Process of Producing Polyolefins Using Metallocene Polymerization Catalysts and Copolymers Therefrom

• US 20140316085A1
• Filed: 04/09/2014
• Published: 10/23/2014
• Est. Priority Date: 04/11/2013
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Stewart, Ian C., Brown, Steven D., Harris, David T., Atienza, Crisita Carmen H., Hollas, Aaron M.
• Granted Patent: US 9,611,348 B2
• Time in Patent Office: Days
• US Class Current: 526/126
• 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 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 2500/20 Activation energy or enthalpy
• 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 4/65927 two cyclopentadienyl rings being mutually bridged

Abstract

An ethylene copolymer, a Group 4 transition metal catalyst compound, and methods for polymerization using such a compound, said compound represented by the formula: (L)_p(R′)_zT(Cp)(A)MX₂, where M is a Group 4 metal; z is 0 to 8; p is 1 to 3; X is an anionic leaving group; T is a bridging group; R¹ to R⁴ are hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, aryl group, substituted aryl group, or a heteroatom-containing group (where adjacent R groups can form rings); R′ is hydrogen, a C₁ to C₁₀ alkyl group, a C₆ to C₂₄ aryl group, or a C₇ to C₄₀ alkylaryl group; and L is a heteroatom or heteroatom-containing group bound to T, Cp is a cyclopentadienyl ring substituted with 0 to 4 substituent groups (where adjacent groups can form C₄ to C₂₀ rings); A is Cp or (JS′_z*-1-y), where J is a Group 15 or 16 element; S′ is a hydrocarbyl, substituted hydrocarbyl, or heteroatom; z* is 2 or 3, and y is 0 or 1, is provided.

Claims

1. A process for producing a polyolefin comprising contacting one or more olefin monomers with a catalyst system comprising:

1) an activator; and

2) a catalyst compound represented by the formula;

(L)_p(R′

)_zT(Cp)(A)MX₂

wherein;

Cp is a cyclopentadienyl ring substituted with 0, 1, 2, 3, or 4 substituent groups S″

, each substituent group S″

being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, or heteroatom or Cp is a cyclopentadienyl ring in which any two adjacent S″

groups are joined forming a C₄ to C₂₀ ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand, such as substituted or unsubstituted indenyl or flourenyl, where A is bound to M and T, Cp is bound to M and T, and L and R′

are bound to T;

M is a Group 4 transition metal;

z is 0, 1, 2, 3, 4, 5, 6, 7, or 8 indicating the number of R′

groups bound to the bridging group T,

p is 1, 2, or 3 indicating the number of L groups bound to the bridging group T;

each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof, provided that two X'"'"'s may form a part of a fused ring or a ring system;

T is a bridging group;

each R¹, R², R³, and R⁴ is, independently, hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, an aryl group, a substituted aryl group, or a heteroatom-containing group, provided that any of adjacent R¹, R², R³, and R⁴ groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated;

each R′

is, independently, hydrogen, a C₁ to C₁₀ alkyl group, a C₆ to C₂₄ aryl group, or a C₇ to C₄₀ alkylaryl group;

each L is a heteroatom or heteroatom-containing group bound to T;

A is Cp or (JS′

_z*-1-y), where JS′

_z*-1-y is a heteroatom ligand in which J is an element from Group 15 with a coordination number of 3 or an element from Group 16 with a coordination number of 2;

S′

is a radical group which is a hydrocarbyl, substituted hydrocarbyl, or heteroatom; and

z* is the coordination number of the element J, and y is 0 or 1.

