IP Library › Granted Patent US 7,619,047

Granted Patent B2

US 7,619,047 · App. 11/359,972 · Granted Nov 17, 2009

Dual metallocene catalysts for polymerization of bimodal polymers

Assignee: Chevron Phillips Chemical Company, LP

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Quick Facts

Patent No.: US 7,619,047
App. No.: 11/359,972
Granted: Nov 17, 2009
Kind: B2

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Abstract

This invention relates to catalyst compositions, methods, and polymers encompassing at least one first Group 4 metallocene compound comprising bridging η 5 -cyclopentadienyl-type ligands, in combination with at least one second Group 4 metallocene with non-bridging η 5 -cyclopentadienyl-type ligands, typically in combination with at least one cocatalyst, and at least one activator. The compositions and methods disclosed herein provide ethylene polymers with a bimodal molecular weight distribution.

Claims (428)

1. A composition comprising a contact product of: 1) at least one first metallocene; 2) at least one second metallocene; and 3) at least one activator-support, wherein:

a) the at least one first metallocene comprises an ansa-metallocene having the formula:

(X 1 )(X 2 )(X 3 )(X 4 )M 1 (M1-A),

wherein

M 1 is titanium, zirconium, or hafnium;

(X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;

one substituent on (X 1 ) and (X 2 ) is a bridging group having the formula ER 1 R 2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X 1 ) and (X 2 ), and wherein R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group;

at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;

(X 3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or 4) OBR A 2 or SO 3 R A , wherein R A is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and

any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently 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, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen;

b) the at least one second metallocene comprises an unbridged metallocene having the formula:

i) (X 5 )(X 6 )(X 7 )(X 8 )M 2 (M2-A),

wherein

M 2 is titanium, zirconium, or hafnium;

(X 5 ) and (X 6 ) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

(X 7 ) and (X 8 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or 4) OBR B 2 or SO 3 R B , wherein R B is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and

any substituent on the substituted cyclopentadienyl or substituted indenyl is independently 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, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen;

ii) (X 9 )(X 10 )(X 11 )(X 12 )M 3 (M3-A),

wherein

M 3 is titanium, zirconium, or hafnium;

(X 9 ) is a substituted cyclopentadienyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;

(X 10 ) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;

(X 11 ) and (X 12 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or 4) OBR C 2 or SO 3 R C , wherein R C is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and

any additional substituent on the substituted cyclopentadienyl or substituted indenyl is independently 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, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen;

iii) any combination thereof;

and

c) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion.

2. A composition according to claim 1 , wherein the metallocene (X 5 )(X 6 )(X 7 )(X 8 )M 2 (M2-A) has the formula:

(X 5 )(X 6 )(X 7 )(X 8 )M 2 (M2-B),

wherein

M 2 is zirconium or hafnium;

(X 5 ) and (X 6 ) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

(X 7 ) and (X 8 ) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH 4 , F, Cl, Br, or I; and

3. A composition according to claim 1 , wherein the metallocene (X 9 )(X 10 )(X 11 )(X 12 )M 3 (M3-A) has the formula:

(X 9 )(X 10 )(X 11 )(X 12 )M 3 (M3-B),

wherein

M 3 is zirconium or hafnium;

(X 9 ) is a substituted cyclopentadienyl group, wherein any substituent is independently a linear or branched alkyl group having up to 12 carbon atoms;

(X 10 ) is a substituted indenyl group, wherein any substituent is independently an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having from 1 to 20 carbon atoms; and

(X 11 ) and (X 12 ) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH 4 , F, Cl, Br, or I.

4. A composition according to claim 1 , wherein the at least one second metallocene comprises an unbridged metallocene having the formula:

i) (X 5 )(X 6 )(X 7 )(X 8 )M 2 (M2-B),

wherein

M 2 is zirconium or hafnium;

(X 5 ) and (X 6 ) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

(X 7 ) and (X 8 ) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH 4 , F, Cl, Br, or I; and

ii) (X 9 )(X 10 )(X 11 )(X 12 )M 3 (M3-B),

wherein

M 3 is zirconium or hafnium;

(X 9 ) is a substituted cyclopentadienyl group, wherein any substituent is independently a linear or branched alkyl group having up from 1 to 12 carbon atoms;

(X 11 ) and (X 12 ) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH 4 , F, Cl, Br, or I;

iii) any combination thereof.

