Bridged metallocenes, preparation, use in catalytic systems

Details Bridged metallocenes, preparation, use in catalytic systems Bridged metallocenes, preparation, use in catalytic systems

2000-07-14

2002-08-13

Nazario-Gonzalez, Porfirio (Department: 1755)

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

Organic compounds

Heavy metal containing

C556S012000, C556S053000, C556S043000, C556S058000, C534S015000, C502S103000, C502S117000, C526S126000, C526S160000, C526S943000

Reexamination Certificate

active

06433203

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a new class of metallocene compounds, to a catalyst for the polymerisation of olefins containing them and to a polymerisation process carried out in the presence of said catalyst. The invention also relates to the corresponding ligands useful as intermediates in the synthesis of said metallocene compounds, as well as to processes for preparing said ligands and said metallocene compounds.
DESCRIPTION OF THE PRIOR ART
Metallocene compounds with two cyclopendadienyl groups are known as catalyst components for the polymerisation of olefins.
European Patent 0 129 368, for instance, describes the polymerisation of olefins in the presence of a bis-cyclopentadienyl co-ordination complex containing a transition metal. The two cyclopentadienyl groups can be linked by a bridging group, which is generally a divalent radical containing one or more carbon atoms or heteroatoms.
Also known are bridged metallocene compounds wherein the cyclopentadienyl moiety is condensed to one aromatic or non aromatic ring, the cyclopentadienyl moieties being linked by an ethylene bridge.
For example, European Patent Application EP-0 891 011 describes a process for the preparation of ethylene-based polymers in the presence of ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride. The polymers obtained are endowed with low molecular weight. Moreover, the manufacture of ethylene-bridged metallocenes involves the use of the carcinogenic 1,2-dibromoethane.
As regards metallocenes having two equally substituted indenyl groups linked by a bridging group longer than two carbon atoms, only a few compounds have been disclosed.
For example, EP-A-0 399 348 and EP-A-0 459 320 describe the polymerisation of ethylene in the presence of propylenebis(1-indenyl)zirconium dichloride. Although the polyethylene obtained has industrially acceptable molecular weight, the metallocene used in the polymerisation process has low polymerisation activity.
W. A. Herrmann et al. in Angew. Chem. Int. Ed. Engl. 28 (1989), No. 11, describes the use of metallocenes containing two indenyl groups linked by a 1,2-bis(dimethylsilyl)ethane group for the polymerisation of olefins. Although completely inactive toward propylene, an activity toward ethylene was observed. However, there are no data reported about the molecular weight of the polymers.
It would be desirable to find carbon-bridged metallocenes which, when used in catalysts for the polymerisation of olefins, are suitable for the preparation of polyolefins, with the advantage of having higher polymerisation activities and of yielding polymers having improved molecular weights. It would also be desirable to avoid using the carcinogenic 1,2-dibromoethane used for the preparation of metallocenes.
A novel class of metallocene compounds has now unexpectedly been found which has two identical indenyl ligands which are linked to one another by a bridging group longer than an ethylene radical and which can advantageously be used as catalyst components for the polymerisation of olefins.
According to a first aspect, the present invention provides a metallocene compound of the formula (Ia):
wherein
R
1
, same or different from each other, are C
1
-C
20
-alkyl, C
3
-C
20
-cycloalkyl, C
2
-C
20
-alkenyl, C
6
-C
20
-aryl, C
7
-C
20
-alkylaryl or C
7
-C
20
-arylalkyl radicals, optionally containing silicon or germanium atoms, and optionally two adjacent R
1
substituents can form a ring comprising from 5 to 8 carbon atoms;
R
2
, same or different, are hydrogen atoms, C
1
-C
20
-alkyl, C
3
-C
20
-cycloalkyl, C
2
-C
20
-alkenyl, C
6
-C
20
-aryl, C
7
-C
20
-alkylaryl, C
7
-C
20
-arylalkyl, NR
3
2
, PR
3
2
, AsR
3
2
, OR
3
, SR
3
or SeR
3
radicals, optionally containing silicon, germanium or halogen atoms; and optionally two adjacent R
2
or R
3
substituents can form a ring comprising from 5 to 8 carbon atoms;
M is an atom of a transition metal selected from those belonging to group 3, 4, 5, 6 or to the lanthanide or actinide groups in the Periodic Table of the Elements (new IUPAC version),
M′ is an atom of a transition metal selected from those belonging to group 3 or to the lanthanide or actinide groups in the Periodic Table of the Elements (new IUPAC version),
X, same or different, is a monoanionic ligand, such as a hydrogen atom, a halogen atom, an R
4
, OR
4
, OSO
2
CF
3
, OCOR
4
, SR
4
, NR
4
2
or PR
4
2
group, wherein the substituents R
4
are a C
1
-C
20
-alkyl, C
3
-C
20
-cycloalkyl, C
2
-C
20
-alkenyl, C
6
-C
20
-aryl, C
7
-C
20
-alkylaryl or C
7
-C
20
-arylalkyl radical, optionally containing silicon or germanium atoms;
and optionally the six-membered rings of the compounds of formula (Ia) and (Ib) are perhydrated;
q is an integer from 3 to 5;
n is an integer from I to 4. when the six-membered rings of the compound of formula (Ia) are not perhydrated, and is an integer of from 0 to 4, when the six-membered rings of the compound of formula (Ia) are perhydrated as well as in the compound of formula (Ib);
p is an integer from 0 to 3, being equal to the oxidation state of the metal M minus two.
The transition metal M in compound of formula (Ia) is preferably selected from the group consisting of titanium, zirconium, hafnium, yttrium and scandium.
Non limiting examples belonging to this class are:
1,3-propandiylbis(4-methyl-1-indenyl)zirconium dichloride and dimethyl,
1,3-propandiylbis(5-methyl-1-indenyl)zirconium dichloride and dimethyl,
1,3-propandiylbis(6-methyl-1-indenyl)zirconium dichloride and dimethyl,
1,3-propandiylbis(4,7-dimethyl-1-indenyl)zirconium dichloride and dimethyl,
1,4-butandiylbis(4,7-dimethyl-1-indenyl)zirconium dichloride and dimethyl,
1,5-pentandiylbis(4,7-dimethyl-1-indenyl)zirconium dichloride and dimethyl,
1,6-hexandiylbis(4,7-dimethyl-1-indenyl)zirconium dichloride and dimethyl,
1,3-propandiylbis(4,7-diethyl-1-indenyl)zirconium dichloride and dimethyl,
1,4-butandiylbis(4,7-diethyl-1-indenyl)zirconium dichloride and dimethyl,
1,5-pentandiylbis(4,7-diethyl-1-indenyl)zirconium dichloride and dimethyl,
1,6-hexandiylbis(4,7-diethyl-1-indenyl)zirconium dichloride and dimethyl,
1,3-propandiylbis(4,7-diisopropyl-1-indenyl)zirconium dichloride and dimethyl,
1,4-butandiylbis(4,7-diisopropyl-1-indenyl)zirconium dichloride and dimethyl,
1,5-pentandiylbis(4,7-diisopropyl-1-indenyl)zirconium dichloride and dimethyl,
1,6-hexandiylbis(4,7-diisopropyl-1-indenyl)zirconium dichloride and dimethyl,
1,3-propandiyl(4,7-diisopropyl-1-indenyl)(4-isopropyl-1-indenyl)zirconium dichloride and dimethyl,
1,4-butandiyl(4,7-diisopropyl-1-indenyl)(4-isopropyl-1-indenyl)zirconium dichloride and dimethyl,
1,5-pentandiyl(4,7-diisopropyl-1-indenyl)(4-isopropyl-1-indenyl)zirconium dichloride and dimethyl,
1,6-hexandiyl(4,7-diisopropyl-1-indenyl)(4-isopropyl-1-indenyl)zirconium dichloride and dimethyl,
1,3-propandiylbis(4,7-dimethyl-1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,3-propandiylbis(1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,4-butandiylbis(4,7-dimethyl-1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,4-butandiylbis(1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,5-pentandiylbis(4,7-dimethyl-1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,5-pentandiylbis(1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,6-hexandiylbis(4,7-dimethyl-1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,6-hexandiylbis(1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,3-propandiylbis(4,7-diethyl-1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,4-butandiylbis(4,7-diethyl-1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,5-pentandiylbis(4,7-diethyl-1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,6-hexandiylbis(4,7-diethyl-1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,3-propandiylbis(4,7-diisopropyl-1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,4-butandiylbis(4,7-diisopropyl-1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,5-pentandiylbis(4,7-diisopropyl-1-tetrahydroindenyl)zirconium dichloride and dimethyl,
1,6-hexandiylbis(4,7-diisopro

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