Polyolefins prepared with metallocene catalysts having...

Details Polyolefins prepared with metallocene catalysts having... Polyolefins prepared with metallocene catalysts having...

1994-10-17

2001-06-05

Teskin, Fred (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S129000, C526S160000, C526S351000, C526S942000, C502S117000, C502S152000, C556S009000, C556S011000, C556S014000, C556S019000, C556S021000, C556S022000, C556S043000, C556S053000, C556S058000

Reissue Patent

active

RE037208

ABSTRACT:

The present invention relates to novel metallocenes which contain ligands of 2-substituted indenyl derivatives and can very advantageously be used as catalysts in the preparation of polyolefins of high melting point (high isotacticity).
Polyolefins of relatively high melting point and thus relatively high crystallinity and relatively high hardness are particularly important as engineering materials (for example large hollow articles, tubes and moldings).
Chiral metallocenes are, in combination with aluminoxanes, active, stereospecific catalysts for the preparation of polyolefins (U.S. Pat. No. 4,769,510). These metallocenes also include substituted indene compounds. Thus, for example, the use of the ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride/aluminoxane catalyst system is known for the preparation of isotactic polypropylene; cf. EP-A 185 918). Both this and numerous other polymerization processes coming under the prior art have, in particular, the disadvantage that, at industrially interesting polymerization temperatures, only polymers of relatively low melting points are obtained. Their crystallinity and thus their hardness are too low for use as engineering materials.
Surprisingly, it has now been found that metallocenes which contain, as ligands, certain 2-substituted indenyl derivatives are suitable catalysts for the preparation of polyolefins of high isotacticity (melting point) and narrow molecular weight distribution.
The present invention therefore provides the compounds of the formula I below
in which
M
1
is a metal from group IVb, Vb or VIb of the Periodic Table,
R
1
and R
2
are identical or different and are a hydrogen atom, a C
1
-C
10
-alkyl group, a C
1
-C
10
-alkoxy group, a C
6
-C
10
-aryl group, a C
6
-C
10
-aryloxy group, a C
2
-C
10
-alkenyl group, a C
7
-C
40
-arylalkyl group, a C
7
-C
40
-alkylaryl group, a C
8
-C
40
-arylalkenyl group or a halogen atom,
R
3
and R
4
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
10
-alkyl group, which may be halogenated, a C
6
-C
10
-aryl group, an —NR
2
15
, —SR
15
, —OSiR
3
15
, —SiR
3
15
or —PR
2
15
radical in which R
15
is a halogen atom, a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group,
R
5
and R
6
are identical or different and are as defined for R
3
and R
4
, with the proviso that R
5
and R
6
are not hydrogen,
R
7
is
where
R
11
, R
12
and R
13
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
10
-alkyl group, a C
1
-C
10
-fluoroalkyl group, a C
6
-C
10
-aryl group, a C
6
-C
10
-fluoroaryl group, a C
1
-C
10
-alkoxy group, a C
2
-C
10
-alkenyl group, a C
7
-C
40
-arylalkyl group, a C
8
-C
40
-arylalkenyl group or a C
7
-C
40
-alkylaryl group, or R
11
and R
12
or R
11
and R
13
, in each case with the atoms connecting them, form a ring,
M
2
is silicon, germanium or tin,
R
8
and R
9
are identical or different and are as defined for R
11
,
m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2, and,
the radicals R
10
are identical or different and are as defined for R
11
, R
12
and R
13
.
Alkyl is straight-chain or branched alkyl. Halogen (halogenated) is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
In the formula I, M
1
is a metal from group IVb, Vb or VIb of the Periodic Table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably zirconium, hafnium or titanium.
R
1
and R
2
are identical or different and are a hydrogen atom, a C
1
-C
10
-, preferably C
1
-C
3
-alkyl group, a C
1
-C
10
-, preferably C
1
-C
3
-alkoxy group, a C
6
-C
10
-, preferably C
6
-C
8
-aryl group, a C
6
-C
10
-, preferably C
6
-C
8
-aryloxy group, a C
2
-C
10
-, preferably C
2
-C
4
-alkenyl group, a C
7
-C
40
, preferably C
7
-C
10