5. A composition according to claim 1 , wherein the at least one first metallocene comprises a compound having the formula:

wherein

M 1A is titanium, zirconium, or hafnium;

X 3A and X 4A are independently F, Cl, Br, I, benzyl, phenyl, or methyl;

E A is C or Si;

R 1A and R 2A are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1A and R 2A is an aryl group;

R 3A and R 4A are independently H or CH 3 ;

n is an integer from 0 to 5 inclusive; and

R 5A and R 6A are independently 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, or a boron group, any of which having from 1 to 12 carbon atoms; or hydrogen.

6. A composition according to claim 1 , wherein the at least one second metallocene comprises a compound having the formula:

or any combination thereof, wherein

M 2A is, independently, zirconium or hafnium;

X 7A and X 8A , in each occurrence, are independently F, Cl, Br, I, benzyl, phenyl, or methyl; and

R 7A and R 8A , in each occurrence, are independently H, methyl, ethyl, n-propyl, n-butyl, n-pentyl, CH 2 CH 2 CH 2 Ph, CH 2 CH═CH 2 , CH 2 CH 2 CH═CH 2 , or CH 2 CH 2 CH 2 CH═CH 2 ;

ii)

wherein

M 3A is zirconium or hafnium;

R 9A is H or CH 3 ;

R 10A is H, CH 2 CH═CH 2 , CH 2 CH 2 CH═CH 2 , CH 2 CH 2 CH 2 CH═CH 2 , CH 2 CH 2 CH 2 Ph, or CH 2 CH 2 CH 2 CH 3 ; and

X 11A and X 12A are independently F, Cl, Br, I, benzyl, phenyl, or methyl;

iii) any combination thereof.

7. A composition according to claim 1 , wherein the at least one activator-support is a solid oxide treated with an electron-withdrawing anion, wherein:

the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and

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

8. A composition according to claim 1 , wherein the solid oxide treated with an electron withdrawing anion further comprises a metal or metal ion selected from zinc, nickel, vanadium, tungsten, molybdenum, silver, tin, or any combination thereof.

9. A composition according to claim 1 , wherein the at least one first metallocene comprises a compound having the formula:

wherein

M 1B is zirconium or hafnium;

R 2B is methyl or phenyl;

R 3B and R 4B are independently H or CH 3 ; and

n is an integer from 0 to 5, inclusive.

10. A composition according to claim 1 , wherein the at least one first metallocene is selected from

or any combination thereof.

11. A composition according to claim 1 , wherein the at least one second metallocene comprises a compound having the formula:

or any combination thereof,

wherein

M 2B is zirconium or hafnium;

X 7B and X 8B are independently benzyl, Cl, or methyl; and

R 7B and R 8B are independently H, methyl, ethyl, n-propyl, n-butyl, CH 2 CH═CH 2 , CH 2 CH 2 CH═CH 2 , or CH 2 CH 2 CH 2 CH═CH 2 .

12. A composition according to claim 1 , wherein the at least one second metallocene comprises a compound having the formula:

or any combination thereof.

13. A composition according to claim 1 , wherein the at least one second metallocene comprises a compound having the formula:

wherein

M 3B is zirconium or hafnium;

R 9B is H or CH 3 ; and

R 10B is H, CH 2 CH═CH 2 , CH 2 CH 2 CH═CH 2 , CH 2 CH 2 CH 2 Ph, or CH 2 CH 2 CH 2 CH 3 .

14. A composition according to claim 1 , wherein the at least one second metallocene is selected from

or any combination thereof.

15. A composition according to claim 1 , wherein:

a) the at least one first metallocene comprises a compound having the formula:

wherein

M 1B is zirconium or hafnium;

R 2B is methyl or phenyl;

R 3B and R 4B are independently H or CH 3 ; and

n is an integer from 0 to 5, inclusive;

b) the at least one second metallocene comprises a compound having the formula:

wherein

M 2C is zirconium or hafnium; and

X 7C and X 8C are independently benzyl, Cl, or methyl;

ii)

wherein

M 3B is zirconium or hafnium;

R 9B is H or CH 3 ; and

R 10B is H, CH 2 CH═CH 2 , CH 2 CH 2 CH═CH 2 , CH 2 CH 2 CH 2 Ph, or CH 2 CH 2 CH 2 CH 3 ;

iii) any combination thereof.

