Claims
- 1. A process for the polymerization of olefins, comprising the step of contacting, at a temperature of about −100° C. to about +200° C., at least one polymerizable olefin with an active polymerization catalyst comprising a Group 3 through 11 (IUPAC) transition metal or a lanthanide metal complex of a ligand of the formula (I), (II) or (XII)
- 2. The process of claim 1, wherein said transition metal is Ni, Pd, Pt, Fe, Co, Ti, Zr, V, Hf, Cr or Cu.
- 3. The process of claim 2, wherein said transition metal is Ni, Pd, Ti or Zr.
- 4. The process of claim 1, wherein the ligand is (I) and:
the transition metal is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11R12, R11 is hydrocarbyl or substituted hydrocarbyl, R12 is hydrocarbyl, substituted hydrocarbyl or a functional group, and Z is O; or the transition metal is Ti, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11R12, R11 is hydrocarbyl or substituted hydrocarbyl, R12 is hydrocarbyl, substituted hydrocarbyl or a functional group, and Z is O; or the transition metal is Zr, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11 R12, R11 is hydrocarbyl or substituted hydrocarbyl, R12 is hydrocarbyl, substituted hydrocarbyl or a functional group, and Z is O; or the transition metal is Ni, m is 0, n is 1, R3 and R4 are hydrogen, R7 is hydrocarbyl or substituted hydrocarbyl, Y is CR11R12, R11 is hydrogen, R12 is hydrocarbyl or substituted hydrocarbyl, and Z is N; or the transition metal is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11R12, R11 and R12 taken together are oxo, and Z is O; or the transition metal is Ni, m is 0, n is 1, R3 and R4 are hydrogen, R7 is hydrocarbyl or substituted hydrocarbyl, Y is CR11R12, R11 and R12 taken together are oxo, and Z is N; or the transition metal is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is S(T), T is ═O and Z is O; or the transition metal is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is S(T), T is ═N-silyl, Z is N and R7 is silyl; or the transition metal is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is S(T), T is ═O, Z is N, and R7 is hydrocarbyl or substituted hydrocarbyl; or the transition metal is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11R12, R11 and R12 taken together are a ring and Z is O; or the transition metal is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11R12, R11 and R12 taken together are N-hydrocarbyl- or N-substituted hydrocarbylimino, Z is N and R7 is hydrocarbyl or substituted hydrocarbyl; or the transition metal is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is S(T), T is ═O and Z is O; or the transition metal is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11R12, R11 and R12 taken together are sulfo, Z is N and R7 is hydrocarbyl or substituted hydrocarbyl.
- 5. A process for the polymerization of olefins, comprising the step of contacting, at a temperature of about −100° C. to about +200° C, at least one polymerizable olefin with a compound of the formula (IV), (V) or (XIII)
- 6. The process of claim 5, wherein M is Ni, Pd, Pt, Fe, Co, Ti, Zr, V, Hf, Cr or Cu.
- 7. The process of claim 6, wherein M is Ni, Pd, Ti or Zr.
- 8. The process of claim 5, wherein the compound is (IV) and:
M is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11R12, R11 is hydrocarbyl or substituted hydrocarbyl, R12 is hydrocarbyl, substituted hydrocarbyl or a functional group, and Z is O; or M is Ti, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11R12, R11 is hydrocarbyl or substituted hydrocarbyl, R12 is hydrocarbyl, substituted hydrocarbyl or a functional group, and Z is 0; or M is Zr, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11R12, R11 is hydrocarbyl or substituted hydrocarbyl, R12 is hydrocarbyl, substituted hydrocarbyl or a functional group, and Z is O; or M is Ni, m is 0, n is 1, R3 and R4 are hydrogen, R7 is hydrocarbyl or substituted hydrocarbyl, Y is CR11R12, R11 is hydrogen, R12 is hydrocarbyl or substituted hydrocarbyl, and Z is N; or M is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11R12, R11 and R12 taken together are oxo, and Z is O; or M is Ni, m is 0, n is 1, R3 and R4 are hydrogen, R7 is hydrocarbyl or substituted hydrocarbyl, Y is CR11R12, R11 and R12 taken together are oxo, and Z is N; or M is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is S(T), T is ═O and Z is O; or M is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is S(T), T is ═N-silyl, Z is N and R7 is silyl; or M is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is S(T), T is ═O, Z is N, and R7 is hydrocarbyl or substituted hydrocarbyl; or M is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11R12, R11 and R12 taken together are a ring and Z is O; or M is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11R12, R11 and R12 taken together are N-hydrocarbyl- or N-substituted hydrocarbylimino, Z is N and R7 is hydrocarbyl or substituted hydrocarbyl; or M is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is S(T), T is ═O and Z is O; or the transition metal is Ni, m is 0, n is 1, R3 and R4 are hydrogen, Y is CR11R12, R11 and R12 taken together are sulfo, Z is N and R7 is hydrocarbyl or substituted hydrocarbyl.
