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Title:
A NEW TRANSITION METAL COMPLEX, ITS PREPARATION AS WELL AS A CATALYST SYSTEM BASED THEREUPON AND ITS USE FOR THE POLYMERIZATION OF OLEFINS
Document Type and Number:
WIPO Patent Application WO/2000/050170
Kind Code:
A2
Abstract:
The invention relates to new triaza transition metal complexes and their use as polymerization catalysts. They have the formula (1): L¿n?MX¿m-n?, wherein each L is independently a ligand which is multidentate by adjacent cooordinating atoms, M is the central atom which is a metal selected from Groups 4-8 of the Periodic Table of the Elements (IUPAC 1990), each X is independently a unidentate organic or halogen ligand, m is the coordination number or number of coordination sites on the central atom M, and n is the number of the ligands L which is an integer from 1 to m. At least one of the ligands L has formula (2), wherein each of R¿1?-R¿6? is independently selected from hydrogen and organic groups having from 1 to 10 carbon atoms and the ligand L is coordinated to the central atom M by one to four of the three nitrogen atoms and/or the carbon atom of the ligand L according to formula (2).

Inventors:
ANDELL OVE (FI)
MAARANEN JANNE (FI)
KETOLA LASSE (FI)
Application Number:
PCT/FI2000/000136
Publication Date:
August 31, 2000
Filing Date:
February 22, 2000
Export Citation:
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Assignee:
BOREALIS AS (DK)
ANDELL OVE (FI)
MAARANEN JANNE (FI)
KETOLA LASSE (FI)
International Classes:
B01J31/18; C07F7/00; C07F11/00; C08F10/00; (IPC1-7): B01J31/00
Foreign References:
GB924364A1963-04-24
US3301854A1967-01-31
US4085106A1978-04-18
Attorney, Agent or Firm:
BERGGREN OY AB (P.O. Box 16 Helsinki, FI)
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Claims:
Claims
1. A triaza transition metal complex having the formula (1) LnMX(1) wherein each L is independently a ligand which is multidentate by adjacent cooordinating atoms, M is the central atom which is a metal selected from Groups 48 of the Periodic Table of the Elements (IUPAC 1990), each X is independently a unidentate organic or halogen ligand, m is the coordination number or number of coordination sites on the central atom M, and n is the number of the ligands L which is an integer from 1 to m, characterized in that at least one of the ligands L has the formula (2) wherein each of RlR6 is independently selected from hydrogen and organic groups having from 1 to 10 carbon atoms and the ligand L is coordinated to the central atom M by one, two, three or four of the three nitrogen atoms and/or the carbon atom of the ligand L according to the formula (2).
2. A transition metal complex according to claim 1, characterized in that said <BR> <BR> <BR> organic groups of at least one of the pairs: R2 and R3, R4 and R5, and R6 and Rl are interconnected to form a bridge structure.
3. A transition metal complex according to claim 1 or 2, characterized in that <BR> <BR> <BR> the groups of all of the pairs: R2 and R3, R4 and R5, R6 and Rl are interconnected to form bridge structures which are selected from unsubstituted 1,3propylene and ethylene.
4. A transition metal complex according to claim 1,2 or 3, characterized in that M of formula (1) is selected from iron Fe, chromium Cr, titanium Ti and zirconium Zr.
5. A transition metal complex according to any preceding claim, characterized in that X of formula (1) is selected from aCIC3alkyl and a halogen.
6. A transition metal complex according to claim 5, characterized in that X is selected from methyl and chlorine Cl.
7. A transition metal complex according to any preceding claim, characterized in that n of formula (1) is selected from 1 and 2.
8. A transition metal complex according to any preceding claim, characterized in that it is a 1,5,9triazatricyclo [7.3.1.0] 5 l3tridecanyl chromium dichloride of the formula (3):.
9. A transition metal complex according to any of claims 17, characterized in that it is a 1,5,9triazatricyclo [7.3.1.0] 5l3tridecanyl zirconium trichloride of the formula(4):.
