Metal complexes of iminohydroxamic acids

Details Metal complexes of iminohydroxamic acids Metal complexes of iminohydroxamic acids

2003-02-12

2004-12-07

Lu, Caixia (Department: 1713)

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

Organic compounds

Heavy metal containing

C556S137000, C556S146000, C526S171000, C526S172000

Reexamination Certificate

active

06828454

ABSTRACT:

The present invention relates to complexes of the formulae I,
where the variables are defined as follows:
Nu is selected from among O, S, N—R
4
*, P—R
4
*,
M is selected from among Ni, Pd;
h is an integer from 0 to 4;
X are identical or different and are selected from among halogen, C
1
-C
8
-alkyl, C
3
-C
12
-cycloalkyl, C
7
-C
13
-aralkyl and C
6
-C
14
-aryl,
R
1
, R
4
, R
4
* are identical or different and are selected from among hydrogen
C
1
-C
18
-alkyl, substituted or unsubstituted,
C
2
-C
18
-alkenyl, substituted or unsubstituted, which has from one to 4 isolated or conjugated double bonds and is bound via a single bond;
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
18
-alkyl, substituted or unsubstituted,
C
2
-C
18
-alkenyl, substituted or unsubstituted,
C
3
-C
12
-cycloalkyl,
C
7
-C
13
-aralkyl,
C
6
-C
14
-aryl,
halogen,
C
1
-C
6
-alkoxy, substituted or unsubstituted,
C
6
-C
14
-aryloxy,
SiR
5
R
6
R
7
and O—SiR
5
R
6
R
7
;
five- to six-membered nitrogen-containing heteroaryl radicals which may be unsubstituted or substituted by one or more identical or different substituents selected from among
C
1
-C
18
-alkyl, substituted or unsubstituted,
C
2
-C
18
-alkenyl, 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
5
R
6
R
7
and O—SiR
5
R
6
R
7
;
and are bound via a single bond;
R
2
is C
6
-C
14
-aryl, unsubstituted or substituted by one or more identical or different substituents, or a five- to six-membered nitrogen-containing heteroaryl radical, unsubstituted or substituted by one or more identical or different substituents, where the substituents are as defined above;
R
3
is C
1
-C
8
-alkyl, C
2
-C
18
-alkenyl, substituted or unsubstituted and having from one to 4 isolated or conjugated double bonds, 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, or a five- to six-membered nitrogen-containing heteroaryl radical, unsubstituted or substituted by one or more identical or different substituents, where the substituents are as defined above;
where adjacent radicals R
1
to R
4
may be joined to one another to form a 5- to 12-membered ring which may in turn bear substituents selected from among C
1
-C
8
-alkyl, substituted or unsubstituted, C
2
-C
8
-alkenyl, substituted or unsubstituted and having from one to 4 isolated or conjugated double bonds, C
3
-C
12
-cycloalkyl, substituted or unsubstituted, C
7
-C
13
-aralkyl and C
6
-C
14
-aryl;
L
1
is an uncharged, organic or inorganic ligand,
R
5
to R
7
are identical or different and are selected from among hydrogen, C
1
-C
8
-alkyl, C
3
-C
12
-cycloalkyl, C
7
-C
13
-aralkyl and C
6
-C
14
-aryl.
The present invention further provides a process for the polymerization of olefins using complexes of the formula I.
Polymers and copolymers of olefins are of great economic importance because the monomers are readily available 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 importance. Apart from Ziegler-Natta catalysts, various types of single-site catalysts are of increasing importance, with metals which have been examined in detail as central atoms being 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). The complexes of Ni, Pd, Fe and Co are also referred to as complexes of late transition metals.
Metallocene catalysts have disadvantages for industrial use. The most frequently used metallocenes, namely zirconocenes and hafnocenes, are sensitive to hydrolysis. In addition, most metallocenes are sensitive toward many catalyst poisons such as alcohols, ethers or CO, which makes it necessary for the monomers to be carefully purified.
While Ni or Pd complexes (WO 96/23010) catalyst the formation of highly branched polymers which are of little commercial interest, the use of Fe or Co complexes leads to the formation of highly linear polyethylene with very small proportions of comonomer.
EP-A 0 874 005 discloses further polymerization-active complexes. These are preferably Ti complexes with salicylaldimine ligands. These, too, bear phenyl substituents or substituted phenyl substituents on the aldimine nitrogen (pages 18-23) or else the aldimine nitrogen is incorporated in a 6-membered ring (pages 31-32). However, they generally produce low molecular weight polyethylenes which are of limited suitability as materials. Furthermore, in all the ligands disclosed in EP-A 0 874 005, the oxygen atom is part of a phenolic system, which restricts the choice of readily available starting materials.
U.S. Pat. No. 2001/0025007 discloses compounds of the formulae A and B
and their use as catalysts for the polymerization of olefins, where G
2
, R and R′ are hydrocarbon radicals, U is a group such as alkoxy and V is selected from among CR, N and PR
2
. However, the synthesis of such complexes A and B is rather complicated. In addition, the process engineering parameters of the complexes A and B are capable of improvement.
As G. J. P. Britovsek et al. in
Angew. Chem.
1999, 111, 448, and
Angew. Chem. Int. Ed. Engl.
1999, 38, 428, show, the search for very versatile polymerization-active complexes continues to be of importance because of the great commercial importance of polyolefins. There is interest in finding polymerization-active complexes which have a particularly advantageous property profile in process engineering terms.
It is an object of the invention
to provide new complexes which are suitable for the polymerization of olefins to form high molecular weight polymers;
to provide a process for preparing the complexes of the present invention;
to provide a process for the polymerization or copolymerization of olefins using the complexes of the present invention;
to provide supported catalysts for the polymerization of olefins and also a process for preparing the supported catalysts of the present invention using the complexes of the present invention;
to polymerize and copolymerize olefins using the supported catalysts of the present invention.
We have found that this object is achieved by means of complexes which have the structures of the formula I defined at the outset.
In formula I, the variables are defined as follows:
Nu is selected from among O, S, N—R
4
* and P—R
4
*, with oxygen and N—R
4
* being preferred;
M is selected from among Ni and Pd in the oxidation state +2, particularly preferably Ni;
h is an integer from 0 to 4, preferably 0;
X are identical or different and are selected from among
halogen, such as fluorine, chlorine, bromine and iodine, preferably chlorine and bromine and particularly preferably chlorine;
C
1
-C
8
-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl and n-octyl; preferably C
1
-C
6
-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, particularly preferably C
1
-C
4
-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
C
3
-C
12
-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferably cyclopentyl, cyclohexyl and cycloheptyl;
C
7
-C
13
-aralkyl, preferably C
7
-C
12
-phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, neophyl (1-methyl-1-phenylethyl), 1-phenylbutyl, 2-

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