Substituted pyridyl amine catalysts and processes for polymerizing and polymers

• US 20020147288A1
• Filed: 11/06/2001
• Published: 10/10/2002
• Est. Priority Date: 11/07/2000
• Status: Active Grant

• Current Assignee: Freeslate Inc. (Unchained Labs Inc.)
• Original Assignee: Anne M. Lapointe, Cheryl Lund, Christopher Goh, Gary M. Diamond, Keith A. Hall, Margarete K. Leclerc, Thomas R. Boussie, Vince Murphy
• Inventors: Boussie, Thomas R., Goh, Christopher, Leclerc, Margarete K., Murphy, Vince, LaPointe, Anne M., Hall, Keith A., Diamond, Gary M., Lund, Cheryl
• Granted Patent: US 6,713,577 B2
• Time in Patent Office: Days
• US Class Current: 526/160
• CPC Class Codes: B01J 2219/00722 Nucleotides
• CPC Class Codes: C07B 2200/11 Compounds covalently bound to a solid support
• CPC Class Codes: C07D 213/38 having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
• CPC Class Codes: C07D 213/61 Halogen atoms or nitro radicals
• CPC Class Codes: C07D 213/68 attached in position 4
• CPC Class Codes: C07D 213/74 Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
• CPC Class Codes: C07F 7/00 Compounds containing elements of Groups 4 or 14 of the Periodic Table
• CPC Class Codes: C07F 7/003 without C-Metal linkages
• CPC Class Codes: C07F 9/58 Pyridine rings
• 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 210/02 Ethene
• CPC Class Codes: C08F 210/10 Isobutene
• 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 212/08 Styrene
• CPC Class Codes: C08F 2500/02 Low molecular weight, e.g. <100,000 Da.
• CPC Class Codes: C08F 2500/15 Isotactic
• CPC Class Codes: C08F 4/64044 NN
• CPC Class Codes: C08F 4/64113 NNN
• CPC Class Codes: C08F 4/64144 : NN(R)C
• CPC Class Codes: C08F 4/659 : Component covered by group C08F4/64 containing a transition metal-carbon bond C08F4/64003 - C08F4/64196 take precedence
• 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 4/65912 : in combination with an organoaluminium compound
• CPC Class Codes: C40B 40/14 : Libraries containing macromolecular compounds and not covered by groups C40B40/06 - C40B40/12

Abstract

New ligands, compositions, metal-ligand complexes and arrays with pyridyl-amine ligands are disclosed that catalyze the polymerization of monomers into polymers. Certain of these catalysts with hafnium metal centers have high performance characteristics, including higher comonomer incorporation into ethylene/olefin copolymers, where such olefins are for example, 1-octene, isobutylene or styrene. Certain of the catalysts are particularly effective at polymerizing propylene to high molecular weight isotactic polypropylene in a solution process at a variety of polymerization conditions.

Claims

1. A process for the polymerization of monomers, said process employing a composition comprising:

(1) a ligand characterized by the following general formula;

wherein Ris selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl and combinations thereof.

T is —

CR²R³— and

R² are R³ are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof,

R⁴, R⁵, R⁶ and R⁷ are each independently selected from the group consisting of is hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof; and

optionally, any combination of R¹, R², R³, R⁴, R⁵, or R⁶ may be joined together in a ring structure;

provided that either R³ or R⁷ is selected only from the group consisting of aryl, substituted aryl, heteroaryl and substituted heteroaryl;

(2) a metal precursor compound characterized by the general formula Hf(L)_n, wherein each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure;

n is 1, 2, 3, 4, 5, or 6; and

(3) optionally, at least one activator.

2. The process of claim 1, wherein said ligand is characterized by the general formula:

3. The process of claim 1, wherein said ligand is characterized by the general formula:

4. The process of claim 3, wherein said ligand is characterized by the formula:

13. The process of either of claims 1,3,5,7,9,10 or 11, wherein R¹ is characterized by the general formula:

14. The process of either of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, wherein said process employs at least one activator.

16. The process of either of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, wherein said process employs at least one monomer that is an olefin, diolefin or unsaturated compound.

