U.S. patent application number 09/756315 was filed with the patent office on 2001-09-13 for metallocenes containing aryl-substituted indenyl derivatives as ligands, process for their preparation, and their use as catalysts.
Invention is credited to Bachmann, Bernd, Kuber, Frank, Rohrmann, Jurgen, Spaleck, Walter, Winter, Andreas.
Application Number | 20010021755 09/756315 |
Document ID | / |
Family ID | 6462039 |
Filed Date | 2001-09-13 |
United States Patent
Application |
20010021755 |
Kind Code |
A1 |
Kuber, Frank ; et
al. |
September 13, 2001 |
Metallocenes containing aryl-substituted indenyl derivatives as
ligands, process for their preparation, and their use as
catalysts
Abstract
Metallocenes containing aryl-substituted indenyl derivatives as
ligands, process for their preparation, and their use as catalysts.
A very effective catalyst system for the polymerization or
copolymerization of olefins comprises a cocatalyst, preferably an
aluninoxane or a supported aluminoxane, and a metallocene of the
formula I 1 in which, in the preferred form, M.sup.1 is Zr or Ef,
R.sup.1 and R.sup.2 are halogen or alkyl, R.sup.3 is alkyl, R.sup.4
to R.sup.12 are alkyl or hydrogen and R.sup.13 is a (substituted)
alkylene or heteroatom bridge. The metallocenes, in particular the
zirconocenes, produce polymers of very high molecular weight, in
the case of prochiral monomers polymers of very high molecular
weight, very high stereotacticity and very high melting point, at
high catalyst activities in the industrially particularly
interesting temperature range between 50 and 80.degree. C. In
addition, reactor deposits are avoided by means of supported
catalyst systems.
Inventors: |
Kuber, Frank; (Oberursel,
DE) ; Bachmann, Bernd; (Eppstein/Taunus, DE) ;
Spaleck, Walter; (Liederbach/Taunus, DE) ; Winter,
Andreas; (Glashutten/Taunus, DE) ; Rohrmann,
Jurgen; (Kelkheim (Taunus), DE) |
Correspondence
Address: |
CONNOLLY, BOVE,
LODGE & HUTZ, LLP
1220 Market Street
P.O. Box 2207
Wilmington
DE
19899
US
|
Family ID: |
6462039 |
Appl. No.: |
09/756315 |
Filed: |
January 8, 2001 |
Related U.S. Patent Documents
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Application
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09756315 |
Jan 8, 2001 |
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09217365 |
Dec 21, 1998 |
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6255506 |
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09217365 |
Dec 21, 1998 |
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09002070 |
Dec 31, 1997 |
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6051727 |
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09002070 |
Dec 31, 1997 |
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08475155 |
Jun 7, 1995 |
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5770753 |
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08475155 |
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08083816 |
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Current U.S.
Class: |
526/127 ;
502/120; 502/155; 526/160; 526/943; 556/11; 556/12; 556/13; 556/19;
556/42; 556/43; 556/51; 556/52; 556/53; 556/7; 556/8; 556/9 |
Current CPC
Class: |
B01J 2231/12 20130101;
C08F 110/06 20130101; Y10S 526/943 20130101; B01J 31/2295 20130101;
C07C 49/67 20130101; C07C 17/14 20130101; C08F 4/63927 20130101;
B01J 2531/40 20130101; C08F 297/083 20130101; Y10S 526/905
20130101; C07C 45/46 20130101; C08F 110/02 20130101; B01J 2531/60
20130101; C08F 10/00 20130101; B01J 2531/48 20130101; B01J 2531/50
20130101; B01J 31/143 20130101; C08F 297/08 20130101; C08F 4/63912
20130101; C08F 4/63916 20130101; C08F 210/06 20130101; C08F 210/16
20130101; C07F 17/00 20130101; Y10S 526/904 20130101; C07C 17/14
20130101; C07C 22/04 20130101; C07C 45/46 20130101; C07C 49/67
20130101; C08F 10/00 20130101; C08F 4/63927 20130101; C08F 110/02
20130101; C08F 2500/17 20130101; C08F 2500/12 20130101; C08F 110/06
20130101; C08F 2500/17 20130101; C08F 2500/03 20130101; C08F 110/06
20130101; C08F 2500/17 20130101; C08F 2500/01 20130101; C08F
2500/03 20130101; C08F 2500/15 20130101; C08F 2500/12 20130101;
C08F 2500/18 20130101; C08F 210/06 20130101; C08F 210/16 20130101;
C08F 2500/17 20130101; C08F 2500/12 20130101; C08F 210/16 20130101;
C08F 210/06 20130101; C08F 2500/17 20130101; C08F 2500/03 20130101;
C08F 110/06 20130101; C08F 2500/17 20130101; C08F 2500/03 20130101;
C08F 2500/15 20130101; C08F 210/06 20130101; C08F 210/16 20130101;
C08F 2500/17 20130101; C08F 2500/03 20130101; C08F 110/06 20130101;
C08F 2500/17 20130101; C08F 2500/12 20130101; C08F 2500/03
20130101; C08F 2500/01 20130101; C08F 2500/18 20130101; C08F
2500/15 20130101 |
Class at
Publication: |
526/127 ;
526/160; 526/943; 556/7; 556/8; 556/9; 556/11; 556/12; 556/13;
556/19; 556/42; 556/43; 556/51; 556/52; 556/53; 502/120;
502/155 |
International
Class: |
C08F 004/44 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 27, 1992 |
DE |
P 42 21 244.8 |
Claims
1. A compound of formula I 11in which M.sup.1 is a metal from group
IVb, Vb or VIb of the Periodic Table, R.sup.1 and R.sup.2 are
identical or different and are a hydrogen atom, a
C.sub.1-C.sub.10-alkyl group, a C.sub.1-C.sub.10-alkoxy group, a
C.sub.6-C.sub.10-aryl group, a C.sub.6-C.sub.10-aryloxy group, a
C.sub.2-C.sub.10-alkenyl group, a C.sub.7-C.sub.40-arylalkyl group,
a C.sub.7-C.sub.40-alkylaryl group, a C.sub.8-C.sub.40-arylalkenyl
group, an OH group or a halogen atom, the radicals R.sup.3 are
identical or different and are a hydrogen atom, a halogen atom, a
C.sub.1-C.sub.10-alkyl group, which may be halogenated, a
C.sub.6-C.sub.10-aryl group, an --NR.sup.16.sub.2, --SR.sup.16,
--OSiR.sup.16.sub.3, --SiR.sup.16.sub.3 or --PR.sup.16.sub.2
radical, in which R.sup.16 is a halogen atom, a
C.sub.1-C.sub.10-alkyl group or a C.sub.6-C.sub.10-aryl group,
R.sup.4 to R.sup.12 are identical or different and are as defined
for R.sup.3, or adjacent radicals R.sup.4 to R.sup.12, together
with the atoms connecting them, form one or more aromatic or
aliphatic rings, or the radicals R.sup.5 and R.sup.8 or R.sup.12,
together with the atoms connecting them, form an aromatic or
aliphatic ring, R.sup.13 is 12.dbd.BR.sup.14, .dbd.AIR.sup.14,
--Ge--, --O--, O--S--, .dbd.SO, .dbd.SO.sub.2, .dbd.NR.sup.14,
.dbd.CO, .dbd.PR.sup.14 or .dbd.P(O)R.sup.14, where R.sup.14 and
R.sup.15 are identical or different and are a hydrogen atom, a
halogen atom, a C.sub.1-C.sub.10-alkyl group, a
C.sub.1-C.sub.10-fluoroalkyl group, a C.sub.1-C.sub.10-alkoxy
group, a C.sub.6-C.sub.10-aryl group, a C.sub.6-C.sub.10-fluoroaryl
group, a C.sub.6-C.sub.10-aryloxy group, a C.sub.2-C.sub.10-alkenyl
group, a C.sub.7-C.sub.40-arylalkyl group, a
C.sub.7-C.sub.40-alkylaryl group or a C.sub.8-C.sub.40-arylalkenyl
group, or R.sup.14 and R.sup.15, in each case together with atoms
connecting them, form one or more rings, and M.sup.2 is silicon,
germanium or tin.