16. A composition according to claim 1 , wherein a molar ratio of the at least one first metallocene to the at least one second metallocene in the composition is from about 1:10 to about 10:1.

17. A composition according to claim 1 , wherein the at least one activator-support is selected from chlorided alumina, fluorided alumina, fluorided aluminophosphate, sulfated alumina, fluorided silica-alumina, or any combination thereof.

18. A composition according to claim 1 , wherein the contact product further comprises: 4) at least one organoaluminum compound having the formula:

Al(X 13 ) n (X 14 ) 3-n ,

wherein (X 13 ) is a hydrocarbyl having from 1 to 20 carbon atoms; (X 14 ) is an alkoxide or an aryloxide, any of which having from 1 to 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive.

19. A composition according to claim 18 , wherein the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof.

20. A composition according to claim 18 , wherein:

a) the at least one first metallocene comprises a compound having the formula:

wherein

M 1A is zirconium or hafnium;

X 3A and X 4A are independently F, Cl, Br, I, benzyl, phenyl, or methyl;

E A is C or Si;

R 1A and R 2A are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1A and R 2A is an aryl group;

R 3A and R 4A are independently H or CH 3 ;

n is an integer from 0 to 5, inclusive; and

R 5A and R 6A are independently a hydrocarbyl group 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, or a boron group, any of which having from 1 to 12 carbon atoms; or hydrogen;

b) the at least one second metallocene comprises a compound having the formula:

or any combination thereof, wherein

M 2A is, independently, zirconium or hafnium;

X 7A and X 8A , in each occurrence, are independently F, Cl, Br, I, benzyl, phenyl, or methyl; and

R 7A and R 8A , in each occurrence, are independently H, methyl, ethyl, n-propyl, n-butyl, n-pentyl, CH 2 CH 2 CH 2 Ph, CH 2 CH═CH 2 , CH 2 CH 2 CH═CH 2 , or CH 2 CH 2 CH 2 CH═CH 2 ;

ii)

wherein

M 3A is zirconium or hafnium;

R 9A is H or CH 3 ;

R 10A is H, CH 2 CH═CH 2 , CH 2 CH 2 CH═CH 2 , CH 2 CH 2 CH 2 CH═CH 2 , CH 2 CH 2 CH 2 Ph, or CH 2 CH 2 CH 2 CH 3 ; and

X 11A and X 12A are independently F, Cl, Br, I, benzyl, phenyl, or methyl;

iii) any combination thereof;

c) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributyl aluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof; and

d) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion, wherein:

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

21. A composition according to claim 18 , wherein:

a) the at least one first metallocene comprises

or any combination thereof;

b) the at least one second metallocene comprises

or any combination thereof;

c) the at least one organoaluminum compound comprises triethylaluminum, tn-n-butylaluminum, triisobutylaluminum, or any combination thereof; and

d) the at least one activator-support comprises a sulfated solid oxide.

22. A composition according to claim 18 , wherein:

a) the at least one first metallocene is selected from

or any combination thereof;

b) the at least one second metallocene is selected from

or any combination thereof;

c) the at least one organoaluminum compound comprises triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof; and

d) the at least one activator-support comprises a sulfated alumina.

23. A composition according to claim 1 , wherein the contact product further comprises: 5) an ionizing ionic compound selected from tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl)ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)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(trifluoromethyl)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-dimethyl-phenyl)borate, potassium tetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, triphenylcarbenium tetrakis(p-tolyl)aluminate, triphenylcarbenium tetrakis(m-tolyl)aluminate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)aluminate, triphenylcarbenium 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, triphenylcarbenium tris(2,2′,2″-nonafluorobiphenyl)fluoroaluminate, silver tetrakis(1,1,1,3,3,3-hexafluoroisopropanolato)-aluminate, or silver tetrakis(perfluoro-t-butoxy)aluminate, or any combination thereof.