-arylalkyl group, a C
7
-C
40
-, preferably C
7
-C
12
-alkylaryl group, a C
8
-C
40
-, preferably C
8
-C
12
-arylalkenyl group or a halogen atom, preferably chlorine.
R
3
and R
4
are identical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C
1
-C
10
-, preferably C
1
-C
4
-alkyl group, which may be halogenated, a C
6
-C
10
-, preferably C
6
-C
8
-aryl group, an —NR
2
15
, —SR
15
, —OSiR
3
15
, —SiR
3
15
or —PR
2
15
radical in which R
15
is a halogen atom, preferably a chlorine atom, or a C
1
-C
10
-, preferably C
1
-C
3
-alkyl group or a C
6
-C
10
-, preferably C
6
-C
8
-aryl group. R
3
and R
4
are particularly preferably hydrogen.
R
5
and R
6
are identical or different, preferably identical, and are as defined for R
3
and R
4
, with the proviso that R
5
and R
6
cannot be hydrogen. R
5
and R
6
are preferably (C
1
-C
4
)-alkyl which may be halogenated, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or trifluoromethyl, in particular methyl.
R
7
is
where R
11
, R
12
and R
13
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
10
-, preferably C
1
-C
4
-alkyl group, in particular a methyl group, a C
1
-C
10
-fluoroalkyl group, preferably a CF
3
group, a C
6
-C
10
-, preferably C
6
-C
8
-aryl group, a C
6
-C
10
-fluoroaryl group, preferably a pentafluorophenyl group, a C
1
-C
10
-, preferably C
1
-C
4
-alkoxy group, in particular a methoxy group, a C
2
-C
10
-, preferably C
2
-C
4
-alkenyl group, a C
7
-C
40
-, preferably C
7
-C
10
-arylalkyl group, a C
8
-C
40
-, preferably C
8
-C
12
-arylalkenyl group or a C
7
-C
40
-, preferably C
7
-C
12
-alkylaryl group, or R
11
and R
12
or R
11
and R
13
, in each case together with the atoms connecting them, form a ring.
M
2
is silicon, germanium or tin, preferably silicon or germanium.
R
7
is preferably ═CR
11
R
12
, ═SiR
11
R
12
, ═GeR
11
R
12
, —O—, —S—, ═SO, ═PR
11
or ═P(O)R
11
.
R
8
and R
9
are identical or different and are as define as for R
11
.
m and n are identical or different and are zero, 1 or 2, preferably zero or 1, where m plus n is zero, 1 or 2, preferably zero or 1.
The radicals R
10
are identical or different and are as defined for R
11
, R
12
and R
13
. The radicals R
10
are preferably hydrogen atoms or C
1
-C
10
, preferably C
1
-C
4
-alkyl groups.
The particularly preferred metallocenes are thus those in which, in the formula I, M
1
is Zr or Hf, R
1
and R
2
are identical or different and are methyl or chlorine, R
3
and R
4
are hydrogen, R
5
and R
6
are identical or different and are methyl, ethyl or trifluoromethyl, R
7
is
radical, n plus m is zero or 1, and R
10
is hydrogen; in particular the compounds I listed in the working examples.
Of the metallocenes I mentioned in the working examples, rac-dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1-indenyl)
2
zirconium dichloride, rac-ethylene(2-methyl-4,5,6,7-tetrahydro-1-indenyl)
2
zirconium dichloride, racdimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1-indenyl)
2
dimethylzirconium and rac-ethylene(2-methyl-4,5,6,7-tetrahydro-1-indenyl)
2
dimethylzirconium are particularly important.
The chiral metallocenes are employed as racemates for the preparation of highly isotactic poly-1-olefins. However, it is also possible to use the pure R- or S-form. These pure stereoisomeric forms allow the preparation of an optically active polymer. However, the meso form of the metallocenes should be separated off since the polymerization-active center (the metal atom) in these compounds is no longer chiral due to mirror symmetry at the central metal, and it is therefore not possible to produce a highly isotactic polymer.
The principle of resolution of the stereoisomers is known.
The present invention furthermore provides a process for the preparation of the metallocenes I, which comprises
a) reacting a compound of the formula II
in which R
3
-R
10
, m and n are defined in the formula I and M
3
is an alkali metal, preferably lithium, with a compound of the formula III
M
1
X
4
  (III)
in which M
3
is a defined in the formula I, and X is a halogen atom, preferably chlorine, and catalytically hydrogenating the reaction product, or
b) reacting a co

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