2. A compound of the formula I as claimed in claim 1, wherein, in
the formula I, M.sup.1 is zirconium or hafnium, R.sup.1 and R.sup.2
are identical and are a C.sub.1-C.sub.3-alkyl group or a halogen
atom, the radicals R.sup.3 are identical and are a
C.sub.1-C.sub.4-alkyl group R.sup.4 to R.sup.12 are identical or
different and are hydrogen or a C.sub.1-C.sub.4-alkyl group, and
R.sup.13 is 13where M.sup.2 is silicon or germanium and R.sup.14
and R.sup.15 are identical or different and are a
C.sub.1-C.sub.4-alkyl group or a C.sub.4-C.sub.10-aryl group.
3. A compound of the formula I as claimed in claim 1, wherein, in
the formula I, R.sup.4 and R.sup.7 are hydrogen, and R.sup.5,
R.sup.6 and R.sup.8 to R.sup.12 are identical or different and are
hydrogen or a C.sub.1-C.sub.4-alkyl group.
4. A compound of the formula I as claimed in claim 1, wherein, in
formula I, M.sup.1 is zirconium, R.sup.1 and R.sup.2 are identical
and are chlorine, the radicals R.sup.3 are identical and are a
C.sub.1-C.sub.4-alkyl group, R.sup.4 and R.sup.7 are hydrogen,
R.sup.5, R.sup.6 and R.sup.8 to R.sup.12 are identical or different
and are a C.sub.1-C.sub.4-alkyl group or hydrogen, and R.sup.13 is
14where M.sup.2 is silicon and R.sup.14 and R.sup.15 are identical
or different and are a C.sub.1-C.sub.4-alkyl group or a
C.sub.6-C.sub.10-aryl group.
5. A compound of formula I as claimed in claim 1, wherein, in the
formula I, M.sup.1 is zirconium, R.sup.1 and R.sup.2 are chlorine,
the radicals R.sup.3 are methyl or ethyl, R.sup.4 to R.sup.12 are
hydrogen, and R.sup.13 is 15where M.sup.2 is silicon, and R.sup.14
and R.sup.15 are identical or different and are methyl, ethyl,
n-propyl, i-propyl or phenyl.
6. A process for the preparation of an olefin polymer by
polymerization or copolymerization of an olefin of the formula
R.sup.a--CH.dbd.CH--R.sup.b, in which R.sup.a and R.sup.b are
identical or different and are a hydrogen atom or a hydrocarbon
radical having 1 to 14 carbon atoms, or R.sup.a and R.sup.b,
together with the atoms connecting them, can form one or more
rings, and at a temperature of from -60 to 200.degree. C., at a
pressure of 0.5 to 100 bar, in solution, in suspension or in the
gas phase, in the presence of a catalyst formed from a metallocene
as transition-metal compound and a cocatalyst, wherein the
metallocene is a compound of the formula I as claimed in claim
1.
7. The process as claimed in claim 6, wherein the cocatalyst used
is an aluminoxane of the formula IIa for the linear type and/or of
the formula IIb for the cyclic type 16where, in the formulae IIa
and IIb, the radicals R.sup.17 are identical or different and are a
C.sub.1-C.sub.6-alkyl group, a C.sub.6-C.sub.18-aryl group, benzyl
or hydrogen, and p is an integer from 2 to 50.
8. The process as claimed in claim 6, wherein the cocatalyst used
is methylaluminoxane.
9. The process as claimed in claim 6, wherein the metallocene of
the formula I is preactivated by means of an aluminoxane of the
formula IIa and/or IIb before use in the polymerization
reaction.
10. The process as claimed in claim 6, wherein a supported
polymerization catalyst is employed which is the product of the
reaction of a metallocene of the formula I with a supported
organoaluminum compound (cocatalyst).
11. The process as claimed in claim 10, wherein the support
material is an oxide of silicon and/or of aluminum, and the
organoaluminum compound is methylaluminoxane.
12. The use of a metallocene of formula I as claimed in claim 1 as
a catalyst component in the polymerization or copolymerization of
olefins.
Description
DESCRIPTION
[0001] Metallocenes containing aryl-substituted indenyl derivatives
as ligands, process for their preparation, and their use as
catalysts.
[0002] The invention relates to novel metallocenes containing
aryl-substituted indenyl derivatives as ligands which can be used
very advantageously as catalysts components in the preparation of
polyolefins of high isotacticity, narrow molecular-weight
distribution and very high molecular weight.
[0003] Polyolefins of high molecular weight are of particular
importance for the production of films, sheets or large hollow
articles or moldings, such as, for example, pipes.
[0004] The literature discloses the preparation of polyolefins
using soluble metallocene compounds in combination with
aluminoxanes or other cocatalysts which, due to their Lewis
acidity, are able to convert the neutral metallocene into a cation
and stabilize it.
[0005] Soluble metallocene compounds based on bis(cyclopentadienyl)
dialkyl zirconium or bis (cyclopentadienyl) zirconium dihalide in
combination with oligomeric aluminoxanes are capable of
polymerizing ethylene in good activity and propylene in moderate
activity. Polyethylene having a narrow molecular-weight
distribution and moderate molecular weight is obtained. The
polypropylene prepared in this way is atactic and has a very low
molecular weight.
[0006] The preparation of isotactic polypropylene is achieved with
the aid of ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium
dichloride together with an aluminoxane in a suspension
polymerization (cf. EP 185 918). The polymer has a narrow
molecular-weight distribution. A particular disadvantage of this
process is that, at industrially relevant polymerization
temperatures, only polymers having a very low molecular weight can
be prepared.
[0007] A special preactivation method for the metallocene using an
aluminoxane has also been proposed, resulting in a significant
increase in the activity of the catalyst system and in a
considerable improvement in the grain morphology of the polymer
(cf. DE 37 26 067). However, the preactivation hardly increases the
molecular weight at all.
