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US 9,040,643 B2Granted
Bridged metallocene catalyst systems with switchable hydrogen and comonomer effects
AssigneeChevron Phillips Chemical Company LP
InventorsRichard M. Buck, Qing Yang, Albert P. Masino, Christopher E. Wittner
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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.
Claims24
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.
23 more elements
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.
22 more elements
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.
19 more elements
Dependencies are inferred from the claim text.