# US 9,040,643 B2 · Bridged metallocene catalyst systems with switchable hydrogen and comonomer effects

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- Number: US 9,040,643 B2
- Document ID: US9040643B2
- Status: Granted
- Kind: B2
- Application number: 14/109,997
- Filed: 2013-12-18
- Published: 2014-04-17
- 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/US9040643B2

## CPC

- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- 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 2420/12: Long bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is composed of at least two atoms which are not part of a cycle and which are not an ethylene bridge
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

The present invention provides polymerization processes utilizing an ansa-metallocene catalyst system for the production of olefin polymers. Polymers produced from the polymerization processes have properties that vary based upon the presence or the absence of hydrogen and/or comonomer in the polymerization process.

## Claims

### Claim 1

An olefin polymerization process, the process comprising:
contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer having less than about 0.002 long chain branches per 1000 total carbon atoms, wherein the catalyst composition comprises:
(i) an activator; and
(ii) 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.

### Claim 2 (depends on 1)

The process of claim 1, wherein the process is conducted in the presence of added hydrogen in a range from about 50 ppm to about 1000 ppm; and wherein:
a Mw/Mn ratio of an olefin polymer produced by the process in the presence of an olefin comonomer is at least 25% greater than a Mw/Mn ratio of an olefin polymer produced by the process under the same polymerization conditions without an olefin comonomer; or
a Mw of an olefin polymer produced by the process in the presence of an olefin comonomer is at least 50% greater than a Mw of an olefin polymer produced by the process under the same polymerization conditions without an olefin comonomer; or
both.

### Claim 3 (depends on 1)

The process of claim 1, wherein the process is conducted in the presence of added hydrogen and the olefin comonomer; and wherein:
a Mw of the olefin polymer is substantially constant over a range of from about 50 ppm to about 1000 ppm added hydrogen; or
an activity of the catalyst composition is substantially constant over a range of from about 50 ppm to about 1000 ppm added hydrogen; or
both.

### Claim 4 (depends on 1)

The process of claim 1, wherein a molar ratio of olefin comonomer to olefin monomer is in a range from about 0.001:1 to about 0.2:1.

### Claim 5 (depends on 4)

The process of claim 4, wherein:
the process is conducted in the absence of added hydrogen; and
a Mw/Mn ratio of the olefin polymer increases as the molar ratio of olefin comonomer to olefin monomer increases from about 0.001:1 to about 0.06:1.

### Claim 6 (depends on 4)

The process of claim 4, wherein an activity of the catalyst composition decreases as the molar ratio of olefin comonomer to olefin monomer increases from about 0.001:1 to about 0.06:1.

### Claim 7 (depends on 1)

The process of claim 1, wherein the olefin polymer has:
an average of from 0 to about 5 short chain branches per 1000 total carbon atoms and a density of greater than about 0.92 g/cm3.

### Claim 8 (depends on 1)

The process of claim 1, wherein the process is conducted in a batch reactor, slurry reactor, gas-phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, or a combination thereof.

### Claim 9 (depends on 1)

The process of claim 1, wherein the olefin monomer is ethylene, and the olefin comonomer comprises propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

### Claim 10 (depends on 1)

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

### Claim 11 (depends on 1)

The process of claim 1, wherein the activator comprises an activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein:
the solid oxide comprises silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; and
the electron-withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, or any combination thereof.

### Claim 12 (depends on 1)

The process of claim 1, wherein the catalyst composition further comprises an organoaluminum compound having the formula:
Al(XA)p(XB)3-p,
wherein:
XA is a hydrocarbyl;
XB is an alkoxide or an aryloxide, a halide, or a hydride; and
p is from 1 to 3, inclusive.

### Claim 13 (depends on 1)

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

### Claim 14

A polymerization process, the process comprising:
contacting a catalyst composition with ethylene and optionally an α-olefin comonomer under polymerization conditions to produce an ethylene polymer, wherein the catalyst composition comprises:
(i) an activator; and
(ii) 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, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxide group having up to 18 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.

