Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2001-04-02
2003-01-14
Nazario-Gonzalez, Porfirio (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C502S167000, C526S172000, C526S192000, C526S194000, C534S015000, C556S009000, C556S042000, C556S057000, C564S336000, C564S372000
Reexamination Certificate
active
06506920
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.
DETAILS OF THE INVENTION
Herein certain terms are used to define certain chemical groups or compounds. These terms are defined below.
By a carboximidamidatonate group is meant a group of the formula (IX)
wherein each R
13
is independently hydrocarbyl, substituted hydrocarbyl or silyl. A bis(carboximidamidatonate) has two such groups in the molecule.
By a bis(alkyl metal salt) is meant a compound which has 2 alkyl carbon atoms which each have a single negative charge and are anions of or associated with one or more metal cations in such a way that the positive charge on the metal cation(s) is balanced by the 2 negative charges on the anion.
A “hydrocarbyl group” is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.
By “substituted hydrocarbyl” herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of “substituted” are heteroaromatic rings. All of the hydrogen atoms in the substituted hydrocarbyl may be substituted for, such as in trifluoromethyl.
By relatively noncoordinating (or weakly coordinating) anions are meant those anions as are generally referred to in the art in this manner, and the coordinating ability of such anions is known and has been discussed in the literature, see for instance W. Beck., et al., Chem. Rev., vol. 88 p. 1405-1421 (1988), and S. H. Stares, Chem. Rev., vol. 93, p. 927-942 (1993), both of which are hereby included by reference. Among such anions are those formed from aluminum compounds such as those described in the immediately subsequent paragraph and X
−
, including R
19
3
AlX
−
, R
19
2
AlClX
−
, R
19
AlCl
2
X
−
, and R
19
AlOX
−
, wherein R
19
is alkyl. Other useful noncoordinating anions include BAF
−
{BAF=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate}, SbF
6
−
, PF
6
−
, and BF
4
−
, trifluoromethanesulfonate, p-toluenesulfonate, (R
f
SO
2
)
2
N
−
, and (C
6
F
5
)
4
B
−
.
By an alkyl aluminum compound is meant a compound in which at least one alkyl group is bound to an aluminum atom. Other groups such as alkoxide, oxygen, and halogen may also be bound to aluminum atoms in the compound.
By “hydrocarbylene” herein is meant a divalent group containing only carbon and hydrogen. Typical hydrocarbylene groups are —(CH
2
)
4
—, —CH
2
CH(CH
2
CH
3
)CH
2
CH
2
— and
If not otherwise stated, it is preferred that hydrocarbylene groups herein contain 1 to about 30 carbon atoms.
By “substituted hydrocarbylene” herein is meant a hydrocarbylene group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbylene groups herein contain 1 to about 30 carbon atoms. Included within the meaning of “substituted” are heteroaromatic rings.
By a styrene herein is meant a compound of the formula
wherein R
26
, R
27
, R
26
, R
29
and R
30
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, all of which are inert in the polymerization process. It is preferred that all of R
26
, R
27
, R
26
, R
29
and R
30
are hydrogen.
By “a norbornene” is meant that the mo
Coughlin Edward Bryan
Ittel Steven Dale
Wang Ying
E. I. du Pont de Nemours and Company
Nazario-Gonzalez Porfirio
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