Tetrahydroindacenyl catalyst composition, catalyst system, and processes for use thereof

• US 9,796,795 B2
• Filed: 05/03/2016
• Issued: 10/24/2017
• Est. Priority Date: 01/14/2015
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Canich, Jo Ann M., Atienza, Crisita Carmen H., Izmer, Vyatcheslav V., Kononovich, Dmitry S., Voskoboynikov, Alexander Z.
• Primary Examiner(s): LU, C CAIXIA
• Application Number:
  US15/145,314
• Publication Number:
  US 20160244535A1
• Time in Patent Office: 539 Days
• CPC Class Codes: C07F 17/00 Metallocenes
• CPC Class Codes: C07F 7/28 Titanium compounds
• 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 110/06 Propene
• CPC Class Codes: C08F 210/02 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 2420/02 Cp or analog bridged to a non-Cp X anionic donor
• 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 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 4/6592 containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: C08F 4/76 selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum

Abstract

This invention relates to a compound represented by the formula: T_yCp′_mMG_nX_q wherein: Cp′ is a tetrahydroindacenyl group which may be substituted or unsubstituted, provided that when Cp′ is tetrahydro-s-indacenyl: 1) the 3 and/or 4 positions are not aryl or substituted aryl, 2) the 3 position is not directly bonded to a group 15 or 16 heteroatom, 3) there are no additional rings fused to the tetrahydroindacenyl ligand, 4) T is not bonded to the 2-position, and 5) the 5, 6, or 7-position is geminally disubstituted; M is a group 3, 4, 5, or 6 transition metal; G is a heteroatom group represented by the formula JRⁱ_z where J is N, P, O or S, Rⁱ is a C₁ to C₂₀ hydrocarbyl group, and z is 1 or 2; T is a bridging group; y is 0 or 1; X is a leaving group; m=1; n=1, 2 or 3; q=1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the transition metal.

Claims

1. A compound represented by the formula:

T_yCp′

_mMG_nX_q

wherein;

Cp′

is a tetrahydroindacenyl group which is optionally substituted or unsubstituted, provided that when Cp′

is tetrahydro-s-indacenyl;

     1) the 3 and/or 4 positions are not aryl or substituted aryl,

     2) the 3 position is not directly bonded to a group 15 or 16 heteroatom,

     3) there are no additional rings fused to the tetrahydroindacenyl ligand,

     4) T is not bonded to the 2-position, and

     5) the 5, 6, or 7-position is geminally disubstituted;

M is a group 3, 4, 5, or 6 transition metal;

G is a heteroatom group represented by the formula JRⁱ_z where J is N, P, O or S, Rⁱ is a C₁ to C₂₀ hydrocarbyl group, and z is 1 or 2;

T is a bridging group;

y is 0 or 1;

X is a leaving group;

m=1;

n=1, 2 or 3;

q=1, 2 or 3; and

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

4. The catalyst compound of claim 1, wherein M is Ti.

5. The compound of claim 1, where J is N, and R′

is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof.

9. The compound of claim 1, wherein the sum of m+n+q is equal to 3, 4, 5, or 6.

10. The compound of claim 1, wherein the Cp′

is tetrahydro-s-indacenyl and the 6 position is geminally disubstituted with two C₁-C₁₀ alkyl groups.

11. The compound of claim 1, wherein the Cp′

is tetrahydro-s-indacenyl and the 6 position is geminally disubstituted with two alkyl groups selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl and isomers thereof.

12. The compound of claim 1, wherein the Cp′

is tetrahydro-s-indacenyl and the 3 and 4 positions are not aryl or substituted aryl.

14. The compound of claim 1, where J is N, and Rⁱ is t-butyl, hexyl, neopentyl, cyclohexyl, cyclooctyl, cyclododecyl, adamantyl, or norbornyl.

17. A catalyst system comprising the compound of claim 1 and an activator.

18. The catalyst system of claim 17, wherein the activator comprises a non-coordinating anion activator and/or an alumoxane.

19. The catalyst system of claim 17, where the catalyst system is supported.

20. A process to produce olefin polymer comprising contacting olefin monomer with the catalyst system of claim 17.

21. The process of claim 20, wherein the monomer comprises ethylene and/or propylene.

22. The process of claim 20, wherein the catalyst system comprises one catalyst compound.

23. The process of claim 20, wherein the process occurs at a temperature of from about 0°

C. to about 300°

C., at a pressure in the range of from about 0.35 MPa to about 16 MPa, and at a time up to 300 minutes.

24. The process of claim 20, wherein the monomer comprises two or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, or dodecene.

25. The process of claim 20, wherein the monomer comprises ethylene, propylene and 5-ethylidene-2-norbornene.

2. A compound represented by the formula (I):

6. The catalyst compound of claim 2 wherein R², R³, R⁴, and/or R⁷, are not aryl or substituted aryl.

8. The compound of claim 2, wherein each R^a is independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof.

3. A compound represented by the formula (III):

7. The catalyst compound of claim 3, wherein R², R³, R⁶, and/or R⁷, are not aryl or substituted aryl.

13. The compound of claim 3, wherein each R^b is independently a C₁-C₁₀ alkyl.

16. The compound of claim 3, wherein the compound is represented by the formula:

15. A composition comprising one or more of:

dimethylsilylene(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R)₂;

dimethylsilylene(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂;

dimethylsilylene(6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R)₂;

dimethylsilylene (6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂;

dimethylsilylene(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R)₂;

dimethylsilylene(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R)₂,

dimethylsilylene(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R)₂;

dimethylsilylene(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R)₂;

μ

-(CH₃)₂Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(2-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(2-methyl-7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂;

μ

-(CH₃)₂Si(6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂;

μ

-(CH₃)₂Si(2-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂;

μ

-(CH₃)₂Si(6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂;

μ

-(CH₃)₂Si(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R)₂;

μ

-(CH₃)₂Si(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R)₂;

μ

-(CH₃)₂Si(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R)₂;

μ

-(CH₃)₂Si(2-methyl-7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R)₂;

μ

-(CH₃)₂Si(7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R)₂;

μ

-(CH₃)₂Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R)₂;

μ

-(CH₃)₂Si(6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R)₂;

μ

-(CH₃)₂Si(2-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R)₂;

μ

-(CH₃)₂Si(6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R)₂;

μ

-(CH₃)₂Si(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R)₂;

μ

-(CH₃)₂Si(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R)₂;

μ

-(CH₃)₂Si(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R)₂;

μ

-(CH₃)₂Si(2-methyl-7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R)₂;

μ

-(CH₃)₂Si(7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R)₂;

μ

-(CH₂)₃Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂;

μ

-(CH₂)₄Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂;

μ

-(CH₂)₅Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂;

μ

-(CH₃)₂C(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂;

μ

-(CH₂)₃Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂;

μ

-(CH₂)₄Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂;

μ

-(CH₂)₅Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂;

μ

-(CH₃)₂C(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R)₂; and

μ

-(CH₃)₂Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(neopentylamido)M(R)₂;

where M is selected from a group consisting of Ti, Zr, and Hf and R is selected from halogen and C₁ to C₅ alkyl.