Nano-linked heteronuclear metallocene catalyst compositions and their polymer products

1. A dinuclear metallocene compound having the formula (IA)=(IB); wherein:

(IA) is

(IB) is

 wherein:

X 1 , X 2 , X 13 , and X 14 independently are hydrogen; BH 4 ; a halide; a hydrocarbyl group, hydrocarbyloxide group, hydrocarbyloxylate group, hydrocarbylamino group, or hydrocarbylsilyl group, any of which having up to 20 carbon atoms; or OBR A 2 or SO 3 R A , wherein R A is an alkyl group or aryl group having up to 12 carbon atoms;

X 3 and X 15 independently are a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X 3 and X 15 independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;

X 4 and X 16 independently are a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X 4 and X 16 other than an alkenyl linking group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;

M 1 and M 4 independently are Zr, Hf, or Ti;

each R X , R Y , and R Z independently is a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; and

each n independently is an integer in a range from 0 to 12, inclusive;

with the proviso that (IA) is not the same as (IB).

2. The compound of claim 1 , wherein:

X 1 , X 2 , X 13 , and X 14 independently are Cl, a methyl group, a phenyl group, or a benzyl group; and

each n independently is 0, 1, 2, 3, 4, 5, or 6.

3. The compound of claim 2 , wherein:

X 3 and X 15 independently are a substituted or unsubstituted cyclopentadienyl group;

X 4 and X 16 independently are a substituted cyclopentadienyl or substituted indenyl group;

M 1 and M 4 independently are Zr or Hf; and

each R X , R Y , and R Z independently is a hydrogen atom or a methyl group.

4. A catalyst composition comprising a contact product of the dinuclear metallocene compound of claim 1 and an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

5. A catalyst composition comprising a contact product of the dinuclear metallocene compound of claim 1 and an activator-support, wherein the activator-support comprises a solid oxide treated with an electron-withdrawing anion, and wherein:

the solid oxide comprises silica, alumina, silica-alumina, aluminum phosphate, 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, or any combination thereof.

6. The catalyst composition of claim 5 , further comprising an organoaluminum compound, 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.

7. A process for polymerizing olefins, the process comprising contacting a catalyst composition with an olefin monomer and an optional olefin comonomer under polymerization conditions to produce an olefin polymer, wherein:

the catalyst composition comprises a contact product of the dinuclear metallocene compound of claim 1 ; an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an activator-support, or any combination thereof; and an optional organoaluminum compound.

8. The process of claim 7 , wherein the olefin monomer comprises 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 mixtures thereof.

9. The process of claim 7 , wherein the process is conducted in a polymerization reactor system comprising a slurry reactor, a loop slurry reactor, a gas phase reactor, a fluidized bed reactor, a solution reactor, a tubular reactor, an autoclave reactor, or any combination thereof.

10. A dinuclear metallocene compound having the formula (IIA)=(IIB); wherein:

(IIA) is

(IIB) is

 wherein:

X 5 , X 6 , X 17 , and X 18 independently are hydrogen; BH 4 ; a halide; a hydrocarbyl group, hydrocarbyloxide group, hydrocarbyloxylate group, hydrocarbylamino group, or hydrocarbylsilyl group, any of which having up to 20 carbon atoms; or OBR A 2 or SO 3 R A , wherein R A is an alkyl group or aryl group having up to 12 carbon atoms;

X 7 and X 19 independently are a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X 7 and X 19 other than a bridging group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;

X 8 and X 20 independently are a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X 8 and X 20 other than a bridging group and an alkenyl linking group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;

A 1 and A 3 independently are a substituted or unsubstituted bridging group comprising either a cyclic group of 5 to 8 carbon atoms, a bridging chain of 2 to 5 carbon atoms, or a carbon, silicon, germanium, tin, boron, nitrogen, or phosphorus bridging atom, any substituents on A 1 and A 3 independently are a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;

M 2 and M 5 independently are Zr, Hf, or Ti;

each E independently is carbon or silicon;

each R X , R Y , and R Z independently is a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; and

each n independently is an integer in a range from 0 to 12, inclusive;

with the proviso that (IIA) is not the same as (IIB).

11. The compound of claim 10 , wherein:

X 5 , X 6 , X 17 , and X 18 independently are Cl, a methyl group, a phenyl group, or a benzyl group;

A 1 and A 3 independently comprise a carbon bridging atom, a silicon bridging atom, or a bridging chain of 2 to 5 carbon atoms; and

each n independently is 0, 1, 2, 3, 4, 5, or 6.

12. The compound of claim 11 , wherein:

X 7 and X 19 independently are substituted fluorenyl groups;

X 8 and X 20 independently are a substituted cyclopentadienyl group or substituted indenyl group;

M 2 and M 5 independently are Zr or Hf; and

each R X , R Y , and R Z independently is a hydrogen atom or a methyl group.