10. A transition metal complex according to any of claims 17, characterized in that it is a bis {1,5,9triazatricyclo [7.3.1.0] 5 l3tridecanyl} zirconium dichloride of the formula (5):.
11. A transition metal complex according to any of claims 17, characterized in that it is a 1,4,7triazatricyclo [5.2.1. 04,10] decanyl chromium dichloride of the formula(6):.
12. A transition metal complex according to any of claims 17, characterized in that it is a 1,4,7triazatricyclo [5.2.1.04 l°] decanyl titanium trichloride of the formula (7):.
13. A transition metal complex according to any of claims 17, characterized in that it is a bis {l, 4,7triazatricyclo [5.2.1. 04,10] decanyl} zirconium dichloride of the formula (8):.
14. A process for the preparation of a transition metal complex according to any of claims 113, characterized by reacting a triaza compound of the formula (9) wherein R is a CzC6 alkyl, a triClC6alkylsilyl or a hydrogen and each of RlR5 is the same as above, a transition metal compound of the formula (10) MX. (10) wherein M, X and m are the same as above, and preferably a strong base, most preferably in the order (triaza compound + transition metal compound) + strong base or the order (triaza compound + strong base) + transition metal compound, to give said transition metal complex.
15. A process according to claim 14, characterized in that said triaza compound is reacted with said transition metal compound and, preferably, a complexating electron donor compound to form a precursor complex comprising said triaza compound, said transition metal compound and, preferably, said complexating electron donor compound, and that said precursor complex is then reacted with said strong base.
16. A process according to claim 15, characterized in that said triaza compound is reacted with a starting complex of said transition metal compound and said complexating electron donor compound.
17. A process according to claim 15 or 16, characterized in that said complexating electron donor compound is tetrahydrofurane.
18. A process according to any of claim 1417, characterized in that said precursor complex has essentially the following formula (11) wherein R, RlR6, M, X, m and n are as defined above, CED is said complexating electron donor and p is an integer 1 to 3.
19. A process according to any of claims 1418, characterized in that said strong base is an organoalkali compound having the formula R'A, wherein R'is a ClCl2 hydrocarbyl and A is an alkali metal.
20. A process according to claim 19, characterized in that said strong base is benzyl potassium.
21. A triNdentate transition metal complex, characterized in that it has the formula (12) wherein the R of the triaza ligand within brackets is a C1C6 alkyl, a triCC6 alkylsilyl or a hydrogen, each of RIR6 is independently selected from organic groups having from 1 to 10 carbon atoms, M is a central atom which is a metal selected from Groups 48 of the Periodic Table of the Elements, each X is independently an unidentate organic or halogen ligand, m is the coordination number or number of coordination sites on the central atom M, and n is the number of the triaza ligands.
22. A transition metal complex according to claim 21, characterized in that said organic groups of at least one of the pairs: R2 and R3, R4 and R5, and R6 and Rl are interconnected to form a bridge structure.
23. A transition metal complex according to claim 21 or 22, characterized in that the groups of all of the pairs: R2 and R3, R4 and R5, R6 and Ri are interconnected to form bridge structures which are selected from unsubstituted 1,3propylene and ethylene.
24. A transition metal complex according to claim 21,22 or 23, characterized in that M of formula (12) is selected from chromium Fe, Cr, titanium Ti and zirconium Zr.
25. A transition metal complex according to any of claims 2124, characterized in that X of formula (12) is selected from a ClC3 alkyl and a halogen.
26. A transition metal complex according to claim 25, characterized in that X is selected from methyl and chlorine Cl.
27. A transition metal complex according to any of claims 2126, characterized in that n of formula (12) is selected from 1 and 2.
28. A catalyst system for the polymerization of ethylenically unsaturated compounds, characterized in that it comprises a transition metal complex according to any of claims 113 or 1827 and a cocatalyst selected from an alumin oxane having one of the following formulas (13) (13 linear) (13 cyclic) (13 general) wherein each R"is independently selected from a ClClo alkyl and q is an integer between 1 and 40, and an organic compound having the formula (14) (R"'rm') Csr) t (14) wherein R"'is a ClClohydrocarbyl, X'is a halogen, r is 1,2 or 3, s is the valency of M', M'is a metal selected from Groups 1 to 3 and 13 of the Periodic Table of the Elements (IUPAC 1990), and t is 1 or 2.
