Polymerization catalyst

Details Polymerization catalyst Polymerization catalyst

2001-04-06

2004-06-01

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S009000, C556S011000, C556S016000, C556S020000, C526S127000, C526S160000, C526S352000, C526S943000, C502S103000, C502S117000, C502S120000

Reexamination Certificate

active

06743932

ABSTRACT:

The present invention relates to an organometallic compound of the formula I,
where the variables are defined as follows:
M
1
is selected from among Fe, Co, Ru and Os,
M
2
is a transition metal of group 4, 5 or 6 of the Periodic Table of the Elements,
Nu
1
and Nu
2
are identical or different and are selected from among N, P and As,
R
1
and R
2
are identical or different and are selected from among
C
1
-C
8
-alkyl, substituted or unsubstituted,
C
3
-C
12
-cycloalkyl, substituted or unsubstituted,
C
7
-C
13
-aralkyl,
C
6
-C
14
-aryl, unsubstituted or substituted by one or more identical or different substituents selected from among
C
1
-C
8
-alkyl, substituted or unsubstituted,
C
3
-C
12
-cycloalkyl,
C
7
-C
13
-aralkyl,
C
6
-C
14
-aryl,
halogen,
C
1
-C
6
-alkoxy,
C
6
-C
14
-aryloxy,
SiR
11
R
12
R
13
and O—SiR
11
R
12
R
13
, where R
11
-R
13
are selected from among C
1
-C
8
-alkyl, C
3
-C
12
-cycloalkyl, C
7
-C
13
-aralkyl and C
6
-C
14
-aryl;
five- to six-membered nitrogen-containing heteroaryl radicals, unsubstituted or substituted by one or more identical or different substituents selected from among
C
1
-C
8
-alkyl, substituted or unsubstituted,
C
3
-C
12
-cycloalkyl,
C
7
-C
13
-aralkyl,
C
6
-C
14
-aryl,
halogen,
C
1
-C
6
-alkoxy,
C
6
-C
14
-aryloxy,
SiR
11
R
12
R
13
and O—SiR
11
R
12
R
13
, where R
11
-R
13
are selected from among C
1
-C
8
-alkyl, C
3
-C
12
-cycloalkyl, C
7
-C
13
-aralkyl and C
6
-C
14
-aryl;
R
3
to R
10
are hydrogen,
C
1
-C
8
-alkyl, substituted or unsubstituted,
C
3
-C
12
-cycloalkyl, substituted or unsubstituted,
NO
2
,
halogen,
C
7
-C
13
-aralkyl,
C
6
-C
14
-aryl, unsubstituted or substituted by one or more identical or different substituents selected from among
C
1
-C
8
-alkyl, substituted or unsubstituted,
C
3
-C
12
-cycloalkyl,
C
7
-C
13
-aralkyl,
C
6
-C
14
-aryl,
halogen,
C
1
-C
6
-alkoxy,
C
6
-C
14
-aryloxy,
SiR
11
R
12
R
13
and O—SiR
11
R
12
R
13
, where R
11
-R
13
are selected from among C
1
-C
8
-alkyl, C
3
-C
12
-cycloalkyl, C
7
-C
13
-aralkyl and C
6
-C
14
-aryl;
five- to six-membered nitrogen-containing heteroaryl radicals, unsubstituted or substituted by one or more identical or different substituents selected from among
C
1
-C
8
-alkyl, substituted or unsubstituted,
C
3
-C
12
-cycloalkyl,
C
7
-C
13
-aralkyl,
C
6
-C
14
-aryl,
halogen,
C
1
-C
6
-alkoxy,
C
6
-C
14
-aryloxy,
SiR
11
R
12
R
13
and O—SiR
11
R
12
R
13
, where R
11
-R
13
are selected from among C
1
-C
8
-alkyl, C
3
-C
12
-cycloalkyl, C
7
-C
13
-aralkyl and C
6
-C
14
-aryl;
where in each case two adjacent radicals R
3
to R
6
or R
7
to R
10
together with the C atoms of the parent aromatic may form a 5- to 8-membered ring or sterically favorably positioned radicals may form a bridge between the two C
5
rings;
L
1
to L
3
are identical or different and are selected from among
NR
14
R
15
, where R
14
and R
15
are identical or different and are selected from among C
1
-C
8
-alkyl, C
3
-C
12
-cycloalkyl, C
2
-C
8
-alkenyl having one or more conjugated or nonconjugated double bonds, C
7
-C
13
-aralkyl, C
6
-C
14
-aryl, SiR
11
R
12
R
13
and O—SiR
11
R
12
R
13
, where R
11
-R
13
are selected from among C
1
-C
8
-alkyl, C
3
-C
12
-cycloalkyl, C
7
-C
13
-aralkyl and C
6
-C
14
-aryl; and where R
14
and R
15
together with N may form a five- to ten-membered, saturated or unsaturated ring which may in turn be substituted by C
1
-C
6
-alkyl,
halide,
C
1
-C
8
-alkyl, substituted or unsubstituted,
C
3
-C
12
-cycloalkyl,
C
7
-C
13
-aralkyl,
C
6
-C
14
-aryl,
C
1
-C
6
-alkoxy;
C
6
-C
14
-aryloxy,
x is an integer from 0 to 3.
The present invention further provides a process for preparing a compound of the formula I, which comprises reacting an organometallic compound of the formula II with a transition metal compound of the formula III
 M
2
L
1
L
2
(L
3
)
x+1
  III
where the variables are as defined above. In this reaction, the organometallic compound of the formula II may, if desired, be doubly deproteinated beforehand. The invention also provides an organometallic compound of the formula II.
