Ethylene-styrene copolymers and phenol-triazole type complexes, catalysts, and processes for polymerizing
View Patent ↗Metal-ligand complexes that are useful as precursors to catalysts for the polymerization of olefins are provided. Certain of the catalysts are particularly effective at polymerizing ethylene and styrene into copolymers having novel properties, including a low molecular weight and close comparison between vinyl and methyl end groups.
1. A process for the production of an ethylene styrene copolymer, comprising contacting at least ethylene and styrene or substituted styrene monomers with a catalyst under polymerization conditions, said catalyst formed from a composition comprising a ligand and metal precursor, wherein said ligand is characterized by the following formula:
wherein X 1 and X 2 are N, and X 3 , X 4 , and X 5 are independently selected from the group consisting of N and CR 15 , where R 15 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof, provided that at least one and not more than two of X 3 , X 4 , and X 5 are N; optionally, X 3 and X 4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; and
R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof, with the exception that R 1 may not be hydrogen, and optionally two or more of R 1 , R 2 , R 3 and R 4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; and
wherein said metal precursor comprises a group 4 metal.
2. The process of claim 1 , wherein said metal precursor is characterized by the formula M(L) n where M is hafnium, zirconium or titanium; 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, hydrido, allyl, diene, seleno, phosphino, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, and combinations thereof; and Lewis base adducts thereof; and n is 3 or 4.
3. The process of claim 2 , wherein each L is independently selected from the group consisting of alkyl, substituted alkyl and amino.
4. The process of claim 3 , wherein each L is independently selected from the group consisting of benzyl and dimethylamino.
5. The process of claim 1 , wherein said ligand is characterized by the general formula:
wherein Q 1 and Q 2 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof; and optionally, Q 1 and Q 2 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms.
6. The process of claim 5 , wherein said ligand is characterized by the general formula:
wherein each of R 5 , R 6 , R 7 and R 8 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; optionally, two or more of R 5 , R 6 , R 7 and R 8 may be joined to form a fused ring system having up to 50 atoms not counting hydrogen atoms.
7. The process of claim 6 , wherein said ligand is characterized by the general formula:
wherein each of R 9 , R 10 , R 11 , R 12 and R 13 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; optionally, two or more of R 9 , R 10 , R 11 , R 12 or R 13 are joined to form a fused ring system having up to 50 atoms not counting hydrogen atoms.
8. The process of claim 7 , wherein said ligand is characterized by the general formula:
wherein G is selected from the group consisting of O, S, N and P, k is 1 when G is O or S, k is 2 when G is N or P, and R 14 is selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, silyl, and combinations thereof.
9. The process of either of claims 1 , 2 , 3 , 4 , 5 , 6 , 7 , or 8 , wherein R 2 and R 4 are both hydrogen.
10. The process of either of claims 6 , 7 , 8 or 9 , wherein one or both of R 6 and R 7 are halo substituents.
11. The process of claim 10 , wherein one or both of R 6 and R 7 are chloro.
12. The process of either of claims 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 or 9 , wherein
R 1 and R 3 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, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof, with the exception that R 1 may not be hydrogen; and
R 2 and R 4 are hydrogen, or two or more of R 1 , R 2 , R 3 and R 4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms.
13. The process of either of claims 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 or 9 , wherein the mole ratio of said ligand to said metal precursor is between about 1.5:1 and 2.5:1.
14. The process of claim 13 , wherein said ratio is about 2:1.
15. The process of claim 1 , wherein said composition further comprises an activator, combination of activators or activating technique.
16. The process of claim 15 , wherein said activator is an ionic activator.
17. The process of claim 15 wherein at least one activator is present and comprises an ion forming activator and, optionally, a group 13 reagent.
18. The process of claim 15 wherein at least one activator is present and comprises an ion forming activator and, optionally, a divalent metal reagent.
19. The process of either of claims 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 or 9 , wherein at least one activator is present and comprises an ion forming activator and, optionally, an alkali metal reagent.
20. A process for the production of an ethylene styrene copolymer, comprising contacting at least ethylene and styrene (or substituted styrene) monomers with a catalyst under polymerization conditions, said catalyst formed from a composition comprising a metal-ligand complex characterized by the following formula:
X 1 and X 2 are N, and X 3 , X 4 , and X 5 are independently selected from the group consisting of N and CR 15 , where R 15 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof, provided that at least one and not more than two of X 3 , X 4 , and X 5 are N; optionally, X 3 and X 4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; and
R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof, with the exception that R 1 may not be hydrogen, and optionally two or more of R 1 , R 2 , R 3 and R 4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms;
M is zirconium, titanium or hafnium; and
L 1 and L 2 are 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, thio, boryl, silyl, amino, hydrido, allyl, seleno, phosphino, carboxylates, and combinations thereof.
21. The process of claim 20 , wherein said metal-ligand complex is characterized by the formula:
wherein Q 1 and Q 2 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof; and optionally, Q 1 and Q 2 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms.
