Polymerization catalysts for producing polymers with low levels of long chain branching

• US 20050288461A1
• Filed: 06/25/2004
• Published: 12/29/2005
• Est. Priority Date: 06/25/2004
• Status: Abandoned Application

• Current Assignee: Chevron Phillips Chemical Company LP (Chevron Corp.)
• Original Assignee: Chevron Phillips Chemical Company LP (Chevron Corp.)
• Inventors: Jensen, Michael D., McDaniel, Max P., Martin, Joel L., Thorn, Matthew G., Yang, Qing, Lanier, Jerry T., Sukhadia, Ashish M., Yu, Youlu, Rolfing, David C.
• Application Number:
  US10/876,891
• Publication Number:
  US 20050288461A1
• Time in Patent Office: Days
• US Class Current: 526/127
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2410/07 Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged

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.

Claims

1. A catalyst composition comprising the contact product of at least one ansa-metallocene, at least one organoaluminum compound, and 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;

(X¹) and (X²) are connected by a substituted bridging group comprising one atom bonded to both (X¹) and (X²), wherein the atom is carbon, silicon, germanium, or tin;

wherein one substituent of the substituted bridging group comprises an unsaturated group, wherein the unsaturated group is an alkenyl group, an alkynyl group, an alkadienyl group, or a substituted analog thereof, any of which having from 1 to about 20 carbon atoms; and

any additional substituent on the substituted bridging group;

any substituent on the substituted alkenyl, substituted alkynyl, or substituted alkadienyl group bonded to the bridging group;

any substituent on (X¹) and (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, an inorganic group, an organometallic group, 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 alkoxide or aryloxide, any of which having from 1 to about 20 carbon atoms, halide, or hydride; and

n is a number from 1 to 3, inclusive; and

c) 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.

2. The catalyst composition of claim 1, wherein the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof.

3. The catalyst composition of claim 1, wherein the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted sulfonate, unsubstituted sulfonate, or any combination thereof.

4. The catalyst composition of claim 1, wherein the electron-withdrawing anion is present in the activator-support, after calcining, from about 0.1% to about 50% by weight relative to the weight of the solid oxide.

5. The catalyst composition of claim 1, wherein the electron-withdrawing anion is present in the activator-support, after calcining, from about 0.5% to about 40% by weight relative to the weight of the solid oxide.

6. The catalyst composition of claim 1, wherein the activator-support further comprises a metal or metal ion such as zinc, nickel, vanadium, tungsten, molybdenum, silver, tin, or any combination thereof.

7. The catalyst composition of claim 1, wherein the activator-support is a clay mineral, a pillared clay, an exfoliated clay, an exfoliated clay gelled into another oxide matrix, a layered silicate mineral, a non-layered silicate mineral, a layered aluminosilicate mineral, a non-layered aluminosilicate mineral, or any combination thereof.

9. The catalyst composition of claim 1, wherein the unsaturated group bonded to the bridging group is 3-butenyl (CH₂CH₂CH═

CH₂), 4-pentenyl (CH₂CH₂CH₂CH═

CH₂), 5-hexenyl (CH₂CH₂CH₂CH₂CH═

CH₂), 6-heptenyl (CH₂CH₂CH₂CH₂CH₂CH═

CH₂), 7-octenyl (CH₂CH₂CH₂CH₂CH₂CH₂CH═

CH₂), 3-methyl-3-butenyl (CH₂CH₂C(CH₃)═

CH₂), 4-methyl-3-pentenyl (CH₂CH₂CH═

C(CH₃)₂), or a substituted analog thereof.

10. The catalyst composition of claim 1, wherein the ansa-metallocene is a compound with the following formula:

11. The catalyst composition of claim 1, wherein the ansa-metallocene is a compound with the following formula:

12. The catalyst composition of claim 1, wherein the ansa-metallocene is a compound with the following formula:

13. The catalyst composition of claim 1, wherein the ansa-metallocene is a compound with the following formula:

14. The catalyst composition of claim 1, wherein the ansa-metallocene is:

methyl-3-butenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-9-fluorenyl)-zirconium dichloride;

methyl-3-butenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-2,7-di-t-butyl-9-fluorenyl)zirconium dichloride;

methyl-4-pentenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-9-fluorenyl)zirconium dichloride;

methyl-4-pentenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-2,7-di-t-butyl-9-fluorenyl)zirconium dichloride;