[0008] Also known are catalysts based on ethylenebisindenylhafnium
dichloride and ethylenebis(4,5,6,7-tetrahydro-1-indenyl)hafnium
dichloride and methylaluminoxane, by means of which relatively
high-molecular-weight polypropylenes can be prepared by suspension
polymerization (cf. J. Am. Chem. Soc. (1987), 109, 6544). However,
the grain morphology of the polymers produced in this way under
industrially relevant polymerization conditions is unsatisfactory,
and the activity of the catalyst systems employed is comparatively
low. Together with the high catalysts costs, inexpensive
polymerization using these systems is thus impossible.
[0009] A significant increase in the molecular weight has been
achieved by using metallocenes in which the aromatic .pi.-ligands
fixed by a bridge carry substituents in the 2-position (cf. DE 40
35 886) or in the 2- and 4-position (cf. DE 41 28 238).
[0010] A further increase in the molecular weight has been achieved
by using aromatic n-ligands containing substituents in the 2-, 4-
and 6-position (cf. DE 41 39 596) and aromatic a-ligands of the
4,5-benzoindenyl type (cf. DE 41 39 595).
[0011] The last-mentioned metallocenes containing said substituents
are already very effective in this respect at the polymerization
temperature of 70.degree. C. Nevertheless, the molecular weights
which can be achieved at the industrially optimum polymerization
temperature of 70.degree. C. are still too low for many industrial
applications, such as, for example, the preparation of polymers for
pipes and large hollow articles, and in particular fibers.
[0012] Under the constraints of inexpensive large-scale production,
polymerizations must be carried out at the highest possible
reaction temperature, since the heat of reaction produced at
relatively high polymerization temperatures can be dissipated using
little cooling medium. The cooling-water circuit can therefore be
made significantly smaller.
[0013] A disadvantage which frequently occurs in soluble
(homogeneous) metallocene/methylaluminoxane catalyst systems in
processes in which the polymer is formed as a solid is the
formation of thick deposits on reactor walls and stirrer. These
deposits are formed by agglomeration of the polymer particles if
the metallocene, or aluminoxane, or both, are in the form of a
solution in the suspension medium. Deposits of this type in the
reactor systems must be removed regularly, since they rapidly
achieve considerable thicknesses, have high strength and hinder
heat exchange with the cooling medium.
[0014] It is therefore advantageous to employ metallocenes in
supported form. An efficient and simple process for supporting
metallocenes which can be employed universally in all
polymerization processes has been proposed (cf. EP 92
107331.8).
[0015] A further disadvantage in the case of stereospecific
polymerization of prochiral monomers, for example of propylene,
using metallocene catalysts is the relatively low isotacticity,
which results in low melting points in the case of isotactic
polypropylene. In particular metallocenes containing substituents
in the 2- and 4-position and specifically rac-dimethylsilylbis
(2-methyl-4-isopropylindenyl) zirconium dichloride in combination
with methylaluminoxane gives, in the case of propylene, a polymer
of high isotacticity and thus high melting point (cf. DE 41 28
238). Nevertheless, the melting points which can be achieved are
too low at industrially relevant polymerization temperatures (for
example 70.degree. C.) for some industrial applications.
[0016] However, there are also industrial applications in which low
melting points are desired.
[0017] The object was to find a process and/or a catalyst system
which produces polymers of very high molecular weight and, in the
case of isospecific polymerization of prochiral monomers, polymers
of high isotacticity in high yield. The use of a support would
prevent the disadvantages known from the prior art caused by
deposit formation and a high proportion of fine particles. The use
of hydrogen as molecular weight regulator should then enable the
entire range of industrially interesting molecular weights to be
covered by means of only a single metallocene.
[0018] It has been found that metallocenes containing specific
indenyl derivatives as ligands are suitable catalysts (catalyst
components) in the preparation of polyolefins of high molecular
weight, in particular on use of prochiral monomers of isotactic
polyolefins of very high molecular weight and very high
isotacticity.
[0019] Reaction of these soluble metallocenes with a supported
organoaluminum catalyst component gives a catalyst system which
requires no additional cocatalyst for activation and completely
prevents formation of reactor deposits.
[0020] The present invention therefore relates to compounds of the
formula I: 2
[0021] in which
[0022] M.sup.1 is a metal from group IVb, Vb or VIb of the Periodic
Table,
[0023] R.sup.1 and R.sup.2 are identical or different and are a
hydrogen atom, a C.sub.1-C.sub.10-alkyl group, a
C.sub.1-C.sub.10-alkoxy group, a C.sub.6-C.sub.10-aryl group, a
C.sub.6-C.sub.10-aryloxy group, a C.sub.2-C.sub.10-alkenyl group, a
C.sub.7-C.sub.10-arylalkyl group, a C.sub.7-C.sub.40-alkylarl
group, a C.sub.8-C.sub.40-arylalkenyl group, an OH group or a
halogen atom, the radicals R.sup.3 are identical or different and
are a hydrogen atom, a halogen atom, a C.sub.1-C.sub.10-alkyl
group, which may be halogenated, a C.sub.6-C.sub.10-aryl group, an
--NR.sup.16.sub.2, --SR.sup.16, --OSiR.sup.16.sub.3,
--SiR.sup.16.sub.3 or --PR.sup.16.sub.2 radical, in which R.sup.16
is a halogen atom, a C.sub.1-C.sub.10-alkyl group or a
C.sub.6-C.sub.10-aryl group, R.sup.4 to R.sup.12 are identical or
different and are as defined for R.sup.3, or adjacent radicals
R.sup.4 to R.sup.12, together with the atoms connecting them, form
one or more aromatic or aliphatic rings, or the radicals R.sup.5
and R.sup.8 or R.sup.12, together with the atoms connecting them,
form an aromatic or aliphatic ring,
[0024] R.sup.13 is 3
[0025] .dbd.BR.sup.14, .dbd.AIR.sup.14, --Ge--, --O--, O--S--,
.dbd.SO, .dbd.SO.sub.2, .dbd.NR.sup.14, .dbd.CO, .dbd.PR.sup.14 or
.dbd.P(O)R.sup.14, where R.sup.14 and R.sup.15 are identical or
different and are a hydrogen atom, a halogen atom, a
C.sub.1-C.sub.10-alkyl group, a C.sub.1-C.sub.10-fluoroalkyl group,
a C.sub.1-C.sub.10-alkoxy group, a C.sub.6-C.sub.10-aryl group, a
C.sub.6-C.sub.10-fluoroaryl group, a C.sub.6-C.sub.10-aryloxy
group, a C.sub.2-C.sub.10-alkenyl group, a
C.sub.7-C.sub.40-arylalkyl group, a C.sub.7-C.sub.40-alkylaryl
group or a C.sub.8-C.sub.40-arylalkenyl group, or R.sup.14 and
R.sup.15, in each case together with atoms connecting them, form
one or more rings, and
[0026] M.sup.2 is silicon, germanium or tin.
