Metallocene compounds, process for their preparation and...

Details Metallocene compounds, process for their preparation and... Metallocene compounds, process for their preparation and...

2001-11-20

2003-10-21

Nazario-Gonzalez, Porfirio (Department: 1621)

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

Organic compounds

Heavy metal containing

C556S012000, C556S021000, C556S028000, C556S030000, C556S043000, C556S053000, C556S056000, C556S070000, C556S087000, C556S406000, C534S011000, C534S015000, C549S003000, C549S032000, C502S103000, C502S117000, C526S160000, C526S943000, C526S128000, C526S149000, C526S150000, C526S348100, C526S348500, C526S351000, C526S352000

Reexamination Certificate

active

06635779

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a new class of metallocene compounds, to a catalyst for the polymerization of olefins containing them and to a polymerization 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 cyclopentadienyl groups are known as catalyst components for the polymerization of olefins. European Patent 129,368, for instance, describes a catalyst system for the polymerization of olefins comprising (a) a biscyclopentadienyl coordination complex with a transition metal and (b) an alumoxane. The two cyclopentadienyl groups can be linked by a divalent group.
More recently, heterocyclic metallocene compounds used in the polymerization of alpha-olefins have been described. For example, U.S. Pat. No. 5,489,659 relates to a class of silicon-containing metallocene compounds for the polymerization of alpha-olefins wherein the silicon atom is part of a non-aromatic ring condensed to the cyclopentadienyl ring. Metallocenes of this type are used in the polymerization of propylene. The activity of these metallocene-based catalysts is not satisfactory.
In International application WO 98/22486 it is described a class of metallocenes containing a cyclopentadienyl radical directly coordinating the central metal atom, to which are fused one or more rings containing at least one heteroatom. These metallocenes, in combination with a suitable cocatalyst, are used in the polymerization of olefins, such as propylene. However, the molecular weights that can be obtained at polymerization temperatures of industrial interest are still too low for most utilization and the activity of those catalyst systems, when used in the polymerization of propylene, is not satisfactory.
It would be desirable to provide a novel class of metallocenes which, when used in catalysts for the polymerization of olefins, in particular of propylene, have high activity such that the amount of the catalyst remaining in the formed polymer is minimized. Furthermore high-activity catalyst capable of yielding polymers endowed with high molecular weight, narrow molecular weight distribution as well as a high degree of isotacticity and thus of crystallinity would be desirable.
A novel class of metallocene compounds has now been unexpectedly found, which achieves the above and other results.
According to a first aspect, the present invention provides a metallocene compound of the general formula (I):
wherein
Y is a moiety of formula (II)
 wherein
A, B and D, same or different from each other, are selected from an element of the groups 14 to 16 of the Periodic Table of the Elements (new IUPAC version), with the exclusion of nitrogen and oxygen;
R
1
, R
2
, R
3
, R
4
and R
5
, same or different from each other, are selected from hydrogen, 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, C
7
-C
20
-arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; wherein two R
3
can form a ring comprising 4 to 8 atoms, or R
3
and R
4
can form a ring comprising 4 to 8 atoms, which can bear substituents; with the proviso that when s is 0 or when R
3
is hydrogen, R
2
is not hydrogen;
m, n and s, equal to or different from each other, are selected from 0, 1 and 2;
m, n and s being 0 when respectively A, B and D are selected from an element of the group 16 of the Periodic Table of the Elements (new IUPAC version);
m, n and s being 1 when respectively A, B and D are selected from an element of the group 15 of the Periodic Table of the Elements (new IUPAC version);
m, n and s being 1 or 2 when respectively A, B and D are selected from an element of the group 14 of the Periodic Table of the Elements (new IUPAC version);
and wherein the ring containing A, B and D can have double bonds in any of the allowed positions, having an aromatic character;
Z is selected from a moiety of formula (II) as described above and from a moiety of formula (III):
 wherein R
6
, R
7
, R
8
and R
9
, same or different from each other, are selected from hydrogen, 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, C
7
-C
20
-arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements, R
7
being different from hydrogen; optionally R
6
and R
7
or R
7
and R
8
can form a ring comprising 4 to 8 carbon atoms, which can bear substituents;
and when Z is a moiety of formula (II), Y and Z can be the same or different from each other;
L is a divalent bridging group; preferably selected from the group consisting of C
1
-C
20
alkylidene, C
3
-C
20
cycloalkylidene, C
6
-C
20
arylidene, C
7
-C
20
alkylarylidene, C
7
-C
20
arylalkylidene optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements and silylidene containing up to 5 silicon atoms such as SiMe
2
, SiP
2
, SiMe
2
SiMe
2
radical;
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),
X, same or different, is a hydrogen atom, a halogen atom, a R
10
, OR
10
, OSO
2
CF
3
, OCOR
10
, SR
10
, NR
10
2
or PR
10
2
group, wherein the substituents R
10
are selected from the group consisting of C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
7
-C
20
alkylaryl and C
7
-C
20
arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements;
p is an integer of from 0 to 3, preferably from 1 to 3, being equal to the oxidation state of the metal M minus 2, preferably p is 2;
The transition metal M is preferably titanium, zirconium or hafnium. More preferably it is zirconium;
Preferably the substituents X are chlorine atoms, methyl groups or benzyl groups.
Preferably the divalent bridging group L is >Si(R
17
)
2
or >C(R
17
)
2
, wherein R
17
, equal or different from each other, are selected from hydrogen, 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, C
7
-C
20
-arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; and wherein two R
17
can form a cycle comprising from 3 to 8 atoms, that can bear substituents.
More preferably the divalent bridging group L is selected from the group consisting of >Si(CH
3
)
2
, >Si(C
6
H
5
)
2
, >CH
2
and >C(CH
3
)
2
.
Preferably A is selected from sulfur, selenium, tellurium and polonium, more preferably it is sulfur.
Preferably B and D are selected from the group 14 of the Periodic Table of the Elements (new IUPAC version), more preferably they are carbon atoms.
When Z is a moiety of formula (III) it is preferably selected among those of formula (IV):
wherein
R
11
, R
12
, R
13
, R
14
, R
15
and R
16
, same or different from each other, are selected from hydrogen, 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, C
7
-C
20
-arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements, optionally R
11
and R
12
, or R
12
and R
13
, or R
13
and R
14
can form a ring comprising 4 to 8 atoms which can bear substituents. Preferably R
14
and R
16
are different from hydrogen. More preferably R
14
is a C
6
-C
20
-aryl group, such as a phenyl or naphtyl group, and R
16
is a C
1
-C
20
-alkyl group, such as a methyl group.
Non limiting examples of the metallocenes of the present invention are:
dimethylsilandiylbis-6-(3-methylcyclopentadienyl-[1,2-b]-thiophene)zirconium dichloride and methyl;
dimethylsilandiylbis-6-(4-methylcyclopentadienyl-[1,2-b]-thiophene)zirconium dichlorid

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