Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-08-09
2001-07-31
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S127000, C526S159000, C526S160000, C526S352000, C526S943000
Reexamination Certificate
active
06268448
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to the use of iminophosphonamide complexes with transition metals for the polymerization of olefins. Generally the iminophosphonamide ligands have the formula [(R
1
)
2
P(═NR
2
)NR
2
]. The complexes may be bis iminophosphonamide complexes or may be mono-iminophosphonamide complexes together with another ligand such as a cyclopentadienyl (Cp) ligand.
BACKGROUND OF THE INVENTION
Iminophosphonamide complexes have been known for some time. However, there has been no disclosure that such compounds may be used to polymerize monomers, such as olefins, more particularly alpha olefins such as ethylene and its higher homologues.
BASF's European Patent 0 687 693 A1 (corresponding to U.S. Pat. No. 5,707,913 issued on Jan. 13, 1998) discloses complexes with following structure used as polymerization catalysts:
where, M represents a metal from IIIb, IVb, Vb or VIb of the periodic table of elements or a metal from the lanthanide group, X is a negative leaving atom or a negative leaving group, which may be identical or different if (n−m)>1, R
1
, R
2
and R
3
are each a C-organic or Si-organic radicals, n is the valence of M in the metal complex, and m is from 1 to 5, with the proviso that n−m=0. The metal complex is activated with an activator in a molar ratio of activator to metal complex from 0.5:1 to 10,000:1. While the complex of the BASF patent to some extent looks similar to those of the present invention the ligands do not contain a phosphorus atom between the two nitrogen atoms of the ligand. Accordingly, the BASF patent does not teach the subject matter of the present invention.
Exxon's U.S. Pat. No. 5,318,935 discloses complexes having the following structure:
wherein M is zirconium, hafnium or titanium, N is a nitrogen atom having three substituents; each “X” is independently, any univalent anionic ligand selected from the group consisting of halide, hydride, straight, branched, or aromatic hydrocarbyl radicals, alkoxide, aryloxide, amide having singly or multiply branched hydrocarbyl radicals having between 3 and 30 carbon atoms or, arylamide, phosphide and arylphosphide. “T” is a covalent bridging group selected from the group consisting of unsubstituted hydrocarbyls and substituted hydrocarbyls containing a Group IV-A or VI-A element; and each “R” is independently or any radical containing a Lewis basic functionality; and alumoxane as cocatalyst. The reference teaches away from the subject matter of the present invention as the bridging group between two nitrogen atoms does not include a phosphorus or arsenic atom required by the present invention.
J. Organomet. Chem. 371 (1989) C40-C44 discloses the synthesis of complexes having the formula:
The reference does not teach the use of the complexes for the polymerization of olefins.
J. Organomet. Chem. 469 (1994) C27-C30 teaches the synthesis of the following complex:
The reference does not teach polymerization of olefins using such a complex.
The following structures have been disclosed in J. Chem. Soc. Dalton Trans 1989, 2173.
The paper contains no polymerization data, nor does it suggest that such complexes may have utility as polymerization catalysts for olefins.
J. Organomet. Chem. 414 (1991) 327-335 discloses the synthesis of the following complexes:
Again no polymerization data is given in the paper nor is there any suggestion that the complexes would be useful in the polymerization of olefins.
The present invention seeks to provide a novel process for the polymerization of olefins using iminophosphonamide complexes with transition metals.
