Highly active supported catalyst compositions

• US 20010051698A1
• Filed: 06/20/2001
• Published: 12/13/2001
• Est. Priority Date: 08/26/1998
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Speca, Anthony N.
• Granted Patent: US 6,524,988 B2
• Time in Patent Office: Days
• US Class Current: 526/133
• 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 110/06 Propene
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 4/025 Metal oxides
• 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
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

This invention relates to metallocene catalyst compositions which are highly active for the polymerization of olefins, particularly prochiral α-olefins. The catalyst compositions contain at least one metallocene, and least one activator and a support that has been fluorided using a fluoride containing compound.

Claims

1. A metallocene supported catalyst composition comprising:

a metallocene catalyst; and

a support composition represented by a formula

Sup F

wherein Sup is a support and F is a fluorine atom bound to the support.

2. The metallocene supported catalyst composition of

claim 1

wherein the metallocene catalyst is represented by a formula:

Cp_mMR_nX_q

wherein Cp is a cyclopentadienyl ring which may be substituted, or derivative thereof which may be substituted, M is a Group 4, 5, or 6 transition metal, R is a hydrocarbyl group or hydrocarboxy group having from one to 20 carbon atoms, X may be a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group and m=1−

3, n=0−

3, q=0−

3, and the sum of m+n+q is equal to the oxidation state of the transition metal.

3. A metallocene supported catalyst composition comprising:

a metallocene catalyst; and

a support composition represented by a formula

Sup L F_n

wherein Sup is a support selected from the group consisting of talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide thoria, aluminum phosphate gel, polyvinylchloride or substituted polystyrene;

“

L”

is a first member selected from the group consisting of (i) bonding, sufficient to bound the F to the Sup;

(ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr bound to the Sup and to the F;

or (iii) O bound to the Sup and bound to a second member selected from the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr which is bound to the F;

“

F”

is a fluorine atom; and

“

n”

is a number from 1-7.

4. The metallocene supported catalyst composition of

claim 3

wherein the support composition is a fluorided support composition.

5. The metallocene supported catalyst composition of

claim 3

wherein the metallocene catalyst is represented by a formula:

Cp_mMR_nX_q

wherein Cp is a cyclopentadienyl ring which may be substituted, or derivative thereof which may be substituted, M is a Group 4, 5, or 6 transition metal, R is a hydrocarbyl group or hydrocarboxy group having from one to 20 carbon atoms, X may be a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group , and m=1−

3, n=0−

3, q=0−

3, and the sum of m+n+q is equal to the oxidation state of the transition metal.

6. The metallocene supported catalyst composition of

claim 3

further including an activator.

7. The metallocene supported catalyst composition of

claim 6

wherein the activator is an alkylalumoxane.

8. The metallocene supported catalyst composition of

claim 6

wherein the activator is a noncoordinating anion activator.

9. The metallocene supported catalyst composition of

claim 3

wherein the metallocene is selected from the group consisting of:

Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl)Zirconium dimethyl Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)Zirconium dimethyl;

Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)Zirconium dimethyl;

Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl)Zirconium dimethyl;

Dimethylsilandiylbis(2-ethyl-4-naphthyl-1-indenyl)Zirconium dimethyl, Dimethylsilandiylbis(2-methyl-4-1-naphthyl)-1-indenyl)Zirconium dimethyl, Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl)Zirconium dimethyl, Dimethylsilandiylbis(2-methyl-indenyl)Zirconium dimethyl, Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl)Zirconium dimethyl, Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl)Zirconium dimethyl, Dimethylsilandiylbis(2-methyl-1-indenyl)Zirconium dimethyl, Dimethylsilandiylbis(2-ethyl-1-indenyl)Zirconium dimethyl, Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl)Zirconium dimethyl, Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl)Zirconium dichloride Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)Zirconium dichloride;

Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)Zirconium dichloride;

Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl)Zirconium dichloride;

Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl)Zirconium dichloride, Dimethylsilandiylbis(2-methyl-4-(-naphthyl)-1-indenyl)Zirconium dichloride, Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl)Zirconium dichloride, Dimethylsilandiylbis(2-methyl-indenyl)Zirconium dichloride, Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl)Zirconium dichloride, Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl)Zirconium dichloride , Dimethylsilandiylbis(2-methyl-1-indenyl)Zirconium dichloride, Dimethylsilandiylbis(2-ethyl-1-indenyl)Zirconium dichloride, or Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl)Zirconium dichloride.