2. The process of claim 1 wherein the catalyst compound is represented by the formula:

3. The process of claim 2, wherein the catalyst compound is represented by the formula:

4. The process of claim 1 wherein the catalyst compound is represented by the formula:

5. The process of claim 1, wherein the olefin monomers are ethylene and one or more C₃ to C₂₀ comonomers.

6. The process of claim 1, wherein L is represented by the formulae:

7. The process of claim 1, wherein each L comprises one or more of perfluoroethyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, nonafluorohexyl, pentafluorophenyl, 2-fluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2-dimethylaminophenyl, 2,3-bis(dimethylamino)phenyl, 2,4-bis(dimethylamino)phenyl, 2,5-bis(dimethylamino)phenyl, 2,6-bis(dimethylamino)phenyl, 2,4,6-tris(dimethylamino)phenyl,2-diethylaminophenyl, 2,3-bis(diethylamino)phenyl, 2,4-bis(diethylamino)phenyl, 2,5-bis(diethylamino)phenyl, 2,6-bis(diethylamino)phenyl, 2,4,6-tris(diethylamino)phenyl,2-diisopropylaminophenyl, 2,3-bis(diisopropylamino)phenyl, 2,4-bis(diisopropylamino)phenyl, 2,5-bis(diisopropylamino)phenyl, 2,6-bis(diisopropylamino)phenyl, 2,4,6-tris(diisopropylamino)phenyl,2-dimethylphosphinophenyl, 2,3-bis(dimethylphosphino)phenyl, 2,4-bis(dimethylphosphino)phenyl, 2,5-bis(dimethylphosphino)phenyl, 2,6-bis(dimethylphosphino)phenyl, 2,4,6-tris(dimethylphosphino)phenyl,2-diethylphosphinophenyl, 2,3-bis(diethylphosphino)phenyl, 2,4-bis(diethylphosphino)phenyl, 2,5-bis(diethylphosphino)phenyl, 2,6-bis(diethylphosphino)phenyl, 2,4,6-tris(diethylphosphino)phenyl,2-diisopropylphosphinophenyl, 2,3-bis(diisopropylphosphino)phenyl, 2,4-bis(diisopropylphosphino)phenyl, 2,5-bis(diisopropylphosphino)phenyl, 2,6-bis(diisopropylphosphino)phenyl, 2,4,6-tris(diisopropylphosphino)phenyl,2-hydroxyphenyl, 2,3-dihydroxyphenyl, 2,4-dihydroxyphenyl, 2,5-dihydroxyphenyl, 2,6-dihydroxyphenyl, 2,4,6-trihydroxylphenyl, 2,3,5,6-tetrahydroxyphenyl, 2,3,4,5,6-pentahydroxyphenyl,2-methoxyphenyl, 2-methoxy-5-fluorophenyl, 2,3-dimethoxyphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxylphenyl, 2,3,5,6-tetramethoxyphenyl, 2,3,4,5,6-pentamethoxyphenyl,2-ethoxyphenyl, 2-ethoxy-5-fluorophenyl, 2,3-diethoxyphenyl, 2,4-diethoxyphenyl, 2,5-diethoxyphenyl, 2,6-diethoxyphenyl, 2,4,6-triethoxylphenyl, 2,3,5,6-tetrathoxyphenyl, 2,3,4,5,6-pentaethoxyphenyl,2-isopropoxyphenyl, 2-isopropoxy-5-fluorophenyl, 2,3-diisopropoxyphenyl, 2,4-diisopropoxyphenyl, 2,5-diisopropoxyphenyl, 2,6-diisopropoxyphenyl, 2,4,6-triisopropoxylphenyl, 2,3,5,6-tetraisoproxyphenyl, 2,3,4,5,6-pentaisopropoxyphenyl, 2-methylthiophenyl, 2-methylthio-5-fluorophenyl, 2,3-dimethylthiophenyl, 2,4-dimethylthiophenyl, 2,5-dimethylthiophenyl, 2,6-dimethylthiophenyl, 2,4,6-trimethylthiolphenyl, 2,3,5,6-tetramethylthiophenyl, 2,3,4,5,6-pentamethylthiophenyl, 2-ethylthiophenyl, 2-ethylthio-5-fluorophenyl, 