24. A catalyst composition comprising a contact product of: 1) at least one first metallocene; 2) at least one second metallocene; 3) optionally, at least one organoaluminum compound; and 4) at least one activator-support, wherein:

a) the at least one first metallocene comprises an ansa-metallocene having the formula:

(X 1 )(X 2 )(X 3 )(X 4 )M 1 (M1-A),

wherein

M 1 is titanium, zirconium, or hafnium;

(X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;

at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;

b) the at least one second metallocene comprises an unbridged metallocene having the formula:

i) (X 5 )(X 6 )(X 7 )(X 8 )M 2 (M2-A),

wherein

M 2 is titanium, zirconium, or hafnium;

(X 5 ) and (X 6 ) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

ii) (X 9 )(X 10 )(X 11 )(X 12 )M 3 (M3-A),

wherein

M 3 is titanium, zirconium, or hafnium;

(X 10 ) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;

iii) any combination thereof;

c) the at least one organo aluminum compound comprises a compound having the formula:

Al(X 13 ) n (X 14 ) 3-n ,

d) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion;

wherein the at least one organoaluminum compound is optional when at least one of the following conditions exist:

1) a) at least one of (X 3 ) and (X 4 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; b) at least one of (X 7 ) and (X 8 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; and c) at least one of (X 11 ) and (X 12 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ;

2) the catalyst composition comprises at least one organoaluminoxane compound; or

3) both conditions 1 and 2 exist.

25. A catalyst composition comprising a contact product of: 1) at least one first metallocene; 2) at least one second metallocene; and 3) at least one activator-support, wherein:

a) the at least one first metallocene comprises an ansa-metallocene having the formula:

(X 1 )(X 2 )(X 3 )(X 4 )M 1 (M1-B),

wherein

M 1 is titanium, zirconium, or hafnium;

(X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;

at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;

b) the at least one second metallocene comprises an unbridged metallocene having the formula:

i) (X 5 )(X 6 )(X 7 )(X 8 )M 2 (M2-C),

wherein

M 2 is titanium, zirconium, or hafnium;

(X 5 ) and (X 6 ) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

ii) (X 9 )(X 10 )(X 11 )(X 12 )M 3 (M3-C),

wherein

M 3 is titanium, zirconium, or hafnium;

(X 10 ) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;

iii) any combination thereof; and

c) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion.

26. A catalyst composition according to claim 25 , wherein the metallocene (X 5 )(X 6 )(X 7 )(X 8 )M 2 (M2-C) has the formula:

(X 5 )(X 6 )(X 7 )(X 8 )M 2 (M2-D),

wherein

M 2 is zirconium or hafnium;

(X 5 ) and (X 6 ) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

(X 7 ) and (X 8 ) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH 4 , F, Cl, Br, or I, wherein at least one of (X 7 ) and (X 8 ) is a hydrocarbyl group, H, or BH 4 ; and

27. A catalyst composition according to claim 25 , wherein the metallocene (X 9 )(X 10 )(X 11 )(X 12 )M 3 (M3-C) has the formula:

(X 9 )(X 10 )(X 11 )(X 12 )M 3 (M3-D),

wherein

M 3 is zirconium or hafnium;

(X 9 ) is a substituted cyclopentadienyl group, wherein any substituent is independently a linear or branched alkyl group having from 1 to 12 carbon atoms;

(X 11 ) and (X 12 ) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH 4 , F, Cl, Br, or I, wherein at least one of (X 11 ) and (X 12 ) is a hydrocarbyl group, H, or BH 4 .

28. A catalyst composition according to claim 25 , wherein the at least one second metallocene comprises an unbridged metallocene having the formula:

i) (X 5 )(X 6 )(X 7 )(X 8 )M 2 (M2-D),

wherein

M 2 is zirconium or hafnium;

(X 5 ) and (X 6 ) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

(X 7 ) and (X 8 ) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH 4 , F, Cl, Br, or I, wherein at least one of (X 7 ) and (X 8 ) is a hydrocarbyl group, H, or BH 4 ; and

ii) (X 9 )(X 10 )(X 11 )(X 12 )M 3 (M3-D),

wherein

M 3 is zirconium or hafnium;

(X 9 ) is a substituted cyclopentadienyl group, wherein any substituent is independently a linear or branched alkyl group having from 1 to 12 carbon atoms;

(X 11 ) and (X 12 ) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH 4 , F, Cl, Br, or I, wherein at least one of (X 11 ) and (X 12 ) is a hydrocarbyl group, H, or BH 4 ;

iii) any combination thereof.