- 9. A polymerization catalyst component comprising a Group 3 through 11 transition metal or lanthanide metal complex of a ligand of the formula
- 10. The component of claim 9, which is on a solid support.
- 11. The component of claim 9, wherein a cocatalyst which is an alkylaluminum compound or a borane or both is also present.
- 12. A process for forming an ethylene/polar monomer copolymer, comprising the step of contacting, under polymerizing conditions, a nickel complex of a bidentate neutral ligand or a bidentate monoanionic ligand, with a monomer component comprising one or more hydrocarbon olefins and one or more polar comonomers (and other optional components such as, for example, one or more cocatalysts and/or other additives), at a temperature of about 60° C. to about 170° C., provided that when CO is present, at least one other polar monomer is present.
- 13. The process of claim 12, wherein ethylene is present and an ethylene partial pressure of at least about 0.67 MPa is used.
- 14. The process of claim 12, wherein said one or more polar comonomers comprises H2C═CHR20C(O)Y, or H2C═CR25C(O)Y, wherein R20 is alkylene or substituted alkylene, R25 is hydrogen, and Y is —OH, —NR21R22, —OR23, or —SR24, wherein R21 and R22 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, R23 and R24 are each hydrocarbyl or substituted hydrocarbyl.
- 15. The process of claim 12, wherein said bidentate ligand is
- 16. A polymer, consisting essentially of repeat units derived from ethylene, and one or more polar olefins of the formula H2C═CHC(O)R32, wherein R32 is —OR34 or any group readily derivable from it, and R34 is hydrocarbyl or substituted hydrocarbyl, wherein:
said polymer contains “first branches” of the formula —(CH2)nCH3 and “second branches” of the formula —(CH2)mC(O)R32, wherein m and n are independently zero or an integer of 1 or more; and said polymer has the following structural characteristics:
(a) one or both of:
(1) the ratio of first branches wherein n is 0 to first branches wherein n is 1 is about 3.0 or more; and (2) the ratio of first branches wherein n is 0 to first branches wherein n is 3 is 1.0 or more; and (b) one or both of:
(1) the total number of first branches in which n is 0, 1, 2 and 3 in said polymer is about 10 or more per 1000 CH2 groups; and (2) the incorporation of repeat units derived from H2C═CHC(O)R32 is 0.3 mole percent or more based on the total repeat units derived from the hydrocarbonolefin and H2C═CHC(O)R32.
- 17. A polymer, consisting essentially of repeat units derived from:
one or more hydrocarbon olefins, such as ethylene, and one or more polar olefins of the formula H2C═CHC(O)R32, wherein R32 is —OR34, or any group readily derivable from it, and R34 is hydrocarbyl or substituted hydrocarbyl; wherein in said polymer incorporation of repeat units derived from H2C═CHC(O)R32 is 0.3 mole percent or more based on the total repeat units; and wherein said polymer has one or both of the following structural characteristics:
at least 5 mole percent of said repeat units derived from H2C═CHC(O)R32 are present in said polymer as end groups; and said end groups are at least 0.001 mole percent of the total repeat units in said polymer; and provided that said end groups have the formula ˜˜˜˜˜˜˜—HC═CH—C(O)—R32 wherein ˜˜˜˜˜˜˜ is the remainder of the polymer chain of said end group.
- 18. A polymer, consisting essentially of:
repeat units derived from ethylene; repeat units derived from one or more monomers of the formula H2C═CHC(O)R32, wherein each R32 is independently —OR34 or any group readily derivable from it, and each R34 is independently hydrocarbyl or substituted hydrocarbyl, and repeat units derived from one or more alpha-olefins of formulas H2C═CH—(CH2)t—H and/or H2C═CH—R75—G, wherein t is an integer of 1 to 20, R75 is alkylene or substituted alkylene, and G is an inert functional group.
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority under 35 U.S.C. §119 from U.S. Provisional Application Ser. Nos. 60/208,087 (filed May 31, 2000), 60/211,601 (filed Jun. 15, 2000), 60/214,036 (filed Jun. 23, 2000) and 60/264,537 (filed Jan. 25, 2001), all of which are incorporated by reference herein as if fully set forth.
Provisional Applications (4)
|
Number |
Date |
Country |
|
60208087 |
May 2000 |
US |
|
60211601 |
Jun 2000 |
US |
|
60214036 |
Jun 2000 |
US |
|
60264537 |
Jan 2001 |
US |