2,3-diethylthiophenyl, 2,4-diethylthiophenyl, 2,5-diethylthiophenyl, 2,6-diethylthiophenyl, 2,4,6-triethylthiolphenyl, 2,3,5,6-tetraethylthiophenyl, 2,3,4,5,6-pentaethylthiophenyl, 2-isopropylthiophenyl, 2-isopropylthio-5-fluorophenyl, 2,3-dimthylthiophenyl, 2,4-diisopropylthiophenyl, 2,5-diisopropylthiophenyl, 2,6-diisopropylthiophenyl, 2,4,6-triisopropylthiolphenyl, 2,3,5,6-tetraisopropylthiophenyl, 2,3,4,5,6-pentaisopropylthiophenyl, 2-tert-butylthiophenyl, 2-tert-butylthio-5-fluorophenyl, 2,3-dimthylthiophenyl, 2,4-ditert-butylthiophenyl, 2,5-ditert-butylthiophenyl, 2,6-ditert-butylthiophenyl, 2,4,6-tritert-butylthiolphenyl, 2,3,5,6-tetratert-butylthiophenyl, 2,3,4,5,6-pentatert-butylthiophenyl, dimethylaminomethyl, diethylaminomethyl, di-n-propylaminomethyl, di-isopropylaminomethyl, diphenylaminomethyl, 2-dimethylaminoethyl, 2-diethylaminoethyl, 2-di-n-propylaminoethyl, 2-di-iso-propylaminoethyl, 2-diphenylaminoethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, 3-di-n-propylaminopropyl, 3-di-isopropylaminopropyl, 3-diphenylaminopropyl, 4-dimethylaminobutyl, 4-diethylaminobutyl, 4-di-n-propylaminobutyl, 4-di-iso-propylaminobutyl, 4-diphenylaminobutyl, dimethylphosphinomethyl, diethylphosphinomethyl, di-n-propylphosphinomethyl, di-isopropylphosphinomethyl, diphenylphosphinomethyl, 2-dimethylphosphinoethyl, 2-diethylphosphinoethyl, 2-di-n-propylphosphinoethyl, 2-di-iso-propylphosphinoethyl, 2-diphenylphosphinoethyl, 3-dimethylphosphinopropyl, 3-diethylphosphinopropyl, 3-di-n-propylphosphinopropyl, 3-di-isopropylphosphinopropyl, 3-diphenylphosphinopropyl, 4-dimethylphosphinobutyl, 4-diethylphosphinobutyl, 4-di-n-propylphosphinobutyl, 4-di-iso-propylphosphinobutyl, 4-diphenylphosphinobutyl, methoxymethyl, ethyoxymethyl, propoxymethyl, isopropoxymethyl, tert-butoxymethyl, phenoxymethyl 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-tert-butoxyethyl, 2-phenoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-n-propoxypropyl, 3-isopropoxypropyl, 3-diphenoxypropyl, 4-methoxybutyl, 4-ethyoxybutyl, 4-n-propoxybutyl, 4-isopropoxybutyl, 4-phenoxybutyl, methylthiomethyl, ethylthiomethyl, propylthiomethyl, isopropylthiomethyl, tert-butylthiomethyl, phenylthiomethyl, 2-methylthioethyl, 2-propylthioethyl, 2-isopropylthioethyl, 2-tert-butylthioethyl, 2-phenylthioethyl, 3-methylthiopropyl, 3-ethylthiopropyl, 3-n-propylthiopropyl, 3-isoprylthiopropyl, 3-diphenylthiopropyl, 4-methylthiobutyl, 4-ethylthiobutyl, 4-n-propylthiobutyl, 4-isopylthiobutyl, 4-phenylthiobutyl, 2-dimethylphosphinophenyl, 2-diphenylphosphinophenl, 2-dicyclohexylphosphinophenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-(4-dimethylaminopyridyl), 3-(4-dimethylaminopyridyl), 4-(4-dimethylaminopyridyl), 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 6-pyrimidyl, 2-quinolyl, 2-isoquinolyl, 2-tetrahydroisoquinolyl, 4-acridinyl, and 4-(5-methylacridinyl).