29. A catalyst composition according to claim 25 , wherein:

a) the at least one first metallocene comprises a compound having the formula:

wherein

M 1A is zirconium or hafnium;

X 3A and X 4A are independently F, Cl Br, I, benzyl, phenyl, or methyl, wherein at least one of X 3A and X 4A is benzyl, phenyl, or methyl;

E A is C or Si;

R 1A and R 2A are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1A and R 2A is an aryl group;

R 3A and R 4A are independently H or CH 3 ;

n is an integer from 0 to 5, inclusive; and

b) the at least one second metallocene comprises a compound having the formula:

or any combination thereof, wherein

M 2A is, independently, zirconium or hafnium;

X 7A and X 8A , in each occurrence, are in dependently F, Cl, Br, I, benzyl, phenyl, or methyl, wherein at least one of X 7A and X 8A is benzyl, phenyl, or methyl;

R 7A and R 8A , in each occurrence, are independently H, methyl, ethyl, n-propyl, n-butyl, n-pentyl, CH 2 CH 2 CH 2 Ph, CH 2 CH═CH 2 , CH 2 CH 2 CH═CH 2 , or CH 2 CH 2 CH 2 CH═CH 2 ;

ii)

wherein

M 3A is zirconium or hafnium;

R 9A is H or CH 3 ;

R 10A is H, CH 2 CH═CH 2 , CH 2 CH 2 CH═CH 2 , CH 2 CH 2 CH 2 CH═CH 2 , CH 2 CH 2 CH 2 Ph, or CH 2 CH 2 CH 2 CH 3 ; and

X 11A and X 12A are independently F, Cl, Br, I, benzyl, phenyl, or methyl, wherein at least one of X 11A and X 12A is benzyl, phenyl, or methyl;

iii) any combination thereof; and

c) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion, wherein:

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

30. A process for producing a composition comprising contacting: 1) at least one first metallocene; 2) at least one second metallocene; and 3) at least one activator-support, wherein:

a) the at least one first metallocene comprises an ansa-metallocene having the formula:

(X 1 )(X 2 )(X 3 )(X 4 )M 1 (M1-A),

wherein

M 1 is titanium, zirconium, or hafnium;

(X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;

at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;

b) the at least one second metallocene comprises an unbridged metallocene having the formula:

i) (X 5 )(X 6 )(X 7 )(X 8 )M 2 (M2-A),

wherein

M 2 is titanium, zirconium, or hafnium;

(X 5 ) and (X 6 ) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

(X 7 ) and (X 8 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or 4) OBR B 2 or SO 3 R B wherein R B is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and

ii) (X 9 )(X 10 )(X 11 )(X 12 )M 3 (M3-A),

wherein

M 3 is titanium, zirconium, or hafnium;

(X 10 ) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;

iii) any combination thereof;

and

c) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion.

31. A process for producing a polymerization catalyst composition comprising contacting: 1) at least one first metallocene; 2) at least one second metallocene; 3) optionally, at least one organoaluminum compound; and 4) at least one activator-support, wherein:

a) the at least one first metallocene comprises an ansa-metallocene having the formula:

(X 1 )(X 2 )(X 3 )(X 4 )M 1 (M1-A),

wherein

M 1 is titanium, zirconium, or hafnium;

(X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;

at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;

b) the at least one second metallocene comprises an unbridged metallocene having the formula:

i) (X 5 )(X 6 )(X 7 )(X 8 )M 2 (M2-A),

wherein

M 2 is titanium, zirconium, or hafnium;

(X 5 ) and (X 6 ) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

(X 7 ) and (X 8 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or 4) OBR B 2 or SO 3 R B wherein R B is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and

ii) (X 9 )(X 10 )(X 11 )(X 12 )M 3 (M3-A),

wherein

M 3 is titanium, zirconium, or hafnium;

(X 10 ) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;

iii) any combination thereof;

c) the at least one organoaluminum compound comprises a compound having the formula:

Al(X 13 ) n (X 14 ) 3-n ,

d) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion;

wherein the at least one organoaluminum compound is optional when at least one of the following conditions exist:

2) the catalyst composition comprises at least one organoaluminoxane compound; or

3) both conditions 1 and 2 exist.