methyl-5-hexenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-9-fluorenyl)zirconium dichloride;

methyl-5-hexenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-2,7-di-t-butyl-9-fluorenyl)zirconium dichloride;

phenyl-3-butenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-9-fluorenyl)zirconium dichloride;

phenyl-3-butenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-2,7-di-t-butyl-9-fluorenyl)zirconium dichloride;

phenyl-4-pentenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-9-fluorenyl)zirconium dichloride;

phenyl-4-pentenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-2,7-di-t-butyl-9-fluorenyl)zirconium dichloride;

phenyl-5-hexenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-9-fluorenyl)zirconium dichloride;

phenyl-5-hexenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-2,7-di-t-butyl-9-fluorenyl)zirconium dichloride;

methyl-3-butenylsilylbis(η

⁵-fluoren-9-yl)zirconium(IV) dichloride;

methyl-4-pentenylsilylbis(η

⁵-fluoren-9-yl)zirconium(IV) dichloride;

methyl-5-hexenylsilylbis(η

⁵-fluoren-9-yl)zirconium(IV) dichloride;

methyl-6-heptenylsilylbis(η

⁵-fluoren-9-yl)zirconium(IV) dichloride;

methyl-7-octenylsilylbis(η

⁵-fluoren-9-yl)zirconium(IV) dichloride;

or any combination thereof.

15. The catalyst composition of claim 1, wherein (X⁵) is methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl, 1-hexyl, 2-hexyl, 3-hexyl, isohexyl, heptyl, or octyl.

16. The catalyst composition of claim 1, wherein (X⁶) is fluoride, chloride, bromide, methoxide, ethoxide, or hydride.

17. The catalyst composition of claim 1, wherein Al(X⁵)_n(X⁶)_3-n is trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof.

18. The catalyst composition of claim 1, wherein the activator-support is chlorided alumina, fluorided alumina, fluorided aluminophosphate, sulfated alumina, fluorided silica-alumina, a pillared clay, or any combination thereof.

19. The catalyst composition of claim 1, further comprising a cocatalyst comprising at least one aluminoxane compound, wherein the aluminoxane comprises

a cyclic aluminoxane having the formula:

wherein R is a linear or branched alkyl having from 1 to 10 carbon atoms, and n is an integer from 3 to about 10;

a linear aluminoxane having the formula;

wherein R is a linear or branched alkyl having from 1 to 10 carbon atoms, and n is an integer from 1 to about 50;

a cage aluminoxane having the formula R^t_5m+α

R^b<sub>m−

α</sub>

Al_4mO_3m, wherein m is 3 or 4 and α

is=n_Al(3)−

n_O(2)+n_O(4);

wherein n_Al(3) is the number of three coordinate aluminum atoms, n_O(2) is the number of two coordinate oxygen atoms, n_O(4) is the number of 4 coordinate oxygen atoms, R^t represents a terminal alkyl group, and R^b represents a bridging alkyl group;

wherein R is a linear or branched alkyl having from 1 to 10 carbon atoms;

or

any combination thereof.

20. The catalyst composition of claim 1, further comprising a cocatalyst comprising an organoboron compound, wherein the organoboron compound is tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)-phenyl]boron, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis-(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, or any mixture thereof.

