Substituted phosphinophenoxide-metal complexes for the...

Details Substituted phosphinophenoxide-metal complexes for the... Substituted phosphinophenoxide-metal complexes for the...

2000-11-15

2003-05-06

Nazario-Gonzalez, Porfirio (Department: 1621)

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

Organic compounds

Heavy metal containing

C556S012000, C556S018000, C556S023000, C556S030000, C556S137000, C556S150000, C526S139000, C526S145000, C526S192000, C526S193000, C526S348000, C526S352000, C502S117000, C502S155000

Reexamination Certificate

active

06559326

ABSTRACT:

Substituted phosphinophenoxide-metal complexes for the polymerization of olefins.
The present invention relates to novel phosphinophenoxide-metal complexes for the polymerization of 1-olefins. The invention further relates to catalysts comprising the novel phosphinophenoxide-metal complexes, a process for the polymerization of 1-olefins using the novel complexes and also the polymers and moldings obtainable in this way.
The metal complexes are obtainable from a metal precursor of a metal of the 6
th
-10
th
groups of the Periodic Table in the oxidation state 0 or +2 and a ligand of the formula I,
where
R
1
, R
2
and R
4
are, independently of one another:
hydrogen,
C
1
-C
12
-alkyl,
C
1
-C
12
-alkyl bearing one or more identical or different C
1
-C
12
-alkyl groups, halogens,
C
1
-C
12
-alkoxy groups or C
1
-C
12
-thioether groups as substituents,
C
7
-C
20
-arylalkyl,
C
2
-C
12
-alkenyl,
C
3
-C
12
-cycloalkyl,
C
3
-C
12
-cycloalkyl bearing one or more identical or different C
1
-C
12
-alkyl groups, halogens,
C
1
-C
12
-alkoxy groups or C
1
-C
12
-thioether groups as substituents,
C
6
-C
14
-aryl,
C
6
-C
14
-aryl bearing one or more identical or different C
1
-C
12
-alkyl groups, halogens,
monohalogenated or polyhalogenated C
1
-C
12
-alkyl groups, C
1
-C
12
-alkoxy groups, silyloxy groups OSiR
7
R
8
R
9
, amino groups NR
10
R
11
or C
1
-C
12
-thioether groups as substituents,
C
1
-C
12
-alkoxy groups,
C
6
-C
14
-aryloxy groups,
C
1
-C
12
-thioether groups,
silyloxy groups OSiR
7
R
8
R
9
,
halogens
or amino groups NR
10
R
11
;
R
3
is selected from among the following groups:
&agr;-branched C
3
-C
12
-alkyl groups,
C
1
-C
12
-alkyl bearing one or more identical or different C
1
-C
12
-alkyl groups, halogens,
C
1
-C
12
-alkoxy groups or C
1
-C
12
-thioether groups as substituents in the &agr; position,
C
7
-C
20
-arylalkyl,
C
2
-C
10
-alkenyl,
C
3
-C
10
-alkenylalkyl having at least one double bond, where at least one C—C double bond is conjugated with the aromatic,
C
3
-C
12
-cycloalkyl,
C
6
-C
14
-aryl,
C
6
-C
14
-aryl bearing one or more identical or different C
1
-C
12
-alkyl groups, halogens, monohalogenated or polyhalogenated C
1
-C
12
-alkyl groups, C
1
-C
12
-alkoxy groups, silyloxy groups OSiR
7
R
8
R
9
, amino groups NR
10
R
11
or C
1
-C
12
-thioether groups as substituents,
C
1
-C
12
-alkoxy groups,
C
6
-C
14
-aryloxy groups,
C
1
-C
12
-thioether groups,
silyloxy groups OSiR
7
R
8
R
9
,
halogens
and amino groups NR
10
R
11
,
where in each case adjacent radicals R
1
to R
4
may together form a 5- to 8-membered ring;
R
5
and R
6
are selected independently from among &agr;-branched C
3
-C
12
-alkyl groups,
C
3
-C
12
-cycloalkyl groups,
C
3
-C
12
-cycloalkyl groups bearing one or more identical or different C
1
-C
12
-alkyl groups,
halogens, monohalogenated or polyhalogenated
C
1
-C
12
-alkyl groups, C
1
-C
12
-alkoxy groups,
silyloxy groups OSiR
7
R
8
R
9
, amino groups NR
10
R
11
or C
1
-C
12
-thioether groups as substituents,
X is oxygen, sulfur, selenium, N—R
12
, P—R
12
or AsR
12
,
Y is hydrogen or
an alkali metal cation,
a C
1
-C
18
-alkylacyl anion,
a C
6
-C
14
-arylacyl anion or SiR
7
R
8
R
9
,
R
7
to R
12
are selected independently from among hydrogen, branched or unbranched C
1
-C
6
-alkyl groups, benzyl radicals and C
6
-C
14
-aryl groups, where in each case two adjacent radicals R
7
and R
8
or R
10
and R
11
may together form a saturated or unsaturated 5- to 8-membered ring.
Polyolefins are of general importance as materials, for example for producing films or sheets, fibers or hollow bodies, for example bottles.
New improved processes for preparing polyolefins are therefore of great economic importance. The type of catalysts used is particularly important in this respect.