8. The process of claim 1, wherein the olefin monomers are ethylene and one or more C₃ to C₂₀ comonomers, said process further comprising obtaining copolymer having a DSC peak melting temperature, T_m, greater than the line represented by T_m=132−

(6.25·

M %), where M % is the mol % comonomer.

9. The process of claim 8, wherein one, two, or three CEF elution peaks are exhibited below 110°

C., and no CEF elution is exhibited above 110°

C.

10. The process of claim 8, wherein a single CEF elution peaks occurs within a range of from 60°

C. to 110°

C.

11. The process of claim 1, wherein no more than one olefin polymerization catalyst is present in the catalyst system.

12. The process of claim 5, wherein the comonomer is propylene, 1-butene, 1-hexene, or 1-octene.

13. The process of claim 1, wherein the process comprises producing an ethylene copolymer having from 0.2 mol % to 20 mol % comonomer and a DSC peak T_m of 100°

C. to 130°

C.

14. The process of claim 1, wherein each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms and halides.

15. The process of claim 3, wherein all R¹ to R¹² groups are hydrogen.

16. The process of claim 3, wherein groups R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are, independently, hydrogen, methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, or phenyl.

17. The process of claim 1, wherein T(L)_p(R′

)_z is represented by one or more of the groups;

R′

₂C, R′

₂Si, R′

₂Ge, R′

₂C═

CR′

₂, R′

₂C═

CR′

₂CR′

₂, R′

₂C═

CR′

₂CR′

₂CR′

₂, R′

C═

CR′

, R′

C═

CR′

CR′

₂, R′

₂C═

CR′

═

CR′

CR′

₂, R′

C═

CR′

CR′

═

CR′

, R′

C═

CR′

CR′

₂CR′

₂, R′

₂C═

SiR′

₂, R′

₂SiSiR′

₂, R₂C═

SiR′

₂CR′

₂, R′

₂Si═

CR′

₂SiR′

₂, R′

C═

CR′

SiR′

₂, R′

₂C═

GeR′

₂, R′

₂Ge═

GeR′

₂, R′

₂C═

GeR′

₂CR′

₂, R′

₂Ge═

CR′

₂GeR′

₂, R′

₂Si═

GeR′

₂, R′

C═

CR′

GeR′

₂, R′

B, R′

₂C—

BR′

, R′

₂C—

BR′

—

CR′

₂, R′

₂C—

O—

CR′

₂, R′

₂CR′

₂C—

O—

CR′

₂CR′

₂, R′

₂C—

O—

CR′

₂CR′

₂, R′

₂C—

O—

CR′

═

CR′

, R′

₂C—

S—

CR′

₂, R′

₂CR′

2C—

S—

CR′

₂CR′

₂, R′

₂C—

S—

CR′

₂CR′

₂, R′

₂C—

S—

CR′

═

CR′

, R′

₂C—

Se—

CR′

₂, R′

₂CR′

₂C—

Se—

CR′

₂CR′

₂, R′

₂C—

Se—

CR₂CR′

₂, R′

₂C—

Se—

CR′

═

CR′

, R′

₂C—

N═

CR′

, R′

₂C—

NR′

—

CR′

₂, R′

₂C—

NR′

—

CR′

₂CR′

₂, R′

₂C—

NR′

—

CR′

═

CR′

, R′

₂CR′

₂C—

NR′

—

CR′

₂CR′

₂, R′

₂C—

P═

CR′

, and R′

₂C—

PR′

—

CR′

₂ where R′

is hydrogen or a C₁ to C₁₀ or C₂₀ hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, aryl, substituted aryl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R′

may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent; and

provided that at least one of the R′

groups is substituted by an L, where L is as defined in claim 1.

