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US 7,470,758 B2Granted
Polymerization catalysts for producing polymers with low levels of long chain branching
AssigneeChevron Phillips Chemical Company LP
InventorsMichael D. Jensen, Joel L. Martin, Max P. McDaniel, David C. Rolfing, Qing Yang, Matthew G. Thorn, Ashish M. Sukhadia, Youlu Yu, Jerry T. Lanier
Life of this patent
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Abstract
This invention relates to catalyst compositions, methods, and polymers encompassing a Group 4 metallocene with bridging η5-cyclopentadienyl-type ligands, in combination with a cocatalyst and an activator-support. The compositions and methods disclosed herein provide ethylene polymers with low levels of long chain branching.
Claims18
A catalyst composition comprising:
- (i) a precontacted mixture comprising at least one ansa-metallocene, at least one organoaluminum compound, and at least one olefin, and
- (ii) at least one activator-support, wherein:
- a) the ansa-metallocene comprises a compound having the formula:
- (X1)(X2)(X3)(X4)M1, wherein
- M1 is titanium, zirconium, or hafnium;
- (X1) and (X2) are independently selected from a cyclopentadienyl, an indenyl, a fluorenyl, or a substituted analog thereof, wherein at least one of (X1) and (X2) is substituted;
- at least one substituent of the substituted (X1) or (X2) comprises an unsaturated group having the formula
- —SiR42R5, wherein
- each R4 is independently selected from a hydrocarbyl group or a substituted hydrocarbyl group having from 1 to about 20 carbon atoms;
- R5 is selected from an alkenyl group, an alkynyl group, an alkadienyl group, or a substituted analog thereof having from 1 to about 20 carbon atoms;
- (X1) and (X2) are connected by a substituted or unsubstituted bridging group comprising one atom bonded to both (X1) and (X2) selected from carbon, silicon, germanium, or tin;
- and
- any substituent on R4, any substituent on R5, any substituent on the substituted bridging group, any additional substituent on (X1) or (X2), and (X3) and (X4) are independently selected from an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, a germanium group, a tin group, a lead group, a boron group, an aluminum group, —SO2X, —OAlX2, —OSiX3, —OPX2, —SX, —OSO2X, —AsX2, —As(O)X2, —PX2, wherein X is a monoanionic group such as halide, hydride, amide, alkoxide, alkyl thiolate or a substituted derivative thereof, any of which having from 1 to about 20 carbon atoms;
- a halide;
- or hydrogen;
- b) the organoaluminum compound comprises a compound with the formula:
- Al(X5)n(X6)3-n,
- wherein (X5) is a hydrocarbyl having from 1 to about 20 carbon atoms;
- (X6) is an alkoxide or an aryloxide having from 1 to about 20 carbon atoms, halide, or hydride;
- and n is a number from 1 to 3, inclusive;
- c) the olefin comprises at least one carbon-carbon double bond and from 2 to about 30 carbon atoms;
- and
- d) the activator-support comprises:
- a solid oxide treated with an electron-withdrawing anion;
- a layered mineral,
- an ion-exchangeable activator-support, or
- any combination thereof.
24 more elements
A process to produce a catalyst composition, comprising:
- contacting an ansa-metallocene, an olefin, and an organoaluminum compound for a first period of time to form a precontacted mixture;
- and
- contacting the precontacted mixture with an activator-support and optionally additional organoaluminum compound for a second period of time to form a postcontacted mixture;
- wherein the ansa-metallocene comprises a compound with the formula:
- (X1)(X2)(X3)(X4)M1, wherein
- M1 is titanium, zirconium, or hafnium;
- (X1) and (X2) are independently selected from a cyclopentadienyl, an indenyl, a fluorenyl, or a substituted analog thereof, wherein at least one of (X1) and (X2) is substituted;
- at least one substituent of the substituted (X1) or (X2) comprises an unsaturated group having the formula
- —SiR42R5, wherein
- each R4 is independently selected from a hydrocarbyl group or a substituted hydrocarbyl group having from 1 to about 20 carbon atoms;
- R5 is an alkenyl group, an alkynyl group, an alkadienyl group, or a substituted analog thereof having from 1 to about 20 carbon atoms;
- (X1) and (X2) are connected by a substituted or unsubstituted bridging group comprising one atom bonded to both (X1) and (X2), wherein the atom is carbon, silicon, germanium, or tin;
- and
- any substituent on R4, any substituent on R5, any substituent on the substituted bridging group, any additional substituent on (X1) or (X2), and (X3) and (X4) are independently selected from an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, a germanium group, a tin group, a lead group, a boron group, an aluminum group, —SO2X, —OAlX2, —OSiX3, —OPX2, —SX, —OSO2X, —AsX2, —As(O)X2, —PX2, wherein X is a monoanionic group such as halide, hydride, amide, alkoxide, alkyl thiolate, or a substituted derivative thereof, any of which having from 1 to about 20 carbon atoms;
- a halide;
- or hydrogen.
13 more elements
A method of polymerizing olefins, comprising:
- (i) contacting an ansa-metallocene, an olefin, and an organoaluminum compound in any order for a first period of time to form a precontacted mixture comprising a precontacted ansa-metallocene, a precontacted organoaluminum compound, and a precontacted olefin;
- (ii) contacting the precontacted mixture with an activator-support and optionally additional organoaluminum compound for a second period of time to form a postcontacted mixture comprising a postcontacted ansa-metallocene, a postcontacted organoaluminum compound, a postcontacted olefin, and a postcontacted activator-support;
- and
- (iii) contacting ethylene and an optional α-olefin comonomer with the postcontacted mixture of step (ii) under polymerization conditions to form a polymer or copolymer;
- wherein the ansa-metallocene, prior to contacting, comprises a compound having the formula:
- (X1)(X2)(X3)(X4)M1, wherein
- M1 is titanium, zirconium, or hafnium;
- (X1) and (X2) are independently selected from a cyclopentadienyl, an indenyl, a fluorenyl, or a substituted analog thereof, wherein at least one of (X1) and (X2) is substituted;
- at least one substituent of the substituted (X1) or (X2) comprises an unsaturated group having the formula
- —SiR42R5, wherein
- each R4 is independently selected from a hydrocarbyl group or a substituted hydrocarbyl group having from 1 to about 20 carbon atoms;
- R5 is an alkenyl group, an alkynyl group, an alkadienyl group, or a substituted analog thereof having from 1 to about 20 carbon atoms;
- (X1) and (X2) are connected by a substituted or unsubstituted bridging group comprising one atom bonded to both (X1) and (X2), wherein the atom is carbon, silicon, germanium, or tin;
- and
- any substituent on R4, any substituent on R5, any substituent on the substituted bridging group, any additional substituent on (X1) or (X2), and (X3) and (X4) are independently selected from an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, a germanium group, a tin group, a lead group, a boron group, an aluminum group, —SO2X, —OAlX2, —OSiX3, —OPX2, —SX, —OSO2X, —AsX2, —As(O)X2, —PX2, wherein X is a monoanionic group such as halide, hydride, amide, alkoxide, alkyl thiolate, or a substituted derivative thereof, any of which having from 1 to about 20 carbon atoms;
- a halide;
- or hydrogen.
14 more elements
Dependencies are inferred from the claim text.