Conventional processes and catalysts such as Ziegler-Natta catalysts (e.g. A. Echte, Lehrbuch der technischen Polymerchemie, VCH, Weinheim, New York, Basle, Cambridge, Tokyo; 1993; pp. 301-3) and metallocenes (e.g. DE-A 30 07 725) frequently have the disadvantage that aluminum alkyls have to be used for activating them. These are extremely sensitive to moisture and to Lewis bases, so that the activity of the catalysts is greatly reduced by any contaminated monomers. In addition, some aluminum alkyls represent a fire hazard.
The nickel complexes described in WO 96/23010 also have to be activated by means of aluminum alkyls or Lewis acids based on borane.
U.S. Pat. No. 4,472,522 and U.S. Pat. No. 4,472,525 disclose nickel complexes having the structure A,
which can be activated without aluminum alkyl. These are suitable for the oligomerization of ethylene to give 1-olefins (SHOP process). This compound was converted into derivatives in various ways. Despite variation of the radicals R (see W. Keim et al., Organometallics 1986, 5, 2356-9), it was not possible to produce suitable materials since the molar masses obtained are too low.
Furthermore, U.S. Pat. No. 4,472,525 discloses a catalyst system comprising ortho-diethylphosphinophenol A′ or ortho-diphenylphosphinophenol A″,
which after reaction with Ni(COD)
2
in situ with ethylene gives linear oligomers, but no polymers which can be used as polymeric materials.
Braunstein et al. attempted to influence the yield and structure by changing the electron density on the chelating phosphorus.
They used the ortho-phosphinophenol derivative B
(J. Pietsch, P. Braunstein, Y. Chauvin,
New J. Chem
. 1998, 467). The products of the reaction of ethylene and compound B were likewise linear 1-olefins having an average degree of oligomerization of 40.
U.S. Pat. No. 3,635,937 discloses selected Ni complexes, for example B′,
where R=methyl or ethyl and L
x
may be a 1,5-cyclooctadiene, which are able to polymerize ethylene to polyethylene without activation by an aluminum alkyl. The molecular weights M
w
are, at from about 95,000 to 162,000, very attractive, but the activities of 0.73 kg of PE/mol of Ni·h (Example II) are too low for industrial applications.
DE-A 33 36 500 and DE-A 34 45 090 disclose Ni catalysts which can be obtained in situ from a tertiary phosphine, a quinoid compound and an Ni(O) compound or a precursor which can readily be reduced to an Ni(O) compound. Although they polymerize ethylene to polyethylene, their preparation requires very air- and moisture-sensitive Wittig reagents as precursors, which is disadvantageous for industrial applications.
In his thesis, U. Jux (U. Jux, Thesis at the University of Greifswald, 1996) showed that it is possible to prepare polyethylene using Ni complexes of the compounds C, C′ and C″ without prior activation by means of an aluminum alkyl.
However, the activities of 1.4 kg of PE/mol of Ni·h (compound C), 1.4 kg of PE/mol of Ni·h (compound C′) and 2.1 kg of PE/mol of Ni·h (compound C″) were still too low for industrial applications.
At the GDCh conference in Munich (Aug. 16-21, 1998, cf. conference proceedings, poster B197), further Ni complexes which are likewise able to polymerize ethylene without prior activation by means of an aluminum alkyl were disclosed. Ligands of the formulae D, D′ and D″ were tested.
These compounds are all triarylphosphinophenols. However, the polymers obtained had molar masses of less than 10,000 g/mol, which is too low for practical materials. Ni complexes of the diarylmonoalkylphosphinophenols D′″ and D″″
likewise displayed polymerization activity toward ethylene, but the molar masses were still below 10,000 g/mol and thus too low for applications as materials.
Finally, secondary phosphinophenol ligands (R
6
in formula I=H) which were reacted with Ni(COD)
2
and produced high molecular weight polyethylene were disclosed at the abovementioned GDCh conference. However, it was found that the secondary phosphinophenols were extremely sensitive toward the slightest traces of atmospheric oxygen. Our own experiments using these metal complex systems displayed poor reproducibility; a number of experiments under apparently identical conditions gave no polymer at all.

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