Ethylene elastomer compositions

• US 20080287620A1
• Filed: 05/14/2007
• Published: 11/20/2008
• Est. Priority Date: 05/14/2007
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Ravishankar, Periagaram Srinivasan
• Granted Patent: US 7,943,711 B2
• Time in Patent Office: Days
• US Class Current: 526/170
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 210/18 with non-conjugated dienes, e.g. EPT rubbers
• CPC Class Codes: C08F 236/20 unconjugated
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/04 Broad molecular weight distribution, i.e. Mw/Mn > 6
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/25 Cycloolefine
• CPC Class Codes: C08F 4/65904 in combination with another component of C08F4/64
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

In a process for producing an elastomer composition, ethylene, at least one alpha-olefin, and at least one diene is contacted with a catalyst system comprising at least one metallocene catalyst compound and a non-coordinating anion activator. The at least one metallocene catalyst compound comprises an indenyl complex having the general formula: (In¹R¹_m)R³(In²R²_p)MX_q; wherein the or each R¹ is a substituent of the indenyl ring In¹ and the or each R² is a substituent of the indenyl ring In², each R¹ and R² is, independently, a halogen or a hydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid or halocarbyl-substituted organometalloid group containing up to about 20 carbon atoms, and at least one R¹ or R² substituent is bonded to the 2-position or the 4-position of its associated indenyl ring; m is 1 to 6; p is 1 to 6; R³ is a bridging group, such that the number of atoms in the direct chain between the (In¹R¹_m) ligand and the (In²R²_p) ligand is 1 to 8, M is a transition metal from Group 3, 4, 5 or 6 of the Periodic Table of the Elements, or an actinide or lanthanide metal atom; q is equal to the valence of M minus 2; and each X is a non-cyclopentadienyl ligand and is, independently, a hydrocarbyl, oxyhydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid, oxyhydrocarbyl-substituted organometalloid or halocarbyl-substituted organometalloid group containing up to about 20 carbon atoms; provided that two X groups may be joined and bound to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms; or two X groups together can be an olefin, diolefin or aryne ligand.

Claims

1. A process for producing an elastomer composition, the process comprising:

contacting a catalyst system comprising at least one metallocene catalyst compound and a non-coordinating anion activator with a monomer mixture comprising ethylene, at least one alpha-olefin, and at least one diene;

wherein said at least one metallocene catalyst compound comprises an indenyl (In) complex having the general formula;

(In¹R¹_m)R³(In²R²_p)MX_q;

wherein the or each R¹ is a substituent of the indenyl ring In¹ and the or each R² is a substituent of the indenyl ring In², each R₁ and R² is, independently, a halogen or a hydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid or halocarbyl-substituted organometalloid group containing up to about 20 carbon atoms, and at least one R¹ or R² substituent is bonded to the 2-position or the 4-position of its associated indenyl ring;

m is 1 to 6;

p is 1 to 6;

R³ is a bridging group, such that the number of atoms in the direct chain between the (In¹R¹_m) ligand and the (In²R²_p) ligand is from 1 to 8, M is a transition metal from Group 3, 4, 5 or 6 of the Periodic Table of the Elements, or an actinide or lanthanide metal atom;

q is equal to the valence of M minus 2; and

each X is a non-cyclopentadienyl ligand and is, independently, a hydrocarbyl, oxyhydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid, oxyhydrocarbyl-substituted organometalloid or halocarbyl-substituted organometalloid group containing up to about 20 carbon atoms;

provided that two X groups may be joined and bound to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms;

or two X groups together can be an olefin, diolefin or aryne ligand.

2. The process of claim 1 wherein each R¹ and R² substituent is bonded to the 2-position or the 4-position of its associated indenyl ring;

m is 1 or 2; and

p is 1 or 2.