SUMMARY OF THE INVENTION
The present invention provides a process for the polymerization of one or more olefins in the presence of a catalyst precursor having an empirical structure of the formula:
wherein A is selected from a phosphorus atom and an arsenic atom; each B is independently selected from the group consisting of an oxygen atom and a radical of the formula NR
2
, wherein each R
2
is independently selected from the group consisting of a hydrogen atom, a C
1-10
alkyl radical which is unsubstituted or up to fully substituted by one or more halogen atoms, a C
6-10
aryl radical which is unsubstituted or up to fully subsituted by one or more halogen atoms, and trialkyl silyl radicals of the formula —Si(R
5
)
3
wherein each R
5
is independently selected from the group consisting of a hydrogen atom and a Cab alkyl radical; each RX is independently selected from the group consisitng of a hydrogen atom, a C
1-10
alkyl radical which is unsubstituted or up to fully substituted by one or more halogen atoms, and a C
6-10
aryl radical which is unsubstituted or up to fully subsituted by one or more halogen atoms; R
3
and R
4
are independently selected from the group consisting of a hydrogen atom, a halogen atom, or a C
1-8
alkyl radical. M is a transition metal selected from the group consisiting of Ti, Zr, Hf, and V; n is 1 or 2; m is 0 or 1 provided that the sum of n+m=2 and Cp is C
5-13
ligand containing a 5-member carbon ring having delocalized bonding within the ring and typically being bound to the transition metal M through covalent &eegr;
5
-bonds which is unsubstituted or up to fully substituted by one or more substituents selected from the group consisting of a halogen atom, a C
1-4
alkyl radical, and an amido radical which is unsubstituted or substituted by up to two C
1-4
alkyl radicals; and an activator.
REFERENCES:
patent: 5318935 (1994-06-01), Canich et al.
patent: 5707913 (1998-01-01), Schlund et al.
patent: 0 687 693 A1 (1995-06-01), None
patent: 09012619-A2 (1997-01-01), None
patent: WO-9618658-A1 (1996-06-01), None
A. Recknagel, M. Witt & F. Edelmann, Synthese von Metallacyclophosphazenen mit Praseodym, Neodym, Uran and Thorium, Journal of Organometalic Chemistry, 371, 1989, The Netherlands (no month).
M. Witt, H. Roesky, D. Stalke, F.Pauer, T. Henkel & G. Sheldrick, Synthesis and Crystal Structures of Three Four-membered Ring Compounds Containing Pn2Ti Skeletons, J.Chem. Soc., 1989, Germany (no month).
Henri-Jean Cristau & Chantal Garcia, Synthesis of Diaminodiphenylphosphonium Salts, C. Synthesis, 1990, 315-317, France (no month).
V. Chandrasekhar, T.Chivers, S. Kumaravel, A. Meetsma, and J. Grampel Prep. of 1,1,5,5-Tetraphenyl-3,7-dairyl-1,5-diphosphatatetrazocines & 1,1,3,3,5-Pentaphenyldiphosphatriazine and the X-ray Structure of 1,5-Ph4P2N4C2(C6H4CH3-4)2, Inorg. Chem. 1991, 30, 3402-3407 (no month).
A. Recknagel, A. Seiner, M. Noltemeyer, S. Brooker, D. Stalke & R. Edelmann, Diiminophosphinate des Litiums, Samariums und Ytterbiums: Molekulstrukturen von Li[Ph2P(NSiMe3) 2ISm(u-I)2(THF)2Journal of Organometallic Chemistry, 414, 1991, 327-335, Germany (no month).
U.Kilimann, M. Noltemeyer, M. Schafer, R. Herbst-Irmer, H. Schmidt & F. Edelmann, Cyclooctatetraenyl-Komplexe der fruhen Ubergangsmetalle und Lanthanoide, Journal of Organmettalic Chemistry, 469, 1994, C27-C30, Germany (no month).
G. Diamond, R. Jordan, and J. Petersen, Efficient Synthesis of Chiral ansa-Metallocenes by Amine Elimination, Synthesis, Structure, and Reactivity of rac-(EBI)Zr(NMe2)2, J. Am. Chem. Soc. 1996, 8024-8033, (no month).
K. Paciorek and R. Kratzer, Reactions of Triphenylsiyl Azide with Tetraphenyldiphosphine and Diphenylphosphine, J. Org. Chemistry, 1996, 31, 2426-2427. (no month).
Collins Scott
Vollmerhaus Rainer
Wang Qinyan
Johnson Kenneth H.
Lu Caixia
University of Waterloo
Wu David W.
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