5. A process for the polymerization of monomers, said process employing a metal-ligand complex characterized by the following formula:

6. The process of claim 5, wherein said metal complex is characterized by the formula:

7. The process of claim 5, wherein said complex is characterized by the formula:

8. The process of claim 7, wherein said complex is characterized by the general formula:

9. A process for the polymerization of monomers, said process employing a metal complex characterized by the formula:

10. The process of claim 9, wherein said complex is characterized by the formula:

11. The process of claim 10, wherein said complex is characterized by the formula:

12. The process of claim 11, wherein said complex is characterized by the formula:

15. The process of claim 14 wherein said at least one activator comprises an ion forming activator and another reagent selected from the group consisting of a group 13 reagent, a divalent reagent and an alkali metal reagent.

17. The process of claim 16, wherein there are at least 2 monomers.

18. The process of claim 17, wherein said at least 2 monomers comprise ethylene and an α

-olefin.

19. The process of claim 17, wherein said at least 2 monomers comprise ethylene and either 1-octene or 1-hexene.

20. The process of claim 17, wherein there are at least 3 monomers in the process, with said monomers comprising ethylene, an α

-olefin and a diolefin.

21. The process of claim 17, wherein said two monomers comprise ethylene and 1-octene.

22. The process of claim 21, wherein R³ is either aryl or substituted aryl.

23. The process of claim 21, wherein R¹ is selected from the group consisting of mesityl;

2-Me-naphthyl;

2,6-(Prⁱ)₂-C₆H₃—

;

2-Pr¹-6-Me-C₆H₃—

2,6-Et₂-C₆H₃—

; and

2-sec-butyl-6-Et-C₆H₃—

.

24. The process of claim 21, wherein, when present, R⁷ is selected from the group consisting of phenyl, napthyl, mesityl, anthracenyl and phenanthrenyl.

30. The catalyst of either of claim 28, wherein Q¹ and Q⁵ are, independently, selected from the group consisting of —

CH₂R¹⁵, —

CHR¹⁶R¹⁷ and methyl, provided that not both Q¹ and Q⁵ are methyl, wherein R¹⁵ is selected from the group consisting of alkyl, substituted alkyl, aryl and substituted aryl;

R¹⁶ and R¹⁷ are independently selected from the group consisting of alkyl, substituted alkyl, aryl and substituted aryl; and

optionally R¹⁶ and R¹⁷ are joined together in a ring structure having from 3-50 non-hydrogen atoms.

31. The catalyst of claim 29, wherein Q², Q³, and Q⁴ are each hydrogen and Q¹ and Q⁵ are both isopropyl;

or both ethyl;

or both sec-butyl;

or Q¹ is methyl and Q⁵ is isopropyl;

or Q¹ is ethyl and Q⁵ is sec-butyl.

32. The catalyst of claim 28, wherein R¹ is selected from the group consisting of mesityl;

2-Me-naphthyl;

2,6-(Pr¹)₂-C₆H₃—

;

2-Pr¹6-Me-C₆H₃—

;

2,6-Et₂-C₆H₃—

; and

2-sec-butyl-6-Et-C₆H₃—

.

25. A catalyst for the production of a polymer comprising a composition comprising:

(1) a ligand characterized by the following general formula;

wherein R¹ is selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl and combinations thereof.

T is —

CR²R³— and

R² are R³ are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof;

R⁴, R⁵, R⁶ and R⁷ are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof, and optionally, any combination of R¹, R², R³, R⁴, R⁵, or R⁶ may be joined together in a ring structure;

provided that either R³ or R⁷ is selected only from the group consisting of aryl, substituted aryl, heteroaryl and substituted heteroaryl;

(2) a metal precursor compound characterized by the general formula Hf(L)_n wherein each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure;

n is 1, 2, 3, 4, 5, or 6; and

(3) optionally, at least one activator.

28. The catalyst of either of claims 25, 26 or 27, wherein R¹ is characterized by the general formula:

29. The catalyst of either of claims 25, 26 or 27, wherein R³ is selected from the group consisting of benzyl, phenyl, naphthyl, 2-biphenyl, 2-dimethylaminophenyl, 2-methoxyphenyl, anthracenyl, mesityl, 2-pyridyl, 3,5-dimethylphenyl, o-tolyl, and phenanthrenyl.

33. The catalyst of either of claims 25, 26 or 27, wherein R⁷ is selected from the group consisting of phenyl, napthyl, mesityl, anthracenyl and phenanthrenyl.

26. A catalyst for the production of a polymer comprising at least one activator and a metal-ligand complex characterized by the following formula:

27. A catalyst for the production of a polymer comprising at least one activator and a metal complex characterized by the formula: