Metallic compounds and the use thereof in the polymerization...

Details Metallic compounds and the use thereof in the polymerization... Metallic compounds and the use thereof in the polymerization...

2003-01-02

2004-11-02

Rabago, Roberto (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S161000, C526S172000, C502S155000, C502S213000, C556S013000, C556S018000, C556S019000, C556S022000, C556S138000, C556S140000, C556S137000

Reexamination Certificate

active

06812306

ABSTRACT:

DESCRIPTION
The present invention relates to metal compounds of the formula I,
where the variables are defined as follows:
M is selected from among Ni and Pd in the oxidation state +II;
Nu
1
, Nu
2
are selected independently from among N, P and As,
E is selected from among
and
E
1
, E
2
, E
3
and E
4
are selected independently from among C, Si and Ge;
R
1
to R
12
are selected independently from among
hydrogen,
C
1
-C
8
-alkyl, substituted or unsubstituted,
C
2
-C
8
-alkenyl, substituted or unsubstituted, 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 monosubstituted or polysubstituted by identical or different substituents selected from among
C
1
-C
8
-alkyl, substituted or unsubstituted,
C
3
-C
12
-cycloalkyl,
C
7
-C13-aralkyl,
C
6
-C
14
-aryl,
halogen,
C
1
-C
6
-alkoxy, substituted or unsubstituted,
C
6
-C
14
-aryloxy,
SiR
18
R
19
R
20
and O—SiR
18
R
19
R
20
, where R
18
-R
20
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;
five- to six-membered nitrogen-containing heteroaryl radicals, unsubstituted or monosubstituted or polysubstituted by 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
18
R
19
R
20
and O—SiR
18
R
19
R
20
, where R
18
-R
20
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;
where adjacent radicals R
1
to R
10
together with E may be joined to form a saturated or olefinically unsaturated 5- to 12-membered ring;
A
1
, A
3
are selected from among C—R
15
, C—R
16
, Si—R
15
, Si—R
16
and N,
A
2
is selected from among C—R
17
, Si—R
17
and N,
where not more than one A
j
is a nitrogen atom and j=1, 2, 3;
R
13
to R
17
are selected from among
hydrogen,
C
1
-C
8
-alkyl, substituted or unsubstituted,
C
2
-C
8
-alkenyl, substituted or unsubstituted, 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 monosubstituted or polysubstituted by 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
18
R
19
R
20
and O—SiR
18
R
19
R
20
, where R
18
-R
20
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;
five- to six-membered nitrogen-containing heteroaryl radicals, unsubstituted or monosubstituted or polysubstituted by 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
18
R
19
R
20
and O—SiR
18
R
19
R
20
, where R
18
-R
20
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 R
13
to R
17
together with one or more atoms A
j
may form a saturated or unsaturated 5- to 12-membered ring
and [Y]
−
is an anion.
These metal compounds can be used for the polymerization and copolymerization of olefins. The present invention also provides a process for the polymerization and copolymerization of olefins using one or more of the metal compounds of the present invention. Furthermore, the present invention provides supported catalysts comprising one or more of the compounds of the present invention for the polymerization or copolymerization of olefins, a process for preparing the supported catalysts of the present invention and a process for the polymerization or copolymerization of olefins using a supported catalyst according to the present invention. Finally, the present invention provides a process for preparing the metal compounds of the present invention.
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 significance. Apart from Ziegler-Natta catalysts, various single-site catalysts are of increasing importance. In these single-site catalysts, central atoms which have been examined in detail in recent times are 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) and 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.
For industrial use, metallocene catalysts have disadvantages. The catalysts are very sensitive to impurities in the industrially available monomers, in the process gas and in the solvents used. Impurities which cause problems are, for example, moisture and oxygen as well as CO, but also Lewis bases in general, e.g. ethers. Furthermore, the price of Zr as central metal in the industrially important zirconocenes is very high.
While Ni or Pd complexes (WO 96/23010) catalyze the formation of highly branched, commercially less interesting polymers, the use of Fe or Co complexes leads to the formation of highly linear polyethylenes.
The abovementioned complexes are polymerization-inactive as such and have to be activated by means of cocatalysts. Cocatalysts used for the polymerization of ethylene are methylaluminoxane (“MAO”) or modified methylaluminoxane (“MMAO”)in which a certain percentage of the methyl groups have been replaced by isobutyl groups.
However, the use of MAO or other aluminoxanes has disadvantages:
MAO and other aluminoxanes have to be used in a large molar excess; from 100- to 1000-fold excesses are customary. The cocatalyst therefore becomes a significant cost factor for the catalysts.
Aluminoxanes are not molecular defined substances and their ability to activate transition metal complexes depends greatly on the method of preparation and impurities. Furthermore, the storage temperature and the storage time play a role. Quality control is difficult.
Aluminoxanes always have to be stored under refrigeration, because otherwise they tend to form gels. Aluminoxane gels are unsuitable as cocatalysts.
Aluminoxanes have to be used in a large excess and increase the residual ash content of the polymer.
Aluminoxanes are provided commercially as solutions, so that much otherwise worthless solvent has to be transported.
Aluminoxanes, particularly those having C
1
-C
4
-alkyl radicals, and their solutions are pyrophoric and require increased safety measures.
Another class of known cocatalysts is made up by strong Lewis acids and salts of noncoordinating or only weakly coordinating anions bearing bulky substituents. Suitable Lewis acids and salts are selected boron compounds bearing electron-withdrawing groups (e.g. trispentafluorophenylborane, N,N-dimethylanilinium tetrakispentafluorophenylborate, tri-n-butylammonium tetrakispentafluorophenylborate, N,N-dimethylanilinium tetrakis(3,5-bisperfluoromethyl)phenylborate, tri-n-butylammonium tetrakis(3,5-bisperfluoromethyl)phenylborate and tritylium tetrakispentafluorophenylborate, usually together with an aluminum alkyl. These activators are described in EP-A 0 468 537 and EP-A 0 426 638. A disadvantage of these catalyst systems is that they are air and moisture sensitive because of the use of aluminum alkyls. Other Lewis bases such as ethers also have to be carefully excluded, likewise CO and CO
2
.
Also known are palladium complexes of the formula A or B,
(EP-A 0 827 515) where R, R′, R″ and R′″ are selected from among various alkyl and aryl radicals, E is a bridging element, Nu
1
and Nu
2
are selected from among N, P and As, and [Z] is a counterion.
If the further ligands X

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