Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-08-26
2001-07-03
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...
C526S172000, C526S281000, C526S335000, C526S346000, C526S352000, C526S161000, C526S116000, C526S117000, C526S119000, C502S117000, C502S162000
Reexamination Certificate
active
06255414
ABSTRACT:
FIELD OF THE INVENTION
Olefins are polymerized by using as polymerization catalysts certain novel transition metal complexes of selected bis(carboximidamidatonates).
TECHNICAL BACKGROUND
The polymerization of olefins such as ethylene, propylene, norbornene and cyclopentene are very important commercial processes. These are most commonly done using polymerization catalyst systems containing certain transition complexes. For instance, the Zielger-Natta-type catalysts and metallocene-type catalysts are some of the more important and well-known catalysts of this type which are used to make billions of kilograms of polyolefins annually. Due to the importance of the polymerization of olefins, new catalyst systems are constantly being sought.
Japanese Patent Application 10/36,424 shows a formula for a bis(carboximidamidatonate), but neither describes how to make such a compound nor actually does a polymerization with such a compound.
A. Littke, et al., Organometallics, vol. 17, p. 446-451 (1998); V. Volkis, et al.,
ibid,
p. 3155-3157; J. C. Flores, et al., Organometallics, vol. 14, p. 2106-2108 (1995); P. J. Stewart, et al.,
ibid,
p. 3271-3281; H. W. Roesky, et al., Chem. Ber., vol. 121, p. 1403-1406 (1988); and D. Herskovics-Korine, et al., J. Organometal. Chem., vol. 503, p. 307-314 (1995); report the synthesis and/or use of transition metal complexes of two independent (mono)carboximidamidatonate ligands as polymerization catalysts. However, in none of these references are the two carboximidamidatonates groups joined by a common moiety such as a benzene ring.
A. Littke, et al., Organometallics, vol. 17, p. 446-451 (1998) and S. L. Aelits, et al.,
ibid,
p. 3265-3270, describes the formation of carboximidamidatonates by the reaction of an organometallic compound with a carbodiimide. The use of a bis(alkyl metal salt) to form a bis(carboximidamidatonate) is not described.
SUMMARY OF THE INVENTION
This invention concerns a first process for the polymerization of olefins, comprising the step of contacting, at a temperature of about −50° C. to about +250°C.:
(a) an olefin selected from the group consisting of an &agr;-olefin, a styrene, a cyclopentene, and a norbornene; and
(b) a first compound of the formula (X)
wherein:
R
1
, R
2
, R
3
and R
4
are each independently hydrocarbyl, substituted hydrocarbyl or silyl;
R
15
is a divalent organic moiety;
each X is independently an anion;
n is an integer equal to the valence of M minus 2; and
M is Ti, Zr, Hf, V, Cr, Sc, Y or a rare earth metal.
Optionally, the olefin, first compound and a second compound W may be contacted, which second compound W is a neutral Lewis acid capable of abstracting an X
−
from the first compound to form WX
−
, provided that the anion formed is a weakly coordinating anion, or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion; and provided that when none of X is alkyl, acyl or hydride, said second compound is capable of transferring hydride or alkyl to M.
This invention also concerns the first compound (X) described above.
In another aspect, the present invention concerns a second process for the polymerization of olefins, comprising the step of contacting, at a temperature of about −50° C. to about +250° C., a transition metal complex of a ligand of the formula
with an olefin, wherein:
said olefin is selected from the group consisting of an &agr;-olefin, a styrene, a cyclopentene, and a norbornene;
said transition metal is Ti, Zr, Hf, V, Cr, Sc, Y or a rare earth metal;
R
1
, R
2
, R
3
and R
4
are each independently hydrocarbyl, substituted hydrocarbyl or silyl; and
R
15
is a divalent organic moiety.
The present invention further concerns an anion which is the ligand of the formula (XI) described above.
In yet another aspect, the present invention concerns a process for preparing a transition metal complex of a bis(carboximidamidatonate), such as used in the first and second processes described above, comprising the step of reacting a salt of said transition metal with a dialkali metal salt and/or alkaline earth metal salt of a bis(carboximidamidatonate).
Still further, the invention concerns a process for the production of a bis(carboximidamidatonate), comprising the step of reacting a bis(alkyl metal salt) with 2 moles of a carbodiimide.
REFERENCES:
patent: 0 763 550 A1 (1997-03-01), None
patent: 10036424 (1998-02-01), None
patent: WO 99/50318 (1999-10-01), None
Adam Littke et al., Bulky Bis(alkylamidinate) Complexes of Group 4. Synthesis and Characterization of M(CyNC(R′)NCy)2Cl2and Zr(CyNC(Me)NCy)2Me2(R′=Me, M=Ti, Zr, Hf; R′=tBu, M=Zr),Organometallics,17, 446-451, 1998 (No Month).
Victoria Volkis, et al., Pressure Modulates Stereoregularities in the Polymerization of Propylene Promoted by rac-Octahedral Heteroallylic Complexes,Organometallics,17, 3155-3157, 1998 (No Month).
Sarah L. Aeilts, et al., Aluminum Alkyl Complexes Containing Guanidinate Ligands,Organometallics,17, 3265-3270, 1998 (No Month).
Peter J. Stewart et al., New Titanium Complexes Containing an Amidinate-Imide Supporting Ligand Set: Cyclopentadienyl, Alkyl, Borohydride, Aryloxide, and Amide Derivatives,Organometallics,17, 3271-3281, 1998 (No Month).
Herskovics-Korine et al., Bis(trimethylsilyl) benzamidinate zirconium dichlorides. Active catalysts for ethylene polymerization,Journal of Organo metallic Chemistry,503, 307-314, 1995 (No Month).
Juan C. Flores et al., (N,N′-Dimethyl-p-toluamidinato)trichlorotitanium: Synthesis, Structure, and Polymerization Catalysis,Organometallics,14, 2106-2108, 1995 (No Month).
H. W. Roesky, et al., Benzamidinato complexes of main group and transition metals-Crystal structures of PhC(NsiMe3)2TiCl2and PhC(NsiMe3)2MoO2.,Chem. Ber.,121, 1403-1406, 1988 (No Month).
M. Busch et al., Magnesium halogen alkyl and carbodiimides,Communication from the chemical laboratory of the University of Erlangen, Germany,40, 4296-4298, 1907 (No Month).
Coughlin Edward Bryan
Ittel Steven Dale
Wang Ying
E. I. Du Pont de Nemours and Company
Harlan R.
Wu David W.
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