3. The process of claim 2 wherein m is 2 and p is 2.

4. The process of claim 1 wherein each R¹ and R² substituent is a hydrocarbyl group.

5. The process of claim 1 wherein each R¹ and R² substituent is a methyl or phenyl group.

6. The process of claim 1 wherein R³ is a bridging group containing a Group 13, 14, 15, or 16 element.

7. The process of claim 1 wherein R³ is selected from —

SiR⁴₂—

, —

CR⁴₂—

, and —

CR⁴₂—

CR⁴₂—

;

wherein R⁴, independently, is selected from hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl, and mixtures thereof.

8. The process of claim 1 wherein R³ is —

SiR⁴₂—

.

9. The process of claim 1 wherein said at least one metallocene catalyst compound comprises rac-(dimethylsilyl)bis(2-methyl-4-phenylindenyl)zirconium dimethyl or rac-(dimethylsilyl)bis(2-methyl-4-phenylindenyl)hafnium dimethyl.

10. The process of claim 1 wherein the catalyst system comprises a further metallocene catalyst compound having the general formula:

11. The process of claim 10 wherein A is a bridging group containing a Group 13, 14, 15, or 16 element.

12. The process of claim 10 wherein A is selected from —

SiR⁴₂—

, —

CR⁴₂—

, and —

CR⁴₂—

CR⁴₂—

;

wherein R⁴, independently, is selected from hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl, and mixtures thereof.

13. The process of claim 10 wherein the further metallocene catalyst compound is selected from:

μ

-(C₆H₅)₂ C(cyclopentadienyl)(fluorenyl)M(CH₃)₂;

μ

-(C₆H₅)₂ C(3-methylcyclopentadienyl)(fluorenyl)M(CH₃)₂;

μ

-(CH₃)₂ C(cyclopentadienyl)(fluorenyl)M(CH₃)₂; and

μ

-(p-triethylsilylphenyl)₂ C(cyclopentadienyl)(3,8-di-t-butylfluorenyl)M(CH₃)₂,

wherein M is Zr or Hf.

14. The process of claim 1 wherein the catalyst system comprises yet a further metallocene catalyst compound having the general formula (III):

(In³)Y(In⁴)M″

X′

_n;

wherein each of In³ and In⁴ is an unsubstituted the indenyl ring;

Y is a bridging group, such that the number of atoms in the direct chain between the In³ ligand and the In⁴ ligand is 1 to 8, M″

is a transition metal from Group 3, 4, 5 or 6 of the Periodic Table of the Elements, or an actinide or lanthanide metal;

n is equal to the valence of M″

minus 2; and

each X′

is a non-cyclopentadienyl ligand and is, independently, a hydrocarbyl, oxyhydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid, oxyhydrocarbyl-substituted organometalloid or halocarbyl-substituted organometalloid group containing up to about 20 carbon atoms;

provided that two X′

groups may be joined and bound to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms;

or two X′

groups together can be an olefin, diolefin or aryne ligand.

15. The process of claim 14 wherein Y is a bridging group containing a Group 13, 14, 15, or 16 element.

16. The process of claim 14 wherein Y is selected from —

SiR⁴₂—

, —

CR⁴₂—

, and —

CR⁴₂—

CR⁴₂—

;

wherein R⁴, independently, is selected from hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl, and mixtures thereof.

17. The process of claim 14 wherein the compound of formula (III) comprises at least one of rac-(dimethylsilyl)bisindenylzirconium dimethyl and rac-(dimethylsilyl)bisindenylhafnium dimethyl.

18. The process of claim 1 wherein the non-coordinating anion activator is selected from N,N-dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronapthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronapthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and triphenylcarbenium tetra(perfluorophenyl)borate.

19. The process of claim 1 wherein said at least one alpha-olefin comprises a C₃ to C₈ alpha olefin.

20. The process of claim 1 wherein said at least one alpha-olefin is propylene.

21. The process of claim 1 wherein said at least one diene comprises vinyl norbornene (VNB).

22. An elastomer composition obtainable by the process of claim 1.