[0027] The present invention also relates to a process for the
preparation of an olefin polymer by polymerization or
copolymerization of an olefin of the formula
R.sup.a--CH.dbd.CH--R.sup.6, in which R.sup.a and R.sup.b are
identical or different and are a hydrogen atom or a hydrocarbon
radical having 1 to 14 carbon atoms, or R.sup.a and R.sup.b,
together with the atoms connecting them, may form one or more
rings, at a temperature of from -60 to 200.degree. C., at a
pressure from 0.5 to 100 bar, in solution, in suspension or in the
gas phase, in the presence of a catalyst formed from a metallocene
as transition-metal compound and a cocatalyst, wherein the
metallocene is a compound of the formula I.
[0028] The compounds according to the invention are metallocenes of
the formula I 4
[0029] in which M.sup.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.
[0030] R.sup.1 and R.sup.2 are identical or different and are a
hydrogen atom, a C.sub.1-C.sub.10-, preferably
C.sub.1-C.sub.3-alkyl group, a C.sub.1-C.sub.10-, preferably
C.sub.1-C.sub.3-alkoxy group, a C.sub.6-C.sub.10-, preferably
C.sub.6-C.sub.8-aryl group, a C.sub.6-C.sub.10-, preferably
C.sub.6-C.sub.8-aryloxy group, a C.sub.2-C.sub.10-, preferably
C.sub.2-C.sub.4-alkenyl group, a C.sub.7-C.sub.40-, preferably
C.sub.7-C.sub.10-arylalkyl group, a C.sub.7-C.sub.40-, preferably
C.sub.7-C.sub.12-alkylaryl group, a C.sub.8-C.sub.40-, preferably
C.sub.8-C.sub.12-arylalkenyl group, or a halogen atom, preferably
chlorine.
[0031] The radicals R.sup.3 to R.sup.12 are identical or different
and are a hydrogen atom, a halogen atom, preferably fluorine,
chlorine or bromine, a C.sub.1-C.sub.10-, preferably
C.sub.1-C.sub.4-alkyl group, which may be halogenated, a
C.sub.6-C.sub.10-, preferably C.sub.6-C.sub.8-aryl group, an
--NR.sup.14.sub.2, --SR.sup.16, --OSiR.sup.16.sub.3,
--SiR.sup.16.sub.3 or --PR.sup.16.sub.2 radical, where R.sup.16 can
be a halogen atom, preferably chlorine, or a C.sub.1-C.sub.10-,
preferably C.sub.1-C.sub.4-alkyl group or a C.sub.6-C.sub.10-,
preferably C.sub.6-C.sub.8-aryl group.
[0032] The adjacent radicals R.sup.4 to R.sup.12, together with the
atoms connecting them, can form an aromatic, preferably 6-membered
aromatic or aliphatic, preferably 4-8-membered aliphatic ring.
[0033] R.sup.13 is 5
[0034] .dbd.BR.sup.14, .dbd.AIR.sup.14, --Ge--, --O--, --S--,
.dbd.SO, .dbd.SO.sub.2, .dbd.NR.sup.14, .dbd.CO, .dbd.PR.sup.14 or
.dbd.P(O)R.sup.14, preferably 6
[0035] .dbd.BR.sup.14, .dbd.AIR.sup.14, --Ge--, --O--, O--S--,
.dbd.SO, .dbd.SO.sub.2, .dbd.NR.sup.14, .dbd.CO, .dbd.PR.sup.14 or
.dbd.P(O)R.sup.14, where R.sup.14 and R.sup.15 are identical or
different and are a hydrogen atom, a halogen atom, a
C.sub.1-C.sub.10-, preferably a C.sub.1-C.sub.4-alkyl, in
particular a methyl group, a C.sub.1-C.sub.10-fluoroalkyl group,
preferably a CF.sub.3 group, a C.sub.6-C.sub.10-, preferably
C.sub.6-C.sub.8-aryl group, a C.sub.6-C.sub.10-fluoroaryl group,
preferably a pentafluorophenyl group, a C.sub.1-C.sub.10-,
preferably C.sub.1-C.sub.4-alkoxy group, in particular a methoxy
group, a C.sub.2-C.sub.10-, preferably C.sub.2-C.sub.4-alkenyl
group, a C.sub.7-C.sub.40-, preferably C.sub.7-C.sub.10- arylalkyl
group, a C.sub.8-C.sub.40-, preferably C.sub.8-C.sub.12-arylalkenyl
group, a C.sub.7-C.sub.40-, preferably C.sub.7-C.sub.12-alkylaryl
group, or R.sup.14 and R.sup.15, in each case with the atoms
connecting them, form a ring.
[0036] M.sup.2 is silicon, germanium or tin, preferably silicon or
germanium.
[0037] For compounds of the formula I, it is preferred that
[0038] M.sup.1 is zirconium or hafnium,
[0039] R.sup.1 and R.sup.2 are identical and are a
C.sub.1-C.sub.3-alkyl group or a halogen atom, the radicals R.sup.3
are identical and are a C.sub.1-C.sub.4-alkyl group, R.sup.4 to
R.sup.12 are identical or different and are hydrogen or a
C.sub.1-C.sub.4-alkyl group,
[0040] R.sup.13 is 7
[0041] where M.sup.2 is silicon or germanium and R.sup.14 and
R.sup.15 are identical or different and a C.sub.1-C.sub.4-alkyl
group or a C.sub.6-C.sub.10-aryl group.
[0042] Preference is furthermore given to the compounds of formula
I in which the radicals R.sup.4 and R.sup.7 are hydrogen, and
R.sup.5, R.sup.6 and R.sup.8 to R.sup.12 are a
C.sub.1-C.sub.4-alkyl group or hydrogen.
[0043] Particular preference is given to compounds of the formula I
in which M.sup.1 is zirconium, R.sup.1 and R.sup.2 are identical
and are chlorine, the radicals R.sup.3 are identical and are a
C.sub.1-C.sub.4-alkyl group, R.sup.4 and R.sup.7 are hydrogen,
R.sup.5, R.sup.6 and is R.sup.8 to R.sup.12 are identical or
different and are a C.sub.1-C.sub.4-alkyl group or hydrogen, and
R.sup.13 is 8
[0044] where M.sup.2 is silicon, and R.sup.14 and R.sup.15 are
identical or different and are a C.sub.1-C.sub.4-alkyl group or a
C.sub.6-C.sub.10-aryl group.
[0045] The preparation of the metallocene I is carried out by
processes known from the literature and is shown in the reaction
scheme below: 9
[0046] The 2-phenylbenzyl halide derivatives of the formula A are
commercially available or can be prepared by methods known from the
literature.
[0047] The conversion to the compounds of the formula B is carried
out by reaction with substituted malonic esters under basic
conditions, such as, for example, in ethanolic solutions of sodium
ethoxide.