18. The process of claim 1, wherein T(L)_p(R′

)_z is selected from C(L)H, C(L)HCH₂, C(L)CH₃, Si(L)CH₃, Si(L)Ph, Si(L)CH₃, C(L)Ph, C(CR₂)_n(L), C(CR₂)_n(CRL), Si(CR₂)_n(L), and Si(CR)_n(CRL), where R is hydrogen or a C₁ to C₈ or C₂₀ containing hydrocarbyl or substituted hydrocarbyl, L is as defined in claim 1 and n is 1, 2, 3, or 4.

19. The process of claim 1, wherein the activator comprises alumoxane.

20. The process of claim 1, wherein the activator comprises a non-coordinating anion activator.

21. The process of claim 1, wherein the activator is represented by the formula:

(Z)_d⁺(Ar^d−

)

wherein Z is (Lb-H) or a reducible Lewis Acid, Lb is a neutral Lewis base;

H is hydrogen;

(Lb-H)⁺ is a Bronsted acid;

Ar^d−

non-coordinating anion having the charge d− and

having the charge d−

; and

d is an integer from 1 to 3.

22. The process of claim 1, wherein the activator is represented by the formula:

(Z)_d⁺(Ar)_d−

wherein Ar^d−

is a non-coordinating anion having the charge d−

;

d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the formula;

(Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀ hydrocarbyl.

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

23. A catalyst compound represented by the formula:

(L)_p(R′

)_zT(Cp)(A)MX₂

wherein;

Cp is a cyclopentadienyl ring substituted with 0, 1, 2, 3, or 4 substituent groups S″

, each substituent group S″

being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, or heteroatom or Cp is a cyclopentadienyl ring in which any two adjacent S″

groups are joined forming a C₄ to C₂₀ ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand, such as substituted or unsubstituted indenyl or flourenyl, where A is bound to M and T, Cp is bound to M and T and L and R′

are bound to T;

M is a Group 4 transition metal;

z is 0, 1, 2, 3, 4, 5, 6, 7, or 8 indicating the number of R′

groups bound to the bridging group T,

p is 1, 2 or 3 indicating the number of L groups bound to the bridging group T;

each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof, provided that two X'"'"'s may form a part of a fused ring or a ring system;

T is a bridging group;

each R¹, R², R³, and R⁴ is, independently, hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, an aryl group, a substituted aryl group, or a heteroatom-containing group, provided that any of adjacent R¹, R², R³, and R⁴ groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated;

each R′

is, independently, hydrogen, a C₁ to C₁₀ alkyl group, a C₆ to C₂₄ aryl group, or a C₇ to C₄₀ alkylaryl group;

each L is a heteroatom or heteroatom-containing group bound to T;

A is Cp or (JS′

_z*-1-y), where JS′

_z*-1-y is a heteroatom ligand in which J is an element from Group 15 with a coordination number of 3 or an element from Group 16 with a coordination number of 2;

S′

is a radical group which is a hydrocarbyl, substituted hydrocarbyl, or heteroatom; and

z* is the coordination number of the element J, and y is 0 or 1.