13. A catalyst composition comprising a contact product of the dinuclear metallocene compound of claim 10 and an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

14. A catalyst composition comprising a contact product of the dinuclear metallocene compound of claim 10 and an activator-support, wherein the activator-support comprises a solid oxide treated with an electron-withdrawing anion, and wherein:

the solid oxide comprises silica, alumina, silica-alumina, aluminum phosphate, 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, or any combination thereof.

15. The catalyst composition of claim 14 , further comprising an organoaluminum compound, 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.

16. A process for polymerizing olefins, the process comprising contacting a catalyst composition with an olefin monomer and an optional olefin comonomer under polymerization conditions to produce an olefin polymer, wherein:

the catalyst composition comprises a contact product of the dinuclear metallocene compound of claim 10 ; an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an activator-support, or any combination thereof; and an optional organoaluminum compound.

17. The process of claim 16 , wherein the olefin monomer comprises 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 mixtures thereof.

18. The process of claim 16 , wherein the process is conducted in a polymerization reactor system comprising a slurry reactor, a loop slurry reactor, a gas phase reactor, a fluidized bed reactor, a solution reactor, a tubular reactor, an autoclave reactor, or any combination thereof.

19. A dinuclear metallocene compound having the formula (IIIA)=(IIIB); wherein:

(IIIA) is

(IIIB) is

 wherein:

X 9 , X 10 , X 21 , and X 22 independently are hydrogen; BH 4 ; a halide; a hydrocarbyl group, hydrocarbyloxide group, hydrocarbyloxylate group, hydrocarbylamino group, or hydrocarbylsilyl group, any of which having up to 20 carbon atoms; or OBR A 2 or SO 3 R A , wherein R A is an alkyl group or aryl group having up to 12 carbon atoms;

X 11 , X 12 , X 23 , and X 24 independently are a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X 11 , X 12 , X 23 , and X 24 other than a bridging group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;

A 2 and A 4 independently are a substituted bridging group comprising either a silicon bridging atom, a germanium bridging atom, a tin bridging atom, a carbon bridging atom, or a bridging chain of 2 to 5 carbon atoms, any substituents on A 2 and A 4 other than an alkenyl linking group independently are a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;

M 3 and M 6 independently are Zr, Hf, or Ti;

each R X , R Y , and R Z independently is a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; and

each n independently is an integer in a range from 0 to 12, inclusive;

with the proviso that (IIIA) is not the same as (IIIB).

20. The compound of claim 19 , wherein:

X 9 , X 10 , X 21 , and X 22 independently are Cl, a methyl group, a phenyl group, or a benzyl group;

A 2 and A 4 independently comprise a carbon bridging atom, a silicon bridging atom, or a bridging chain of 2 to 5 carbon atoms; and

each n independently is 0, 1, 2, 3, 4, 5, or 6.

21. The compound of claim 20 , wherein:

at least one of X 11 and X 12 is a substituted fluorenyl group;

at least one of X 23 and X 24 is a substituted fluorenyl group;

M 3 and M 6 independently are Zr or Hf; and

each R X , R Y , and R Z independently is a hydrogen atom or a methyl group.

22. A catalyst composition comprising a contact product of the dinuclear metallocene compound of claim 19 and an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

23. A catalyst composition comprising a contact product of the dinuclear metallocene compound of claim 19 and an activator-support, wherein the activator-support comprises a solid oxide treated with an electron-withdrawing anion, and wherein:

the solid oxide comprises silica, alumina, silica-alumina, aluminum phosphate, 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, or any combination thereof.

24. The catalyst composition of claim 23 , further comprising an organoaluminum compound, 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.

25. A process for polymerizing olefins, the process comprising contacting a catalyst composition with an olefin monomer and an optional olefin comonomer under polymerization conditions to produce an olefin polymer, wherein:

the catalyst composition comprises a contact product of the dinuclear metallocene compound of claim 19 ; an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an activator-support, or any combination thereof; and an optional organoaluminum compound.

26. The process of claim 25 , wherein the olefin monomer comprises 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 mixtures thereof.

27. The process of claim 25 , wherein the process is conducted in a polymerization reactor system comprising a slurry reactor, a loop slurry reactor, a gas phase reactor, a fluidized bed reactor, a solution reactor, a tubular reactor, an autoclave reactor, or any combination thereof.

28. The process of claim 7 , wherein the catalyst composition is contacted with ethylene and a comonomer selected from 1-butene, 1-hexene, 1-octene, or a combination thereof.

29. The process of claim 16 , wherein the catalyst composition is contacted with ethylene and a comonomer selected from 1-butene, 1-hexene, 1-octene, or a combination thereof.

30. The process of claim 25 , wherein the catalyst composition is contacted with ethylene and a comonomer selected from 1-butene, 1-hexene, 1-octene, or a combination thereof.