[0048] The compounds of the formula B are hydrolyzed by means of
alkali metal hydroxides, such as potassium hydroxide or sodium
hydroxide, and the resultant dicarboxylic acids are decarboxylated
by treatment at elevated temperature to give the compounds of
formula C.
[0049] The ring closure to give the corresponding
phenyl-1-indanones of the formula D is carried out by reaction with
chlorinating reagents, such as, for example, SOCl.sub.2, to give
the corresponding acid chlorides and subsequent cyclization by
means of a Friedel-Crafts catalyst in an inert solvent, such as,
for example, AlCl.sub.3 or polyphosphoric acid in methylene
chloride or CS.sub.2.
[0050] The conversion to the 7-phenylindene derivatives of the
formula E is carried out by reduction using a hydride-transferring
reagent, such as, for example, sodium borohydride or lithium
aluminum hydride or hydrogen and an appropriate catalyst in an
inert solvent, such as, for example, diethyl ether or
tetrahydrofuran, to give the corresponding alcohols and dehydration
of the alcohols under acidic conditions, such as, for example,
p-toluene-sulfonic acid or an aqueous mineral acid, or by reaction
with dehydrating substances, such as magnesium sulfate, anhydrous
copper sulfate or molecular sieve.
[0051] The preparation of the ligand systems of the formula G and
the conversion to the bridged, chiral metallocenes of the formula E
and the isolation of the desired racemic form are known in
principle. To this end, the phenylindene derivative of the formula
E is deprotonated using a strong base, such as, for example,
butyllithium or potassium hydride in an inert solvent, and is
reacted with a reagent of the formula F to give the ligand system
of the formula G. This is subsequently deproteinated by means of
two equivalents of a strong base, such as, for example butyllithium
or potassium hydride in an inert solvent, and is reacted with the
appropriate metal tetrahalide, such as, for example, zirconium
tetrachloride, in a suitable solvent. Suitable solvents are
aliphatic or aromatic solvents, such as, for example, hexane or
toluene, ethereal solvents, such as, for example, tetrahydrofuran
or diethyl ether, or halogenated hydrocarbons, such as, for
example, methylene chloride or halogenated aromatic hydrocarbons,
such as, for example, o-dichlorobenzene. Separation of the racemic
and meso forms is effected by extraction or recrystallization using
suitable solvents.
[0052] The derivatization to give the metallocenes of the formula I
can be carried out, for example, by reaction with alkylating
agents, such as methyllithium.
[0053] Metallocenes I according to the invention are highly active
catalyst components for the polymerization of olefins. The chiral
metallocenes are preferably employed as racemates. However, it is
also possible to use the pure enantiomers in the (+) or (-) form.
The pure enantiomers allow an optically active polymer to be
prepared. However, the meso form of the metallocenes should be
removed, since the polymerization-active center (the metal atom) in
these compounds is no longer chiral due to the mirror symmetry at
the central metal atom and it is therefore not possible to produce
a highly isotactic polymer. If the meso form is not removed,
atactic polymer is formed in addition to isotactic polymer. For
certain applications, for example soft moldings, this may be
entirely desirable.
[0054] According to the invention, the cocatalyst used is
preferably an aluminoxane of the formula IIa for the linear type
and/or of the formula IIb for the cyclic type 10
[0055] where, in the formulae IIa and IIb, the radicals R.sup.17
may be identical or different and are a C.sub.1-C.sub.6-alkyl
group, a C.sub.6-C.sup.18-aryl group, benzyl or hydrogen, and p is
an integer from 2 to 50, preferably 10 to 35.
[0056] Radicals R.sup.17 are preferably identical and are
preferably methyl, isobutyl, phenyl or benzyl, particularly
preferably methyl.
[0057] If the radicals R.sup.17 are different, they are preferably
methyl and hydrogen or alternatively methyl and isobutyl, where
hydrogen or isobutyl is preferably present to the extent of
0.01-40% (number of radicals R.sup.17).
[0058] The aluminoxane can be prepared in various ways by known
processes. One of the methods is, for example, to react an aluminum
hydrocarbon compound and/or a hydridoaluminum hydrocarbon compound
with water (in gas, solid, liquid or bound form--for example as
water of crystallization) in an inert solvent (such as, for example
toluene). In order to prepare an aluminoxane containing different
radicals R.sup.17, two different trialkylaluminum compounds, for
example, according to the desired composition are reacted with
water.
[0059] The precise structure of the aluminoxanes IIa and Ilb is
unknown.
[0060] Irrespective of the preparation method, all aluminoxane
solutions have in common a varying content of unreacted aluminum
starting compound, which is in free form or as an adduct.
[0061] It is possible to reactivate metallocene by means of
aluminoxane of the formula IIa and/or IIb before use in the
polymerization reaction. This significantly increases the
polymerization activity and improves the grain morphology.
Reactivation of the transition-metal compound is carried out in
solution. The metallocene is preferably dissolved in a solution of
the aluminoxane in an inert hydrocarbon. Suitable inert
hydrocarbons are aliphatic or aromatic hydrocarbons. Toluene is
preferred.
[0062] The concentration of the aluminoxane in the solution is in
the range from about 1% by weight to the saturation limit,
preferably from 5 to 30% by weight, in each case based on the total
amount of solution. The metallocene can be employed in the same
concentration, but is preferably employed in an amount of from
10.sup.-4 to 1 mol per mol of aluminoxane. The preactivation is
carried out for from 5 minutes to 60 hours, preferably for from 5
to 60 minutes. The temperature is -78 to 100.degree. C., preferably
from 0 to 70.degree. C.
[0063] The metallocene can be used to carry out a
prepolymerization, preferably using the (or one of the) olefin(s)
employed in the polymerization.
[0064] The metallocene can also be applied to a support. Suitable
support materials are, for example, silica gels, aluminum oxides,
solid aluminoxane or other inorganic support materials, such as,
for example, magnesium chloride. Another suitable support material
is a polyolefin powder in finely divided form.
[0065] It is preferred to apply the cocatalyst, i.e. the
organoaluminum compound, to a support, such as, for example, silica
gels, aluminum oxides, solid aluminoxane, other inorganic support
materials or alternatively a polyolefin powder in finely divided
form, and then to react it with the metallocene.
[0066] Inorganic supports which can be employed are oxides produced
by flame pyrolysis by combustion of element halides in an
oxyhydrogen flame, or can be prepared as silica gels in certain
particle size distributions and particle shapes.
[0067] The preparation of the supported cocatalyst can be carried
out, for example, as described in EP 92 107 331.8 in the following
way in an explosion-proofed stainless-steel reactor with a 60 bar
pump system, with inert-gas supply, temperature control by jacket
cooling and second cooling circuit via a heat exchanger on the
forced-circulation system. The pump system aspirates the reactor
contents via a connection in the reactor bottom and forces them
into a mixer and back into the reactor through a rising line via a
heat exchanger. The mixture is designed so that the feed contains a
narrowed tube cross section, where an increased flow rate is
produced and in whose turbulence zone a narrow feed line is
installed axially and against the flow direction and which can be
fed--in cycles--in each case with a defined amount of water under
40 bar of argon. The reaction is monitored via a sampler in the
pump circuit.