24. The catalyst compound of claim 23 wherein the compound is represented by the formula:

25. The catalyst compound of claim 24, wherein the catalyst compound is represented by the formula:

26. The catalyst compound of claim 23, wherein the catalyst compound is represented by the formula:

27. The catalyst compound of claim 23, wherein L is represented by the formula:

28. The catalyst compound of claim 23, wherein each L comprises one or more of perfluoroethyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, nonafluorohexyl, pentafluorophenyl, 2-fluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2-dimethylaminophenyl, 2,3-bis(dimethylamino)phenyl, 2,4-bis(dimethylamino)phenyl, 2,5-bis(dimethylamino)phenyl, 2,6-bis(dimethylamino)phenyl, 2,4,6-tris(dimethylamino)phenyl,2-diethylaminophenyl, 2,3-bis(diethylamino)phenyl, 2,4-bis(diethylamino)phenyl, 2,5-bis(diethylamino)phenyl, 2,6-bis(diethylamino)phenyl, 2,4,6-tris(diethylamino)phenyl,2-diisopropylaminophenyl, 2,3-bis(diisopropylamino)phenyl, 2,4-bis(diisopropylamino)phenyl, 2,5-bis(diisopropylamino)phenyl, 2,6-bis(diisopropylamino)phenyl, 2,4,6-tris(diisopropylamino)phenyl,2-dimethylphosphinophenyl, 2,3-bis(dimethylphosphino)phenyl, 2,4-bis(dimethylphosphino)phenyl, 2,5-bis(dimethylphosphino)phenyl, 2,6-bis(dimethylphosphino)phenyl, 2,4,6-tris(dimethylphosphino)phenyl,2-diethylphosphinophenyl, 2,3-bis(diethylphosphino)phenyl, 2,4-bis(diethylphosphino)phenyl, 2,5-bis(diethylphosphino)phenyl, 2,6-bis(diethylphosphino)phenyl, 2,4,6-tris(diethylphosphino)phenyl,2-diisopropylphosphinophenyl, 2,3-bis(diisopropylphosphino)phenyl, 2,4-bis(diisopropylphosphino)phenyl, 2,5-bis(diisopropylphosphino)phenyl, 2,6-bis(diisopropylphosphino)phenyl, 2,4,6-tris(diisopropylphosphino)phenyl,2-hydroxyphenyl, 2,3-dihydroxyphenyl, 2,4-dihydroxyphenyl, 2,5-dihydroxyphenyl, 2,6-dihydroxyphenyl, 2,4,6-trihydroxylphenyl, 2,3,5,6-tetrahydroxyphenyl, 2,3,4,5,6-pentahydroxyphenyl,2-methoxyphenyl, 2-methoxy-5-fluorophenyl, 2,3-dimethoxyphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxylphenyl, 2,3,5,6-tetramethoxyphenyl, 2,3,4,5,6-pentamethoxyphenyl,2-ethoxyphenyl, 2-ethoxy-5-fluorophenyl, 2,3-diethoxyphenyl, 2,4-diethoxyphenyl, 2,5-diethoxyphenyl, 2,6-diethoxyphenyl, 2,4,6-triethoxylphenyl, 2,3,5,6-tetrathoxyphenyl, 2,3,4,5,6-pentaethoxyphenyl,2-isopropoxyphenyl, 2-isopropoxy-5-fluorophenyl, 2,3-diisopropoxyphenyl, 2,4-diisopropoxyphenyl, 2,5-diisopropoxyphenyl, 2,6-diisopropoxyphenyl, 2,4,6-triisopropoxylphenyl, 2,3,5,6-tetraisoproxyphenyl, 2,3,4,5,6-pentaisopropoxyphenyl, 2-methylthiophenyl, 2-methylthio-5-fluorophenyl, 2,3-dimethylthiophenyl, 2,4-dimethylthiophenyl, 2,5-dimethylthiophenyl, 2,6-dimethylthiophenyl, 2,4,6-trimethylthiolphenyl, 2,3,5,6-tetramethylthiophenyl, 2,3,4,5,6-pentamethylthiophenyl, 2-ethylthiophenyl, 2-ethylthio-5-fluorophenyl, 2,3-diethylthiophenyl, 