depends on 18)

The composition of claim 18, wherein:
the catalyst composition further comprises an organoaluminum compound; and
the activator comprises an activator-support comprising a solid oxide treated with an electron-withdrawing anion.

### Claim 20

A catalyst composition capable of producing an ethylene polymer having a narrower molecular weight distribution as hydrogen addition during polymerization is increased, the catalyst composition comprising:
(i) an ansa-metallocene compound having formula (I):
E(CpARAm)(CpBRBn)MXq (I),
wherein:
M is Ti, Zr, or Hf;
CpA and CpB independently are a cyclopentadienyl, indenyl, or fluorenyl group;
each RA and RB independently is H or a hydrocarbyl group having up to 12 carbon atoms;
E is —SiMe2-SiMe2-;
each X independently is F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;
m is 0, 1, 2, 3, or 4;
n is 0, 1, 2, 3, or 4; and
q is 2;
(ii) a second metallocene compound; and
(iii) an activator.

### Claim 21 (depends on 20)

The composition of claim 20, wherein an activity of the catalyst composition in an ethylene/α-olefin polymerization is substantially constant over a range of from about 50 ppm to about 1000 ppm added hydrogen and/or an activity of the catalyst composition decreases as the molar ratio of α-olefin to ethylene increases from about 0.001:1 to about 0.06:1, under slurry polymerization conditions, using isobutane as a diluent, with a polymerization temperature of 90° C., and a reaction pressure of 390 psig.

### Claim 22 (depends on 20)

The composition of claim 20, wherein:
the catalyst composition further comprises an organoaluminum compound; and
the activator comprises an activator-support comprising a solid oxide treated with an electron-withdrawing anion.

### Claim 23 (depends on 20)

The composition of claim 20, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

### Claim 24 (depends on 20)

The composition of claim 20, wherein:
M is Zr or Hf;
CpA and CpB are indenyl groups;
each X independently is F, Cl, Br, I, methyl, benzyl, or phenyl;
m is 0, 1, or 2; and
n is 0, 1, or 2.

### Claim 25 (depends on 24)

The composition of claim 24, wherein the second metallocene compound comprises a bridged metallocene compound having formula (C2):
wherein:
M3 is Ti, Zr, or Hf;
X4 and X5 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;
E3 is a bridging group having the formula >E3AR7AR8A, wherein E3A is C or Si, and R7A and R8A are independently H or a hydrocarbyl group having up to 18 carbon atoms;
R9 and R10 are independently H or a hydrocarbyl group having up to 18 carbon atoms; and
Cp1 is a cyclopentadienyl or indenyl group, any substituent on Cp1 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms.

### Claim 26 (depends on 25)

The composition of claim 25, wherein:
M3 is Zr or Hf;
X4 and X5 are independently F, Cl, Br, I, methyl, benzyl, or phenyl;
E3A is C, and at least one of R7A and R8A is phenyl or a terminal alkenyl group having up to 6 carbon atoms;
R9 and R10 are independently H or an alkyl group having up to 8 carbon atoms; and
Cp1 is a cyclopentadienyl group.