10. The metallocene supported catalyst composition of

claim 3

wherein the fluorine concentration is in the range of from 0.01 to 10.0 millimoles of fluorine per gram of support.

11. A method of making a metallocene supported catalyst composition comprising the step of:

contacting a metallocene catalyst with a support composition under suitable conditions and for a sufficient time, wherein the support composition is represented by a formula

Sup L F_n

wherein Sup is a support selected from the group consisting of talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide thoria, aluminum phosphate gel, polyvinylchloride and substituted polystyrene;

“

L”

is a first member selected from the group consisting of (i) bonding, sufficient to bound the F to the Sup;

(ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr bound to the Sup and to the F;

or (iii) O bound to the Sup and bound to a second member selected from the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr which is bound to the F_n;

“

F”

is a fluorine atom; and

“

n”

is a number from 1-7.

12. The method of

claim 11

comprising the step of contacting the metallocene catalyst with an activator before contacting the metallocene with the support composition.

13. The method of

claim 11

wherein the support composition is a fluorided support composition.

14. A polymerization method comprising the step of:

contacting a polymerizable olefin with a metallocene supported catalyst composition under suitable conditions and for a sufficient time wherein the metallocene supported catalyst composition comprises

a metallocene catalyst;

a support composition represented by a formula

Sup L F_n

wherein Sup is a support selected from the group consisting of talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide thoria, aluminum phosphate gel, polyvinylchloride and substituted polystyrene;

“

L”

is a first member selected from the group consisting of (i) bonding, sufficient to bound the F to the Sup;

(ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr bound to the Sup and to the F;

or (iii) O bound to the Sup and bound to a second member selected from the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr which is bound to the F;

“

F”

is a fluorine atom; and

“

n”

is a number from 1-7.

15. The method of

claim 14

wherein the polymerizable olefin is propylene.

16. An article incorporating a polymer product of

claim 14

.

17. The article of

claim 16

comprising a member selected from the group consisting of films, fibers, fabrics, and molded structures.

18. The method of

claim 14

wherein the support composition is a fluorided support composition.

19. A metallocene supported catalyst composition consisting essentially of:

one or more metallocene catalyst;

activator; and

a support composition represented by a formula

Sup L F_n

wherein Sup is a support selected from the group consisting of talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide thoria, aluminum phosphate gel, polyvinylchloride or substituted polystyrene and mixtures thereof;

“

L”

is a first member selected from the group consisting of (i) bonding, sufficient to bound the F to the Sup;

(ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr bound to the Sup and to the F;

or (iii) O bound to the Sup and bound to a second member selected from the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr which is bound to the F;

“

F”

is a fluorine atom; and

“

n”

is a number from 1-7.

20. The metallocene supported catalyst composition of

claim 19

wherein the support composition is a fluorided support composition.

21. The metallocene supported catalyst composition of

claim 19

wherein the metallocene catalyst is represented by a formula:

Cp_mMR_nX_q

wherein Cp is a cyclopentadienyl ring which may be substituted, or derivative thereof which may be substituted, M is a Group 4, 5, or 6 transition metal, R is a hydrocarbyl group or hydrocarboxy group having from one to 20 carbon atoms, X may be a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group, and m=1−

3, n=0−

3, q=0−

3, and the sum of m+n+q is equal to the oxidation state of the transition metal.

22. The metallocene supported catalyst composition of

claim 19

wherein the fluorine concentration is in the range of from 0.6 to 3.5 wt. % of support.