[0068] In principle, however, other reactors are also suitable.
[0069] In the above-described reactor having a volume of 16
dm.sup.3, 5 dm.sup.3 of decane are introduced under inert
conditions. 0.5 dm.sup.3 (=5.2 mol) of trimethylaluminum are added
at 25.degree. C. 250 g of silica gel SD 3216-30 (Grace AG) which
had previously been dried at 120.degree. C. in an argon fluidised
bed are then metered into the reactor through a solids funnel and
homogeneously distributed with the aid of the stirrer and the pump
system. A total amount of 76.5 g of water is introduced to the
reactor in portions of 0.1 cm.sup.3 every 15 seconds over the
course of 3.25 hours. The pressure, caused by argon and the evolved
gases, is kept constant at 10 bar by a pressure-regulation valve.
When all the water has been introduced, the pump system is switched
off and the stirring is continued for a further 5 hours at
25.degree. C.
[0070] The supported cocatalyst prepared in this way is employed as
a 10% strength suspension in n-decane. The aluminum content is 1.06
mmol of Al per cm.sup.3 of suspension. The isolated solid contains
31% by weight of aluminum, and the suspension medium contains 0.1%
by weight of aluminum.
[0071] Further ways of preparing a supported cocatalyst are
described in EP 92 107331.8.
[0072] The metallocene according to the invention is then applied
to the supported cocatalyst by stirring the dissolved metallocene
with the supported cocatalyst. The solvent is removed and replaced
by a hydrocarbon in which both the cocatalyst and the metallocene
are insoluble.
[0073] The reaction to give the supported catalyst system is
carried out at a temperature of from -20 to +120.degree. C.,
preferably at from 0 to 100.degree. C., particularly preferably at
from 15 to 40.degree. C. The metallocene is reacted with the
supported cocatalyst by combining the cocatalyst as a from 1 to 40%
strength by weight suspension, preferably with a from 5 to 20%
strength by weight suspension, in an aliphatic, inert suspension
medium, such as n-decane, hexane, heptane or diesel oil, with a
solution of the metallocene in an inert solvent, such as toluene,
hexane, heptane or dichloromethane, or with the finely ground solid
of the metallocene. Conversely, it is also possible to react a
solution of the metallocene with the solid of the cocatalyst.
[0074] The reaction is carried out by vigorous mixing, for example
by stirring at a molar Al/M.sup.1 ratio of from 100/1 to 10,000/1,
preferably from 100/1 to 3,000/1, and for a reaction time of from 5
to 120 minutes, preferably from 10 to 60 minutes, particularly
preferably from 10 to 30 minutes, under inert conditions.
[0075] During the reaction time for the preparation of the
supported catalyst system, in particular on use of metallocenes
according to the invention having absorption maxima in the visible
region, changes in the color of the reaction mixture occur which
can be used to monitor the progress of the reaction.
[0076] When the reaction time is complete, the supernatant solution
is separated off, for example by filtration or decanting. The solid
which remains is washed from 1 to 5 times with an inert suspension
medium, such as toluene, n-decane, hexane, diesel oil or
dichloromethane, in order to remove soluble constituents in the
catalyst formed, in particular to remove unreacted and thus soluble
metallocene.
[0077] The supported catalyst system prepared in this way can be
dried in vacuo as a powder or resuspended with adhering solvent and
metered into the polymerization system as a suspension in one of
the abovementioned inert suspension media.
[0078] According to the invention, compounds of the formulae
R.sup.18.sub.xNH.sub.4-xBR.sup.19.sub.4,
R.sup.18.sub.xPH.sub.4-xBR.sup.1- 9.sub.4,
R.sup.18.sub.3CBR.sup.19.sub.4 and BR.sup.19.sub.3 can be used as
suitable cocatalysts in place of or in addition to an aluminoxane.
In these formulae, x is a number from 1 to 4, preferably 3, the
radicals R.sup.18 are identical or different, preferably identical,
and are C.sub.1-C.sub.10-alkyl, C.sub.6-C.sub.18-aryl or 2 radicals
R.sup.18, together with the atom connecting them, form a ring, the
radicals R.sup.19 are identical or different, preferably identical,
and are C.sub.6-C.sub.18-aryl, which may be substituted by alkyl,
haloalkyl or fluorine. In particular, R.sup.18 is ethyl, propyl,
butyl or phenyl and R.sup.19, phenyl, pentafluorophenyl,
3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (cf. EP 277
003, EP 277 004 and EP 426 638).
[0079] If the abovementioned cocatalysts are used, the actual
(active) polymerization catalyst comprises the product of the
reaction of the metallocene and one of said compounds. For this
reason, this reaction product is preferably prepared in advance
outside the polymerization reactor in a separate step using a
suitable solvent.
[0080] In principle, the cocatalyst can be, according to the
invention, any compound which, due to its Lewis acidity, is able to
convert the neutral metallocene into a cation and stabilize the
latter ("labile coordination"). In addition, the cocatalyst or the
anion formed therefrom should not undergo any further reactions
with the metallocene cation formed (cf. EP 427 697).
[0081] In order to remove catalyst poisons present in the olefin,
purification using an alkylaluminum compound, for example
trimethylaluminum or triethylaluminum, is advantageous. This
purification can be carried out either in the polymerization system
itself, or the olefin is brought into contact with the Al compound
before introduction into the polymerization system and is
subsequently removed again.
[0082] The polymerization or copolymerization is carried out in a
known manner in solution, in suspension or in the gas phase,
continuously or batchwise, in one or more steps, at a temperature
of from -60 to 200.degree. C., preferably from 30 to 80.degree. C.,
particularly preferably from 50 to 80.degree. C. The polymerization
or copolymerization is carried out using olefins of the formula
R.sup.4--CH.dbd.CH--R.sup.b. In this formula, R.sup.a and R.sup.b
are identical or different and are a hydrogen atom or an alkyl
radical having 1 to 14 carbon atoms. However, R.sup.a and R.sup.b
may alternatively form a ring together with the carbon atoms
connecting them. Examples of such olefins are ethylene, propylene,
1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, norbornene and
norbornadiene. In particular, propylene and ethylene are
polymerized.
[0083] If necessary, hydrogen is added as a molecular-weight
regulator and/or in order to increase the activity. The overall
pressure polymerization system is from 0.5 to 100 bar.
Polymerization is preferably carried out in the industrially
particularly interesting pressure range from 5 to 64 bar.
[0084] The metallocene is used in the polymerization in a
concentration, based on the transition metal, of from 10.sup.-3 to
10.sup.-4 mol, preferably from 10.sup.-4 to 10.sup.-7 mol, of
transition metal per dm.sup.3 of solvent or per dm.sup.3 of reactor
volume. The aluminoxane is used in a concentration of from
10.sup.-5 to 10.sup.-1 mol. preferably from 10.sup.-4 to 10.sup.-2
mol, per dm.sup.3 of solvent or per dm.sup.3 of reactor volume. The
other cocatalysts mentioned are used in an approximately equimolar
amount with respect to the metallocene. In principle, however,
higher concentrations are also possible.