### Claim 15 (depends on 14)

The process of claim 14, wherein:
the catalyst composition further comprises an organoaluminum compound;
the activator comprises an activator-support comprising a solid oxide treated with an electron-withdrawing anion; and
the α-olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a combination thereof.

### Claim 16 (depends on 14)

The process of claim 14, wherein the process is conducted in the presence of added hydrogen in a range from about 50 ppm to about 1000 ppm; and wherein:
a Mw/Mn ratio of an ethylene polymer produced by the process in the presence of an α-olefin comonomer is at least 25% greater than a Mw/Mn ratio of an ethylene polymer produced by the process under the same polymerization conditions without an α-olefin comonomer; or
a Mw of an ethylene polymer produced by the process in the presence of an α-olefin comonomer is at least 50% greater than a Mw of an ethylene polymer produced by the process under the same polymerization conditions without an α-olefin comonomer; or
both.

### Claim 17 (depends on 14)

The process of claim 14, wherein the process is conducted in the presence of added hydrogen and the α-olefin comonomer, and wherein:
a Mw of the ethylene polymer is substantially constant over a range of from about 50 ppm to about 1000 ppm added hydrogen; or
an activity of the catalyst composition is substantially constant over a range of from about 100 ppm to about 500 ppm added hydrogen; or
both.

### Claim 18 (depends on 14)

The process of claim 14, wherein a molar ratio of α-olefin comonomer to ethylene is in a range from about 0.001:1 to about 0.2:1.

### Claim 19 (depends on 18)

The process of claim 18, wherein:
the process is conducted in the absence of added hydrogen; and
a Mw/Mn ratio of the ethylene polymer increases as the molar ratio of α-olefin comonomer to ethylene increases from about 0.001:1 to about 0.06:1.

### Claim 20 (depends on 18)

The process of claim 18, wherein an activity of the catalyst composition decreases as the molar ratio of α-olefin comonomer to ethylene increases from about 0.001:1 to about 0.06:1.

### Claim 21 (depends on 14)

The process of claim 14, wherein:
M is Zr or Hf;
CpA is a cyclopentadienyl or indenyl group;
CpB is an indenyl or fluorenyl group;
each RA and RB independently is H or a hydrocarbyl group having up to 12 carbon atoms;
m is 0, 1, or 2; and
n is 0, 1, or 2.

### Claim 22 (depends on 21)

The process of claim 21, wherein:
M is Zr;
CpA is a cyclopentadienyl or indenyl group;
CpB is an 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
each X independently is F, Cl, Br, I, methyl, benzyl, or phenyl.

### Claim 23

A polymerization process, the process comprising:
contacting a catalyst composition with ethylene and an α-olefin comonomer under polymerization conditions to produce an ethylene polymer, wherein a Mw of the ethylene polymer 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 is substantially constant over a range of from about 100 ppm to about 500 ppm added hydrogen, wherein the catalyst composition comprises:
(i) an activator-support comprising a solid oxide treated with an electron-withdrawing anion; and
(ii) an ansa-metallocene compound having formula (II), (III), (IV), (V), (VI), or (VII):
wherein:
M is Ti, Zr, or Hf;
each RA and RB independently is a H or a hydrocarbyl, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxide 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;
each m is 0, 1, 2, 3, or 4, m′ is 0, 1 or 2, and m″ is 0, 1, or 2;
each n is 0, 1, 2, 3, or 4, each n′ is 0, 1, or 2, and each n″ is 0, 1, or 2; and
each RE, RF, RG, and RH independently is H or a hydrocarbyl group having up to 18 carbon atoms.

### Claim 24 (depends on 23)

The process of claim 23, wherein the process is conducted in the presence of added hydrogen, and wherein:
the catalyst composition further comprises an organoaluminum compound;
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;
the α-olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a combination thereof;
M is Zr or Hf;
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;
each X independently is F, Cl, Br, I, methyl, benzyl, or phenyl;
each m is 0, 1, or 2, m′ is 0 or 1, and m″ is 0 or 1;
each n is 0, 1, or 2, each n′ is 0 or 1, and each n″ is 0 or 1; and
each RE, RF, RG, and RH 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.