32. A process for producing a polymerization catalyst composition comprising contacting: 1) at least one first metallocene; 2) at least one second metallocene; and 3) at least one activator-support, wherein:

a) the at least one first metallocene comprises an ansa-metallocene having the formula:

(X 1 )(X 2 )(X 3 )(X 4 )M 1 (M1-B),

wherein

M 1 is titanium, zirconium, or hafnium;

(X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;

at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;

b) the at least one second metallocene comprises an unbridged metallocene having the formula:

i) (X 5 )(X 6 )(X 7 )(X 8 )M 2 (M2-C),

wherein

M 2 is titanium, zirconium, or hafnium;

(X 5 ) and (X 6 ) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

ii) (X 9 )(X 10 )(X 11 )(X 12 )M 3 (M3-C),

wherein

M 3 is titanium, zirconium, or hafnium;

(X 10 ) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;

iii) any combination thereof; and

c) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion.

33. A composition according to claim 18 , wherein:

a) the at least one first metallocene comprises a compound having the formula:

wherein

M 1B is zirconium or hafnium;

R 2B is methyl or phenyl;

R 3B and R 4B are independently H or CH 3 ; and

n is an integer from 0 to 5, inclusive;

b) the at least one second metallocene comprises a compound having the formula:

or any combination thereof, wherein

M 2B is zirconium or hafnium;

X 7B and X 8B are independently benzyl, Cl, or methyl; and

R 7B and R 8B are independently H, methyl, ethyl, n-propyl, n-butyl, CH 2 CH═CH 2 , CH 2 CH 2 CH═CH 2 , or CH 2 CH 2 CH 2 CH═CH 2 ;

c) the at least one activator-support is chlorided alumina, fluorided alumina, sulfated alumina, fluorided silica-alumina, or any combination thereof; and

d) the at least one organo aluminum compound is triethylaluminum, tributylaluminum, triisobutylaluminum, or any combination thereof.

34. A composition according to claim 18 , wherein:

a) the at least one first metallocene comprises a compound having the formula:

wherein

M 1B is zirconium or hafnium;

R 2B is methyl or phenyl;

R 3B and R 4B are independently H or CH 3 ; and

n is an integer from 0 to 5, inclusive;

b) the at least one second metallocene comprises a compound having the formula:

wherein

M 3B is zirconium or hafnium;

R 9B is H or CH 3 ; and

R 10B is H, CH 2 CH═CH 2 , CH 2 CH 2 CH═CH 2 , CH 2 CH 2 CH 2 Ph, or CH 2 CH 2 CH 2 CH 3 ;

c) the at least one activator-support is chlorided alumina, fluorided alumina, sulfated alumina, fluorided silica-alumina, or any combination thereof; and

d) the at least one organoaluminum compound is triethylaluminum, tributylaluminum, triisobutylaluminum, or any combination thereof.

35. A composition according to claim 18 , wherein the contact product further comprises at least one organoaluminoxane compound, at least one organoboron or organoborate compound, or a combination thereof.

36. A composition according to claim 18 , wherein the at least one first metallocene comprises a compound having the formula:

wherein

M 1A is titanium, zirconium, or hafnium;

X 3A and X 4A are independently Cl or Ph;

E A is C or Si;

R 1A and R 2A are Ph;

R 3A and R 4A are independently H or CH 3 ;

n is an integer from 0 to 5, inclusive; and

R 5A and R 6A are t-Bu.

37. A composition according to claim 1 , wherein the at least one first metallocene comprises a compound having the formula:

wherein

M 1A is titanium, zirconium, or hafnium;

X 3A and X 4A are independently Cl or Ph;

E A is C or Si;

R 1A and R 2A are Ph;

R 3A and R 4A are independently H or CH 3 ;

n is an integer from 0 to 5, inclusive; and

R 5A and R 6A are t-Bu.

Assignments (1)

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 8, 2006

From: YANG, QING; JAYARATNE, KUMUDINI C.; JENSEN, MICHAEL D.; MCDANIEL, MAX P.; MARTIN, JOEL L.; THORN, MATTHEW G.; LANIER, JERRY T.; CRAIN, TONY R.

To: CHEVRON PHILLIPS CHEMICAL COMPANY, L.P.

Reel/Frame 017594/0950 →

Continuity (1)

Related Publication 20070197374A1 · Aug 23, 2007