2,4-diethylthiophenyl, 2,5-diethylthiophenyl, 2,6-diethylthiophenyl, 2,4,6-triethylthiolphenyl, 2,3,5,6-tetraethylthiophenyl, 2,3,4,5,6-pentaethylthiophenyl, 2-isopropylthiophenyl, 2-isopropylthio-5-fluorophenyl, 2,3-dimthylthiophenyl, 2,4-diisopropylthiophenyl, 2,5-diisopropylthiophenyl, 2,6-diisopropylthiophenyl, 2,4,6-triisopropylthiolphenyl, 2,3,5,6-tetraisopropylthiophenyl, 2,3,4,5,6-pentaisopropylthiophenyl, 2-tert-butylthiophenyl, 2-tert-butylthio-5-fluorophenyl, 2,3-dimthylthiophenyl, 2,4-ditert-butylthiophenyl, 2,5-ditert-butylthiophenyl, 2,6-ditert-butylthiophenyl, 2,4,6-tritert-butylthiolphenyl, 2,3,5,6-tetratert-butylthiophenyl, 2,3,4,5,6-pentatert-butylthiophenyl, dimethylaminomethyl, diethylaminomethyl, di-n-propylaminomethyl, di-isopropylaminomethyl, diphenylaminomethyl, 2-dimethylaminoethyl, 2-diethylaminoethyl, 2-di-n-propylaminoethyl, 2-di-iso-propylaminoethyl, 2-diphenylaminoethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, 3-di-n-propylaminopropyl, 3-di-isopropylaminopropyl, 3-diphenylaminopropyl, 4-dimethylaminobutyl, 4-diethylaminobutyl, 4-di-n-propylaminobutyl, 4-di-iso-propylaminobutyl, 4-diphenylaminobutyl, dimethylphosphinomethyl, diethylphosphinomethyl, di-n-propylphosphinomethyl, di-isopropylphosphinomethyl, diphenylphosphinomethyl, 2-dimethylphosphinoethyl, 2-diethylphosphinoethyl, 2-di-n-propylphosphinoethyl, 2-di-iso-propylphosphinoethyl, 2-diphenylphosphinoethyl, 3-dimethylphosphinopropyl, 3-diethylphosphinopropyl, 3-di-n-propylphosphinopropyl, 3-di-isopropylphosphinopropyl, 3-diphenylphosphinopropyl, 4-dimethylphosphinobutyl, 4-diethylphosphinobutyl, 4-di-n-propylphosphinobutyl, 4-di-iso-propylphosphinobutyl, 4-diphenylphosphinobutyl, methoxymethyl, ethyoxymethyl, propoxymethyl, isopropoxymethyl, tert-butoxymethyl, phenoxymethyl 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-tert-butoxyethyl, 2-phenoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-n-propoxypropyl, 3-isopropoxypropyl, 3-diphenoxypropyl, 4-methoxybutyl, 4-ethyoxybutyl, 4-n-propoxybutyl, 4-isopropoxybutyl, 4-phenoxybutyl, methylthiomethyl, ethylthiomethyl, propylthiomethyl, isopropylthiomethyl, tert-butylthiomethyl, phenylthiomethyl, 2-methylthioethyl, 2-propylthioethyl, 2-isopropylthioethyl, 2-tert-butylthioethyl, 2-phenylthioethyl, 3-methylthiopropyl, 3-ethylthiopropyl, 3-n-propylthiopropyl, 3-isoprylthiopropyl, 3-diphenylthiopropyl, 4-methylthiobutyl, 4-ethylthiobutyl, 4-n-propylthiobutyl, 4-isopylthiobutyl, 4-phenylthiobutyl, 2-dimethylphosphinophenyl, 2-diphenylphosphinophenl, 2-dicyclohexylphosphinophenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-(4-dimethylaminopyridyl), 3-(4-dimethylaminopyridyl), 4-(4-dimethylaminopyridyl), 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 6-pyrimidyl, 2-quinolyl, 2-isoquinolyl, 2-tetrahydroisoquinolyl, 4-acridinyl, and 4-(5-methylacridinyl).