Furthermore, the present invention provides a process for preparing an organometallic compound II by reacting an organometallic compound of the formula IV
with a hydroxide compound M
3
OH or M
4
(OH)
2
, where
M
3
is Li, Na, K, Rb or Cs and
M
4
is Mg, Ca, Sr or Ba and
R
16
and R
17
are selected independently from among C
1
-C
8
-alkyl, C
3
-C
12
-cycloalkyl, C
7
-C
13
-aralkyl and C
6
-C
14
-aryl and the remaining variables are as defined above, and also provides the organometallic compound of the formula IV.
The present invention further provides a process for preparing an organometallic compound of the formula IV by deproteinating one or two carboxylic acid derivatives R
16
—CO—Nu
1
R
1
H and R
17
—CO—Nu
2
R
2
H and subsequently reacting the product with an organometallic compound of the formula V
where X
1
and X
2
are selected independently from among F, Cl and Br and the remaining variables are as defined above, in the presence of a copper(I) compound and a cosolvent.
The present invention also provides a catalyst system for the polymerization or copolymerization of olefins, comprising one or more organometallic compounds of the formula I and at least one activator, and also a process for the polymerization or copolymerization of olefins using the catalyst system of the present invention. In addition, the present invention provides a solid catalyst comprising an organometallic compound of the formula I, at least one activator and a solid support, and finally provides a process for preparing the solid catalyst of the present invention by impregnation of a support material with one or more organometallic compounds and at least one activator, and a process for the polymerization or copolymerization of olefins in bulk, in suspension or in the gas phase using the solid catalyst of the present invention.
Polymers and copolymers of olefins are of great economic importance because the monomers are readily obtainable in large quantities and because the polymers can be varied within a wide range by variation of the production process or the processing parameters. In the production process, the catalyst used is of particular significance. Apart from Ziegler-Natta catalysts, various single-site catalysts are of increasing importance. As central atoms, not only Zr as in metallocene catalysts ((H.-H. Brintzinger et al., Angew. Chem. 1995, 107, 1255) but also Ni or Pd (WO 96/23010) or Fe and Co (e.g. WO 98/27124) have been examined in detail in recent times.
In the synthesis of catalytically active metallocenes for the polymerization of propylene, there is the problem that most metallocenes are usually obtained as a mixture of the desired racemate form and the unwanted meso form. Suggestions for remedies are known from the literature. Thus, it has been proposed that racemate form and meso form be separated from one another (for example by means of alcoholytic decomposition of the meso isomer as described in DE-A 195 47 247, by complexation with tetramethylethylenediamine “TMEDA” as described in EP-A 0 854 876 and crystallization, or by transformation in a separate step as described in EP-A 0 837 865) or else using specific reaction conditions in the presence of expensive reagents as described in EP-A 0 891 980 (organostannyl reagents). All previously known methods require additional process steps and are therefore costly and disadvantageous.
The use of amido complexes as described in EP-A 0 763 044 is restricted to a few metallocenes which are not relevant to industrial-scale polymerization.
In the search for new catalytically active substances, bis-amide ligands for tetravalent metals of the groups IV to VI of the Periodic Table are of particular interest (G. J. P. Britovsek et al., Angew. Chem. 1999, 111, 448). Their polymerization properties can be controlled within a wide range (cf., for example, N. A. H. Male et al., J. Chem. Commun., Dalton Trans. 1997, 2487; H. Mack et al., J. Organomet. Chem. 1996, 525, 81; C. Averbuj et al., J. Am. Chem. Soc. 1998, 120, 8640; V

Affiliated with

Also associated with

Rating

Polymerization catalyst does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Polymerization catalyst, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Polymerization catalyst will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3338233