29. A catalyst system according to claim 28, characterized in that said cocatalyst is a C1C10 aluminoxane, preferably a ClC6 aluminoxane, most preferably methyl aluminoxane.
30. Process for the polymerization of one or several ethylenically unsaturated compounds, characterized in that, under polymerization conditions, at least one polymerizable ethylenically unsaturated compound is contacted with a catalyst system according to one of claims 28 or 29.
31. Process according to claim 30, characterized in that the atomic ratio Al/M or M'/M is between 10 and 10000, preferably between 100 and 2000.
32. Process according to claim 30 or 31, characterized in that said polymerizable ethylenically unsaturated compound is selected from ethylene, a C3C20aolefin, a conjugated C4CI2 diene and a CSC14awdiolefin and polymerizable combinations thereof.
33. Process according to claim 32, characterized in that said polymerizable ethylenically unsaturated compound is ethylene.
Description:
INTERNATIONAL SEARCH REPORT International application No. PCT/FI00/00136 Box I Observations where certain claims were found unsearchable (Continuation of item 1 of first sheet) This international search report has not been established in respect of certain claims under Article 17 (2) (a) for the following reasons: 1.2Claims Nos.: because they relate to subject matter not required to be searched by this Authority, namely: 2. n Claims Nos.: because they relate to parts of the international application that do not comply with the prescribed requirements to such an extent that no meaningful international search can be carried out, specifically: 3.2 Claims Nos.: because they are dependent claims and are not drafted in accordance with the second and third sentences of Rule 6.4 (a).: Box II Observations where unity of invention is lacking (Continuation of item 2 of first sheet) This International Searching Authority found multiple inventions in this international application, as follows: I. Claims 1-13 directe to a triaza transition metal complex with at least one ligand L II. Claims 21-27 directe to a tri-N-dentate transition metal complex see next page 1. As all required additional search fees were timely paid by the applicant, this international search report covers all searchable claims. 2.3 As all searchable claims could be searched without effort justifying an additional fee, this Authority did not invite payment of any additional fee. 3. j As only some of the required additional search fees were timely paid by the applicant, this international search report covers only those claims for which fees were paid, specifically claims Nos.: 4. n No required additional search fees were timely paid by the applicant. Consequently, this international search report is restricted to the invention first mentioned in the claims; it is covered by claims Nos.: Remark on Protest! The additional search fees were accompanied by the applicant's protest. No protest accompanied the payment of additional search fees. Form PCT/ISA/2 10 (continuation of first sheet (1)) (July 1992) INTERNATIONAL SEARCH REPORT International application No. PCT/FI00/00136 The"special technical feature"of group I relate to a triaza transition metal complex with at least one ligand L while the "special technical feature"of group II relate to a tri-N-dentrate transition complex where the complex contains a complexing electron donor and the triaza ligand contains a group R which is a C1-C6 alkyl, a tri-C1-C6 alkylsilyl or a hydrogen.

These groups of inventions are not so linked as to form a single general inventive concept. There is no technical relationship among those inventions involving one or more of the same or corresponding technical features. Sf'70480 INTERNATIONAL SEARCH REPORT International application No. Information on patent family members 02/12/99 PCT/FI 00/00136 02/12/99 PCT/FI 00/00136 Patent document Publication Patent family Publication cited in search report date member (s) date GB 924364 A 24/04/63 BE 614149 A 00/00/00 BE 614150 A 00/00/00 FR 1316772 A 26/04/63 FR 1316773 A 00/00/00 GB 933150 A 00/00/00 NL 274901 A 00/00/00 NL 274902 A 00/00/00 US 3132141 A 05/05/64 US 3301854 A 31/01/67 NONE US 4085106 A 18/04/78 US 4130715 A 19/12/78