[0085] If the polymerization is carried out as a suspension or
solution polymerization, an inert solvent which is customary for
the Ziegler low-pressure process is used. For example, the
polymerization is carried out in an aliphatic or cycloaliphatic
hydrocarbon; examples which may be mentioned are propane, butane,
hexane, heptane, isooctane, cyclohexane and methylcyclohexane. It
is furthermore possible to use a benzine or hydrogenated diesel oil
fraction. Toluene can also be used. The polymerization is
preferably carried out in the liquid monomer.
[0086] If inert solvents are used, the monomers are metered in in
gas or liquid form.
[0087] The polymerization can have any desired duration, since the
catalyst system to be used according to the invention exhibits only
a slight time-dependent drop in polymerization activity.
[0088] Before addition of the catalyst, in particular of the
supported catalyst system (comprising a metallocene according to
the invention and a supported cocatalyst or a metallocene according
to the invention and an organoaluminum compound on a polyolefin
powder in finely divided form), another alkylaluminum compound,
such as, for example, trimethylaluminum, triethylaluminum,
triisobutylaluminum, trioctylaluminum or isoprenylaluminum, may
additionally be introduced into the reactor in order to render the
polymerization system inert (for example to remove catalyst poisons
present in the olefin). This compound is added to the
polymerization system in a concentration of from 100 to 0,01 mmol
of Al per kg of reactor contents. Preference is given to
triisobutylaluminum and triethylaluminum in a concentration of from
10 to 0.1 mmol of Al per kg of reactor contents. This allows the
molar Al/M.sup.1 ratio to be selected at a low level in the
synthesis of a supported catalyst system.
[0089] In principle, however, the use of further substances for
catalysis of the polymerization reaction is unnecessary, i.e. the
systems according to the invention can be used as the only
catalysts for the polymerization of olefins.
[0090] The process according to the invention is distinguished by
the fact that the metallocenes described give polymers of very high
molecular weight, in the case of prochiral monomers very high
molecular weight and very high stereo-tacticity, with high catalyst
activities in the industrially particularly interesting temperature
range from 50 to 80.degree. C.
[0091] In particular, the zirconocenes according to the invention
are distinguished by the fact that, in the case of stereospecific
polymerization of prochiral olefins, for example polypropylene,
polymers of high isotacticity are obtained.
[0092] In particular in the case of isospecific polymerization of
propylene, isotactic polypropylene having long isotactic sequence
lengths and high melting point are obtained.
[0093] In addition, the catalyst systems supported according to the
invention prevent reactor deposits.
[0094] The examples below serve to illustrate the invention in
greater detail.
[0095] All glass equipment was dried by heating in vacuo and was
flushed with argon. All operations were carried out in Schlenk
vessels with exclusion of moisture and oxygen. The solvents used
were in each case freshly distilled over Na/K alloy under argon and
stored in Schlenk vessels.
[0096] The determination of the Al/CH.sub.3 ratio in the
aluminoxane was carried out by decomposition of the sample using
H.sub.2SO.sub.4 and determination of the volume of the resultant
hydrolysis gases under standard conditions and by complexometric
titration of the aluminum in the sample, then dissolved, by the
Schwarzenbach method.
[0097] For Example Nos. 3 to 5 with the supported aluminum compound
(methylaluminoxane on silica gel), referred to below as "MAO on
SiO.sub.2", an approximately 10% strength by weight suspension in
n-decane was prepared, containing, according to aluminum
determination, 60 mg of Al/cm.sup.3.
[0098] For Examples 26 to 30 with the supported aluminum compound
(methylaluminoxane on silica gel SD 3216-30/Grace), referred to
below as "FMAO on SiO.sub.2", a solvent-free powder was used
containing 20% by weight of aluminum in the solid.
[0099] Toluene-soluble methylaluminoxane was employed as a 10%
strength by weight toluene solution for the examples for suspension
polymerization and for bulk polymerization with unsupported
metallocene and contained, according to aluminum determination, 36
mg of Al/cm.sup.3. The mean degree of oligomerization, according to
freezing point depression in benzene, was n=20. For the
toluene-soluble methylaluminoxane, an Al:CH.sub.3 ratio of 1:1.55
was determined.
[0100] The following abbreviations are used
[0101] VI=viscosity index in cm.sup.3/g
[0102] M.sub.w=weight average molecular weight in g/mol (determined
by gel permeation chromatography)
[0103] M.sub.w/M.sub.n=molecular weight dispersity
[0104] M.p.=melting point in IC (determined by DSC, heating/cooling
rate 20.degree. C./min)
[0105] II=Isotactic index (II=mm+1.2 mr, determined by .sup.13C-NMR
spectroscopy)
[0106] MFI 230/5=meltflow index, measured in accordance with DIN
53735, in dg/min
[0107] BD=polymer bulk density in g/dm.sup.3.
[0108] Synthesis of the metallocenes I used in the polymerization
examples (the starting materials employed are commercially
available):
[0109] A. rac-Dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium
dichloride (5)
[0110] 1. (.+-.)-2-(2-phenylbenzyl)propionic acid (1).
[0111] 48.6 g (0.279 mol) of diethylmethyl malonate were added
dropwise at room temperature to 6.5 g (0.285 mol) of sodium in 160
cm.sup.3 of H.sub.2O-free EtOE. 70.4 g (0.285 mol) of
2-phenylbenzyl bromide in 20 cm.sup.3 of H.sub.2O-free EtOR were
subsequently added dropwise, the batch was refluxed for 3 hours.
The solvent was stripped off, and 200 cm.sup.3 of H.sub.2O were
added to the residue. The organic phase was separated off, and the
aqueous phase was saturated with NaCl and extracted twice with 200
cm.sup.3 of Et.sub.2O in each case. The organic phase combined with
the extracts was dried (MgSo.sub.4).
[0112] The residue remaining after the solvent had been stripped
off was taken up in 500 cm.sup.3 of EtOH and 50 cm.sup.3 of
H.sub.2O, and 56 g (1 mol) of KOH were added. The reaction mixture
was refluxed for 4 hours. The solvent was stripped off in vacuo,
the residue was taken up in 500 cm.sup.3 of H.sub.2O, and the
solution was acidified to pH 1 by means of concentrated aqueous
HCl. The precipitate which deposited was filtered off with suction
and heated for 30 minutes at 250.degree. C. in a bulb tube with
vigorous foaming, giving 58.3 g (85%) of 1 as a viscous oil.
[0113] .sup.1H-NMR (100 MHz, CDCl.sub.3): 11.7 (s, 1H, COOH),
7.1-7.5 (m, 9H, arom. H) 2.3-3.2 (m, 3H, CH and CH.sub.2), 0.9 (d,
3H, CH.sub.3).
