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Title:
POLYMERIZATION OF OLEFINS
Document Type and Number:
WIPO Patent Application WO/2001/092348
Kind Code:
A2
Abstract:
Olefins are polymerized by novel transition metal complexes of selected iminocarboxylate and iminoamido ligands, sometimes in the presence of cocatalysts such as alkylaluminum compounds or neutral Lewis acids. Olefins which may be (co)polymerized include ethylene, a-olefins, and olefins containing polar groups such as olefinic esters for example acrylate esters. Also described are certain 'Zwitterionic' transition metal complexes as polymerization catalysts for making polar copolymers. The resulting polymers are useful as thermoplastics and elastomers.

Inventors:
WANG LIN (US)
JOHNSON LYNDA K (US)
IONKIN ALEX S (US)
Application Number:
PCT/US2001/017636
Publication Date:
December 06, 2001
Filing Date:
May 31, 2001
Export Citation:
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Assignee:
DU PONT (US)
WANG LIN (US)
JOHNSON LYNDA K (US)
IONKIN ALEX S (US)
International Classes:
C07F7/00; B01J31/00; C07F7/28; C07F15/00; C07F15/04; C08F4/06; C08F4/44; C08F4/605; C08F4/64; C08F4/642; C08F4/70; C08F10/00; (IPC1-7): C08F10/00
Domestic Patent References:
WO1998030609A11998-07-16
Foreign References:
US6174976B12001-01-16
Other References:
SEVERIN, KAY ET AL: "Metal complexes of biologically important ligands. LXXV. Synthesis of organometallic cobalt(III), iridium(III) and ruthenium(II) complexes with.alpha.-iminocarboxylate ligands" Z. NATURFORSCH., B: CHEM. SCI. (1995), 50(2), 265-74 , XP001064853
KOMON, ZACHARY J. A. ET AL: "Synthesis of butene-ethylene and hexene-butene-ethylene copolymers from ethylene via tandem action of well-defined homogeneous catalysts" J. AM. CHEM. SOC. (2000), 122(8), 1830 -1831 , XP001065492 cited in the application
LEE, BUN YEOUL ET AL: ".alpha.-Iminocarboxamidato-Nickel(II) Ethylene Polymerization Catalysts" JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2001), 123(22), 5352-5353 , XP001066396
Attorney, Agent or Firm:
Lerman, Bart E. (DE, US)
Download PDF:
Claims:
CLAIMS What is claimed is:
1. A transition metal complex of a ligand of the for mula (I) wherein: Y is oxo, NR12 or PRl2 Z is O, NR", S or PR each of Rl, R2 and R3 is independently hydrogen, hydro carbyl, substituted hydrocarbyl or a functional group; n is 0 or 1 ; each Rl2 is independently hydrogen, hydrocarbyl, substi tuted hydrocarbyl or a functional group; each R13 is independently hydrogen, hydrocarbyl, substi tuted hydrocarbyl or a functional group; and provided that any two of R1, R2 and R3 geminal or vicinal to one another taken together may form a ring.
2. The transition metal complex of claim 1, character ized in that the transition metal is a Group 311 transition metal.
3. The transition metal complex of claim 2, character ized in that the transition metal is selected from the group consisting of Ni, Zr, Ti, Fe, Co and Cu.
4. The transition metal complex of claim 1, character ized in that Z is O or NR13, and n is 0.
5. The transition metal complex of claim 1, character ized in that: Y is oxo ; Z is Nu 13 ; Ru ils hydrogen or hydrocarbyl ; n is 0; and R13 is hydrocarbyl or substituted hydrocarbyl having an Es of less than1. 0 or aryl or substituted aryl in which at least one bond vicinal to the free bond of the aromatic group is substituted; or Y is NRl2 ; Z is NRl3 ; n is 0; Ru ils hydrogen or hydrocar byl; R12 and R13 are each independently hydrocarbyl or substi tuted hydrocarbyl, one or both having an Es of less than 1. 0, or aryl or substituted aryl in which at least one bond vicinal to the free bond of the aromatic group is substi tuted.
6. The transition metal complex of claim 1, character ized in that it has the formula (Ll) X (Lz) y (L3) zM (VIII), wherein L3 is (I); z is 1 or 2; M is a transition metal of oxidation state q; y is an integer of 1 to 3; x= (qz); each Ll is independently a monodentate, monoanionic ligand, wherein at least one Ll group is a ligand that may add to an olefin; and L2 is a monodentate neutral ligand which may be displaced by an olefin, or an empty coordination site; or and L2 taken together are a monoanionic, bidentate ligand into which an olefin molecule may insert between the ligand and M.
7. The transition metal complex of claim 1, character ized in that it has the formula (III), (IV), (V) or (VI): wherein M is. the transition metal; each Lis independently a monodentate, monoanionic ligand, wherein at least one Ll group is a ligand that may add to an olefin; and L is a monodentate neutral ligand which may be displaced by an ole fin, or an empty coordination site; or Ll and L2 taken to gether are a monoanionic, bidentate ligand into which an olefin molecule may insert between the ligand and M.
8. A process for the polymerization of olefins, com prising the step of contacting, under olefin polymerizing conditions: a monomer component comprising one or more of olefins of the formula H2C=CHR4, a norbornene, a styrene, a cyclopen tene or a polar olefin, especially an olefin of the formula H2C=CHR4 and/or a polar olefin of the formula H2C=CHR5CO2R6, wherein R4 is hydrogen, alkyl or substituted alkyl, R5 is a covalent bond, alkylene or substituted alkylene, and R6 is hydrogen, a metal cation, hydrocarbyl or substituted hydro carbyl, with a transition metal polymerization catalyst, characterized in that the transition metal polymerization catalyst comprises a transition metal complex as set forth in any one of claims 17.
9. The process of claim 8, characterized in that a co catalyst is present.
10. The process of claim 8, characterized in that the monomer component comprises ethylene.
11. A process for the manufacture of a polar copolymer, wherein one or more hydrocarbon olefins, one or more polar olefins, and a polymerization catalyst system having a tran sition metal complex component containing a transition metal of groups 611 or a lanthanide metal, are contacted under polymerizing conditions to form said polar copolymer, char acterized in that the transition metal complex component comprises a Zwitterionic complex.
12. The process of claim 11, characterized in that said transition metal is from Groups 811.
13. The process of claim 12, characterized in that said transition metal is Pd, Ni or Cu.
14. The process of claim 13, characterized in that said transition metal is Ni.
15. The process of claim 11, characterized in that said Zwitterionic complex is a Lewis acid adduct of a transition metal complex, the transition metal complex comprising a transition metal complexed to a ligand, wherein a Lewis base is present in the ligand, and wherein the Lewis acid is co ordinated to the Lewis base.
16. The process of claim 15, characterized in that the transition metal complex is as set forth in any one of claims 17.
17. The process of claim 11, characterized in that said Zwitterionic complex is a Lewis acid adduct of a transition metal complex, wherein said Lewis acid is a borane or an aluminane.
18. The process of claim 17, characterized in that said Lewis acid is a tris (pentafluorophenyl) borane, triphenylbo rane or a trihydrocarbylaluminum.
19. The process of any one of claims 1118, character ized in that said hydrocarbon olefin is ethylene, and said polar olefin is one or more of H2C=CHR5C02R6, wherein R5 is n alkylene or a covalent bond, and R6 is hydrocarbyl or substi tuted hydrocarbyl.
20. The process of claim 19, characterized in that an ethylene pressure is about 700 kPa or more, and said process is run at about 50°C to about 170°C.