22. The process of claim 21 , wherein said metal-ligand complex is characterized by the formula:
wherein each of R 5 , R 6 , R 7 and R 8 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; optionally, two or more of R 5 , R 6 , R 7 and R 8 may be joined to form a fused ring system having up to 50 atoms not counting hydrogen atoms.
23. The process of claim 22 , wherein said metal-ligand complex is characterized by the formula:
wherein each of R 9 , R 10 , R 11 , R 12 and R 13 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; optionally, two or more of R 9 , R 10 , R 11 , R 12 or R 13 are joined to form a fused ring system having up to 50 atoms not counting hydrogen atoms.
24. The process of claim 23 , wherein said metal-ligand complex is characterized by the formula:
wherein G is selected from the group consisting of O, S, N and P, k is 1 when G is O or S, k is 2 when G is N or P, and R 14 is selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, silyl, and combinations thereof.
25. The process of either of claims 20 , 21 , 22 , 23 or 24 , wherein said composition further comprises an activator, combination of activators or activating technique.
26. The process of claim 25 , wherein said activator is an ionic activator.
27. The process of claim 25 wherein at least one activator is present and comprises an ion forming activator and, optionally, a group 13 reagent.
28. The process of either of claims 20 , 21 , 22 , 23 or 24 , wherein at least one activator is present and comprises an ion forming activator and, optionally, a divalent metal reagent.
29. The process of either of claims 20 , 21 , 22 , 23 or 24 , wherein L 1 and L 2 are each independently selected from the group consisting of alkyl, substituted alkyl and amino.
30. The process of claim 29 , wherein L 1 and L 2 are each independently selected from the group consisting of benzyl and dimethylamino.
31. The process of either of claims 20 , 21 , 22 , 23 or 24 , wherein said polymerization conditions comprise a solution process at a temperature of at least 100° C.
32. The process of either of claims 20 , 21 , 22 , 23 or 24 , wherein said process is a solution polymerization process.
33. The process of either of claims 20 , 21 , 22 , 23 or 24 , wherein R 2 and R 4 are both hydrogen.
34. The process of either of claims 22 , 23 or 24 , wherein one or both of R 6 and R 7 are halo substituents.
35. The process of claim 34 , wherein one or both of R 6 and R 7 are chloro.
36. The process of either of claims either of claims 20 , 21 , 22 , 23 or 24 , wherein
R 1 and R 3 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, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof, with the exception that R 1 may not be hydrogen; and
R 2 and R 4 are hydrogen, or two or more of R 1 , R 2 , R 3 and R 4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms.
37. A polymerization process employing a catalyst formed from a group 4 metal precursor and a ligand characterized by the general formula:
wherein R 2 , R 3 and R 4 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof, and optionally two or more of R 2 , R 3 and R 4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms;
R 5 , R 6 , R 7 and R 8 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof, optionally, two or more of R 5 , R 6 , R 7 and R 8 may be joined to form a fused ring system having up to 50 atoms not counting hydrogen atoms;
each of R 9 , R 10 , R 11 , R 12 and R 13 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; optionally, two or more of R 9 , R 10 , R 11 , R 12 or R 13 are joined to form a fused ring system having up to 50 atoms not counting hydrogen atoms; and
G is selected from the group consisting of O, S, N and P, k is 1 when G is O or S, k is 2 when G is N or P, and R 14 is selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, silyl, and combinations thereof.
38. The process of claim 37 , wherein monomers that are olefins or α-olefins are polymerized.
39. The process of claim 38 , wherein the process is a copolymerization of ethylene and one or more α-olefins.
40. A process for polymerizing a monomer, comprising providing a reactor with at least one polymerizable monomer and providing a catalyst to said reactor, wherein said catalyst is defined as in claim 37 and subjecting said reactor contents to polymerization conditions.
41. A polymerization process employing a catalyst formed from an activator, combination of activators or an activating technique and a metal-ligand complex characterized by the general formula:
wherein M is zirconium, titanium or hafnium;
L 1 and L 2 are 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, thio, boryl, silyl, amino, hydrido, allyl, seleno, phosphino, carboxylates, and combinations thereof;
R 2 , R 3 and R 4 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof, and optionally two or more of R 2 , R 3 and R 4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms;
R 5 , R 6 , R 7 and R 8 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; optionally, two or more of R 5 , R 6 , R 7 and R 8 may be joined to form a fused ring system having up to 50 atoms not counting hydrogen atom; and
R 9 , R 10 , R 11 , R 12 and R 13 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; optionally, two or more of R 9 , R 10 , R 11 , R 12 or R 13 are joined to form a fused ring system having up to 50 atoms not counting hydrogen atoms.
42. The polymerization process of claim 41 , wherein R 2 and R 4 are both hydrogen.
43. The polymerization process of claim 41 , wherein one or both of R 6 and R 7 are halo substituents.
44. The polymerization process of claim 43 , wherein one or both of R 6 and R 7 are chloro.
45. The polymerization process of claim 41 wherein said metal-ligand complex is characterized by the formula:
wherein G is selected from the group consisting of O, S, N and P, k is 1 when G is O or S, k is 2 when G is N or P, and R 14 is selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, silyl, and combinations thereof.