21. The catalyst composition of claim 1, further comprising a cocatalyst comprising an ionizing ionic compound, wherein the ionizing ionic compound is tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl)-ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammonium tetrakis(2,4-dimethyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl) ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate, N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylanilinium tetrakis-(pentafluorophenyl)borate, triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate, triphenylcarbenium tetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropylium tetrakis(2,4-dimethylphenyl)borate, tropylium tetrakis(3,5-dimethylphenyl)borate, tropylium tetrakis[3,5-bis(trifluoromethyl)phenyl]-borate, tropylium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetrakis(phenyl)borate, lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithium tetrakis(2,4-dimethylphenyl)borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetrakis(pentafluorophenyl)borate, sodium tetrakis(phenyl) borate, sodium tetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodium tetrakis(2,4-dimethylphenyl)borate, sodium tetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis-(pentafluorophenyl)borate, potassium tetrakis(phenyl)borate, potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate, potassium tetrakis(2,4-dimethylphenyl)borate, potassium tetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, tri(n-butyl)ammonium tetrakis(p-tolyl)aluminate, tri(n-butyl)ammonium tetrakis(m-tolyl)aluminate, tri(n-butyl)ammonium tetrakis(2,4-dimethyl)aluminate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)aluminate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)aluminate, N,N-dimethylanilinium tetrakis(p-tolyl)-aluminate, N,N-dimethylanilinium tetrakis(m-tolyl)aluminate, N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)aluminate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)aluminate, N,N-dimethylanilinium tetrakis (pentafluorophenyl)aluminate, triphenylcarbenium tetrakis(p-tolyl)aluminate, triphenylcarbenium tetrakis(m-tolyl)aluminate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)aluminate, triphenyl-carbenium tetrakis(3,5-dimethylphenyl)aluminate, triphenylcarbenium tetrakis(pentafluorophenyl)aluminate, tropylium tetrakis(p-tolyl)aluminate, tropylium tetrakis(m-tolyl)aluminate, tropylium tetrakis(2,4-dimethylphenyl)aluminate, tropylium tetrakis(3,5-dimethylphenyl)aluminate, tropylium tetrakis(pentafluorophenyl)aluminate, lithium tetrakis(pentafluorophenyl)aluminate, lithium tetrakis(phenyl)aluminate, lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate, lithium tetrakis(2,4-dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate, sodium tetrakis(pentafluorophenyl)aluminate, sodium tetrakis(phenyl)aluminate, sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m-tolyl)aluminate, sodium tetrakis(2,4-dimethylphenyl)aluminate, sodium tetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate, potassium tetrakis(pentafluorophenyl)aluminate, potassium tetrakis(phenyl)aluminate, potassium tetrakis(p-tolyl)aluminate, potassium tetrakis(m-tolyl)aluminate, potassium tetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis (3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, or any combination thereof.

22. The catalyst composition of claim 1, wherein:

a) the ansa-metallocene comprises;

or any combination thereof;

b) the organoaluminum compound comprises triethylaluminum, triisobutylaluninum, or a combination thereof; and

c) the activator-support comprises a sulfated solid oxide.

23. The catalyst composition of claim 1, wherein:

a) the ansa-metallocene comprises;

or any combination thereof;

b) the organoaluminum compound comprises triethylaluminum, triisobutylaluminum, or a combination thereof; and

c) the activator-support comprises sulfated alumina.

8. The catalyst composition of claim 8, wherein the clay mineral comprises an allophane;

a smectite;

a montmorillonite;

a nontronite;

a hectorite;

a laponite;

a halloysite;

a vermiculite;

a mica;

a fluoromica;

a chlorite;

a mixed-layer clay;

a fiberous clay;

a sepiolite, an attapulgite, a palygorskite;

a serpentine clay;

an illite;

a saponite;

or any combination thereof.

24. A catalyst composition comprising at least one ansa-metallocene, at least one organoaluminum compound, and 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;

(X¹) and (X²) are connected by a substituted bridging group comprising one atom bonded to both (X¹) and (X²), wherein the atom is carbon, silicon, germanium, or tin;

wherein one substituent of the substituted bridging group comprises an unsaturated group, wherein the unsaturated group is an alkenyl group, an alkynyl group, an alkadienyl group, or a substituted analog thereof, any of which having from 1 to about 20 carbon atoms; and

any additional substituent on the substituted bridging group;

any substituent on the substituted alkenyl, substituted alkynyl, or substituted alkadienyl group bonded to the bridging group;

any substituent on (X¹) and (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, an inorganic group, an organometallic group, 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 alkoxide or aryloxide, any of which having from 1 to about 20 carbon atoms, halide, or hydride; and

n is a number from 1 to 3, inclusive; and

c) 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.

25. The catalyst composition of claim 24, wherein the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof.

26. The catalyst composition of claim 24, wherein the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted sulfonate, unsubstituted sulfonate, or any combination thereof.

27. The catalyst composition of claim 24, wherein the activator-support further comprises a metal or metal ion such as zinc, nickel, vanadium, tungsten, molybdenum, silver, tin, or any combination thereof.

28. The catalyst composition of claim 24, wherein the activator-support comprises a clay mineral, a pillared clay, an exfoliated clay, an exfoliated clay gelled into another oxide matrix, a layered silicate mineral, a non-layered silicate mineral, a layered aluminosilicate mineral, a non-layered aluminosilicate mineral, or any combination thereof.