29. The catalyst compound of claim 23, wherein the catalyst compound is part of an olefin polymerization catalyst system further comprising an activator.

30. The catalyst compound of claim 29, wherein no more than one olefin polymerization catalyst is present in the catalyst system.

31. The catalyst compound of claim 23, wherein each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms and halides.

32. The catalyst compound of claim 25, wherein all R¹ to R¹² groups are hydrogen.

33. The catalyst compound of claim 25, wherein groups R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are, independently, hydrogen, methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, or phenyl.

34. The catalyst compound of claim 23, wherein T(L)p(R′

)z is represented by one or more of the groups;

R′

₂C, R′

₂Si, R′

₂Ge, R′

₂C═

CR′

₂, R′

₂C═

CR′

₂CR′

₂, R′

₂C═

CR′

₂CR′

₂CR′

₂, R′

C═

CR′

, R′

C═

CR′

CR′

₂, R′

₂C═

CR′

═

CR′

CR′

₂, R′

C═

CR′

CR′

═

CR′

, R′

C═

CR′

CR′

₂CR′

₂, R′

₂C═

SiR′

₂, R′

₂SiSiR′

₂, R₂C═

SiR′

₂CR′

₂, R′

₂Si═

CR′

₂SiR′

₂, R′

C═

CR′

SiR′

₂, R′

₂C═

GeR′

₂, R′

₂Ge═

GeR′

₂, R′

₂C═

GeR′

₂CR′

₂, R′

₂Ge═

CR′

₂GeR′

₂, R′

₂Si═

GeR′

₂, R′

C═

CR′

GeR′

₂, R′

B, R′

₂C—

BR′

, R′

₂C—

BR′

—

CR′

₂, R′

₂C—

O—

CR′

₂, R′

₂CR′

₂C—

O—

CR′

₂CR′

₂, R′

₂C—

O—

CR′

₂CR′

₂, R′

₂C—

O—

CR′

═

CR′

, R′

₂C—

S—

CR′

₂, R′

₂CR′

2C—

S—

CR′

₂CR′

₂, R′

₂C—

S—

CR′

₂CR′

₂, R′

₂C—

S—

CR′

═

CR′

, R′

₂C—

Se—

CR′

₂, R′

₂CR′

₂C—

Se—

CR′

₂CR′

₂, R′

₂C—

Se—

CR₂CR′

₂, R′

₂C—

Se—

CR′

═

CR′

, R′

₂C—

N═

CR′

, R′

₂C—

NR′

—

CR′

₂, R′

₂C—

NR′

—

CR′

₂CR′

₂, R′

₂C—

NR′

—

CR′

═

CR′

, R′

₂CR′

₂C—

NR′

—

CR′

₂CR′

₂, R′

₂C—

P═

CR′

, and R′

₂C—

PR′

—

CR′

₂ where R′

is hydrogen or a C₁ to C₂₀ hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, aryl, substituted aryl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R′

may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent;

provided that at least one of the R′

groups is substituted by an L, where each L is a heteroatom or heteroatom-containing group.

35. The catalyst compound of claim 23, wherein T(L)_p(R′

)_z is selected from C(L)H, C(L)HCH₂, C(L)CH₃, Si(L)CH₃, Si(L)Ph, Si(L)CH₃, C(L)Ph, C(CR₂)_n(L), C(CR₂)_n(CRL), Si(CR₂)_n(L), Si(CR)_n(CRL), where R′

is hydrogen or a C₁ to C₈ or C₂₀ containing hydrocarbyl or substituted hydrocarbyl, and n is 1, 2, 3, or 4, and each L is a heteroatom or heteroatom-containing group.

36. An ethylene copolymer comprising ethylene and a C₃ to C₂₀ α

-olefin, wherein the copolymer has a DSC peak melting temperature, T_m, greater than the line represented by T_m=132−

(6.25·

M %), where M % is the mol % comonomer.

37. The copolymer of claim 36, wherein one, two, or three CEF elution peaks are exhibited below 110°

C., and no CEF elution is exhibited above 110°

C.

38. The copolymer of claim 36, wherein a single CEF elution peaks occurs within a range of from 60°

C. to 110°

C.

39. The copolymer of claim 36, having an Mw of 10,000 to 2,000,000 g/mol.

40. The copolymer of claim 36, made by a process comprising contacting ethylene and one or more C₃ to C₂₀ comonomers;

with a catalyst system comprising;

1) an activator; and

2) a catalyst compound represented by the formula;