29. A catalyst composition comprising at least one precontacted ansa-metallocene, at least one precontacted organoaluminum compound, at least one precontacted olefin, and at least one postcontacted 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;

(X¹) and (X²) are connected by a substituted bridging group comprising one atom bonded to both (X¹) and (X²), wherein the atom is carbon, silicon, germanium, or tin;

wherein one substituent of the substituted bridging group comprises an unsaturated group, wherein the unsaturated group is an alkenyl group, an alkynyl group, an alkadienyl group, or a substituted analog thereof, any of which having from 1 to about 20 carbon atoms;

any additional substituent on the substituted bridging group;

any substituent on the substituted alkenyl, substituted alkynyl, or substituted alkadienyl group bonded to the bridging group;

any substituent on (X¹) and (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, an inorganic group, an organometallic group, 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)<sub>3−

n</sub>,

wherein (X⁵) is a hydrocarbyl having from 1 to about 20 carbon atoms;

(X⁶) is alkoxide or aryloxide, any of which having from 1 to about 20 carbon atoms, halide, or hydride; and

n is a number from 1 to 3, inclusive;

c) the precontacted 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.

30. The catalyst composition of claim 29, wherein the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof.

31. The catalyst composition of claim 29, wherein the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted sulfonate, unsubstituted sulfonate, or any combination thereof.

32. The catalyst composition of claim 29, wherein the activator-support further comprises a metal or metal ion such as zinc, nickel, vanadium, tungsten, molybdenum, silver, tin, or any combination thereof.

33. The catalyst composition of claim 29, wherein the activator-support comprises a clay mineral, a pillared clay, an exfoliated clay, an exfoliated clay gelled into another oxide matrix, a layered silicate mineral, a non-layered silicate mineral, a layered aluminosilicate mineral, a non-layered aluminosilicate mineral, or any combination thereof.

34. A catalyst composition comprising at least one precontacted metallocene, at least one precontacted organoaluminum compound, at least one precontacted olefin, and at least one postcontacted acidic activator-support, wherein:

the precontacted metallocene has the general formula

wherein E is carbon, silicon, germanium, or tin;

R¹ is phenyl or methyl;

R² is 3-butenyl (CH₂CH₂CH═

CH₂), 4-pentenyl (CH₂CH₂CH₂CH═

CH₂), or 5-hexenyl (CH₂CH₂CH₂CH₂CH═

CH₂); and

R³ is independently selected from H or t-butyl;

the precontacted organoaluminum compound is triisobutyl aluminum or triethyl aluminum;

the precontacted olefin is ethylene or 1-hexene; and

the postcontacted acidic activator-support comprises alumina which has been treated with sulfate ion, chloride ion, or fluoride ion;

silica-alumina which has been treated with fluoride ion, or any combination thereof.

35. 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 comprising a precontacted ansa-metallocene, a precontacted organoaluminum compound, and a precontacted olefin; 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 comprising a postcontacted ansa-metallocene, a postcontacted organoaluminum compound, a postcontacted olefin, and a postcontacted activator-support.

36. The process of claim 35, wherein the precontacted 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;

(X¹) and (X²) are connected by a substituted bridging group comprising one atom bonded to both (X¹) and (X²), wherein the atom is carbon, silicon, germanium, or tin;

wherein one substituent of the substituted bridging group comprises an unsaturated group, wherein the unsaturated group is an alkenyl group, an alkynyl group, an alkadienyl group, or a substituted analog thereof, any of which having from 1 to about 20 carbon atoms; and

any additional substituent on the substituted bridging group;

any substituent on the substituted alkenyl, substituted alkynyl, or substituted alkadienyl group bonded to the bridging group;

any substituent on (X¹) and (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, an inorganic group, an organometallic group, or a substituted derivative thereof, any of which having from 1 to about 20 carbon atoms;

a halide;

or hydrogen.

37. The process of claim 35, wherein the ansa-metallocene, the olefin, and the organoaluminum compound are contacted in the precontacted mixture for a first period of time from about 1 minute to about 24 hours.

38. The process of claim 35, wherein the precontacted mixture, the activator-support, and the optional additional organoaluminum compound are contacted in the postcontacted mixture for a second period of time from about 1 minute to about 24 hours.

39. A process for producing a polymerization catalyst composition comprising contacting at least one ansa-metallocene compound, at least one organoaluminum compound, and at least one activator-support to produce the composition, 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;

(X¹) and (X²) are connected by a substituted bridging group comprising one atom bonded to both (X¹) and (X²), wherein the atom is carbon, silicon, germanium, or tin;

wherein one substituent of the substituted bridging group comprises an unsaturated group, wherein the unsaturated group is an alkenyl group, an alkynyl group, an alkadienyl group, or a substituted analog thereof, any of which having from 1 to about 20 carbon atoms; and

any additional substituent on the substituted bridging group;

any substituent on the substituted alkenyl, substituted alkynyl, or substituted alkadienyl group bonded to the bridging group;

any substituent on (X¹) and (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, an inorganic group, an organometallic group, 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 alkoxide or aryloxide, any of which having from 1 to about 20 carbon atoms, halide, or hydride; and

n is a number from 1 to 3, inclusive; and

c) 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.

40. The process of claim 39, wherein the activator-support comprises a solid oxide treated with an electron-withdrawing anion;

wherein the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof; and

the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted sulfonate, unsubstituted sulfonate, or any combination thereof.

41. The process of claim 39, wherein the ansa-metallocene is a compound with the following formula:

42. The process of claim 39, wherein the ansa-metallocene is a compound with the following formula:

43. The process of claim 39, wherein the ansa-metallocene is a compound with the following formula:

44. The process of claim 39, wherein the ansa-metallocene is a compound with the following formula:

45. The process of claim 39, wherein the ansa-metallocene is:

methyl-3-butenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-9-fluorenyl)-zirconium dichloride;

methyl-3-butenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-2,7-di-t-butyl-9-fluorenyl)zirconium dichloride;

methyl-4-pentenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-9-fluorenyl)zirconium dichloride;

methyl-4-pentenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-2,7-di-t-butyl-9-fluorenyl)zirconium dichloride;

methyl-5-hexenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-9-fluorenyl)zirconium dichloride;

methyl-5-hexenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-2,7-di-t-butyl-9-fluorenyl)zirconium dichloride;

phenyl-3-butenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-9-fluorenyl)zirconium dichloride;

phenyl-3-butenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-2,7-di-t-butyl-9-fluorenyl)zirconium dichloride;

phenyl-4-pentenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-9-fluorenyl)zirconium dichloride;

phenyl-4-pentenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-2,7-di-t-butyl-9-fluorenyl)zirconium dichloride;

phenyl-5-hexenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-9-fluorenyl)zirconium dichloride;

phenyl-5-hexenylmethylidene(η

⁵-cyclopentadienyl)(η

⁵-2,7-di-t-butyl-9-fluorenyl)zirconium dichloride;

methyl-3-butenylsilylbis(η

⁵-fluoren-9-yl)zirconium(IV) dichloride;

methyl-4-pentenylsilylbis(η

⁵-fluoren-9-yl)zirconium(IV) dichloride;

methyl-5-hexenylsilylbis(η

⁵-fluoren-9-yl)zirconium(IV) dichloride;

methyl-6-heptenylsilylbis(η

⁵-fluoren-9-yl)zirconium(IV) dichloride;

methyl-7-octenylsilylbis(η

⁵-fluoren-9-yl)zirconium(IV) dichloride;

or any combination thereof.

46. A method of polymerizing olefins, comprising:

contacting ethylene and an optional α

-olefin comonomer with a catalyst composition under polymerization conditions to form a polymer or copolymer;

wherein the catalyst composition comprises the contact product of at least one ansa-metallocene, at least one organoaluminum compound, and 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,

(X¹) and (X²) are connected by a substituted bridging group comprising one atom bonded to both (X¹) and (X²), wherein the atom is carbon, silicon, germanium, or tin;

wherein one substituent of the substituted bridging group comprises an unsaturated group, wherein the unsaturated group is an alkenyl group, an alkynyl group, an alkadienyl group, or a substituted analog thereof, any of which having from 1 to about 20 carbon atoms; and

any additional substituent on the substituted bridging group;

any substituent on the substituted alkenyl, substituted alkynyl, or substituted alkadienyl group bonded to the bridging group;

any substituent on (X¹) and (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, an inorganic group, an organometallic group, 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 alkoxide or aryloxide, any of which having from 1 to about 20 carbon atoms, halide, or hydride; and

n is a number from 1 to 3, inclusive; and

c) 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.

47. The method of claim 46, wherein the activator-support comprises a solid oxide treated with an electron-withdrawing anion;

wherein the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof; and

the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted sulfonate, unsubstituted sulfonate, or any combination thereof.

48. A polymer produced by the method of claim 46.

49. An article comprising a polymer produced by the method of claim 46.