[0114] 2. (.+-.)-2-Methyl-4-phenylindan-1-one (2)
[0115] A solution of 58 g (0.242 mol) of 1 in 60 cm.sup.3 (0.83
mol) of thionyl chloride was stirred at room temperature for 18
hours. Excess thionyl chloride was removed at 10 mbar, and the oily
residue was freed from adhering residues of thionyl chloride by
repeated dissolution in 100 cm.sup.3 of toluene in each case and
stripping off in vacuo.
[0116] The acid chloride was taken up in 150 cm.sup.3 of toluene
and added dropwise at 10.degree. C. to a suspension of 48 g (0.363
mol) of AlCl.sub.3 in 400 cm.sup.3 of toluene. When the addition
was complete, the mixture was refluxed for a further 3 hours. The
reaction mixture was poured into 500 g of ice and acidified to pH 1
by means of concentrated aqueous HCl. The organic phase was
separated off, the aqueous phase was then extracted three times
with 100 cm.sup.3 of Et.sub.2O in each case. The combined organic
phases were washed with saturated aqueous NaHCO.sub.3 solution and
saturated aqueous NaCl solution and then dried (MgSO.sub.4), giving
50.4 g (93%) of 2, which was reacted further without further
purification.
[0117] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.2-7.8 (m, 8H, arom. H),
3.3 (dd, 1H, .beta.-H), 2.5-2.9 (m, 2H, .alpha.- and .beta.-H), 1.3
(d, 3H, CH.sub.3).
[0118] 3. 2-Methyl-7-phenylindene (3)
[0119] 50 g (0.226 mmol) of 2 were dissolved in 450 cm.sup.3 of
THF/MeOH (2:1), and 12.8 g (0.34 mol) of sodium borohydride were
added in portions at 0.degree. C. with stirring. The reaction
mixture was stirred for a further 18 hours and poured into ice,
concentrated HCl was added to pH 1 and the mixture was extracted a
number of times with Et.sub.2O. The combined organic phases were
washed with saturated aqueous NaHCO.sub.3 solution and NaCl
solution and then dried (MgSO.sub.4). The solvent was removed in
vacuo, and the crude product, without further purification, was
taken up in 1 dm.sup.3 of toluene, 2 g of p-toluene sulfonic acid
were added, and the mixture was refluxed for 2 hours. The reaction
mixture was washed with 200 cm.sup.3 of saturated aqueous
NaHCO.sub.3 solution, and the solvent was removed in vacuo. The
crude product was purified by filtration through 500 g of silica
gel (hexane/CH.sub.2Cl.sub.2), giving 42 g (90%) of 3 as a
colorless oil.
[0120] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-7.6 (m, 8H, arom. H),
6.5 (m, 1H, H-C(3)), 3.4 (s, 2H, CH.sub.2), 2.1 (s, 3H,
CH.sub.3).
[0121] 4. Dimethylbis(2-methyl-4-phenylindenyl)silane (4)
[0122] 29 cm.sup.3 (73 mmol) of a 2.5 M solution of butyllithium in
hexane were added at room temperature under argon to a solution of
15 g (72.7 mmol) of 3 in 200 cm.sup.3 of H.sub.2O- and O.sub.2-free
toluene and 10 cm.sup.3 of H.sub.2O- and O.sub.2-free THF and
heated at 80.degree. C. for 1 hour. The batch was subsequently
cooled to 0.degree. C., and 4.7 g (36.4 mmol) of
dimethyldichlorosilane were added. The mixture was heated at
80.degree. C. for 1 hour and subsequently poured into 100 cm.sup.3
of H.sub.2O. The mixture was extracted a number of times with
Et.sub.2O, and the combined organic phases were dried (MgSO.sub.4).
The crude product remaining after the solvent had been stripped off
was chromatographed on 300 g of silica gel
(hexane/CH.sub.2Cl.sub.2), giving 12.0 g (70%) of 4.
[0123] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.10-7.70 (m, 16H, arom.
H), 6.80 (m, 2H, H-C(3)), 3.80 (8, 2H, H--C(1)), 2.20 (m, 6H,
CH.sub.3) -0.20 (m, 6H, CH.sub.3Si).
[0124] 5. rac-Dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium
dichloride (5)
[0125] 10.6 cm.sup.3 (26 mmol) of a 2.5 M solution of butyllithium
in hexane were added at room temperature under argon to a solution
of 6.0 g (12.9 mmol) of 4 in 100 cm.sup.3 of H.sub.2O- and
O.sub.2-free toluene, and the mixture was refluxed for 3 hours. The
suspension of the dilithio salt was subsequently cooled to
-25.degree. C., and 3.2 g (13.6 mmol) of zirconium tetrachloride
were added. The batch was warmed to room temperature over the
course of 1 hour, stirred for a further hour and then filtered
through a G3 frit. The residue was extracted with 50 cm.sup.3 of
toluene, and the combined filtrates were freed from solvent under
an oil-pump vacuum, giving 9.0 g of the metallocene in the form of
a yellow powder as a mixture of the racemic and meso forms in the
ratio 1:1. Pure racemate (5) was isolated by stirring the crude
mixture a number of times with 20 cm.sup.3 of methylene chlorine in
each case, the racemate remaining as a yellow crystal powder and
the meso form being washed out. 2.74 g (33%) of the pure racemate
were obtained.
[0126] .sup.1H-NMR (300 MHz, CDCl.sub.3): 7.0-7.7 (m, 16H, arom.
H), 6.9 (s, 2H, H--C(3)), 2.2 (s, 6H, CH.sub.3), 1.3 (m, 6H,
CH.sub.3Si). Molecular weight : 626 M.sup.+, correct decomposition
pattern.
EXAMPLE B
rac-Methylphenylsilanediylbis-(2-methyl-4-phenylindenyl)zirconium
dichloride (7)
[0127] 1. Methylphenylbis-(2-methyl-4-phenylindenyl)silane (6)
[0128] 21 ml (52 mmol) of a 2.5 M solution of butyllithium in
hexane were added at room temperature under argon to a solution of
10.3 g (50 mmol) of 3 in 90 ml of H.sub.2O- and O.sub.2-free
toluene and 10 ml of H.sub.2O- and O.sub.2-free THF. The mixture
was heated at 80.degree. C. for 1 hour and subsequently cooled to
0.degree. C. 4.8 g (25 mmol) of methylphenyldichlorosilane were
added, and stirring was continued overnight at room temperature.
The precipitated LiCl was separated off by filtration, and the
crude product remaining after the solvent had been stripped off in
vacuo was chromatographed on 300 g of silica gel
(hexane/CH.sub.2Cl.sub.2 9:1), giving 4.6 g (35%) of 6.
[0129] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-7.8 (m, 16H, arom.
H), 6.9 (m, 2H, H--C(3)), 3.9 (m, 2H, H--C(1)), 2.3 (m, 6H,
CH.sub.3), -0.1 (s, 3H, CH.sub.3Si).
[0130] 2.
rac-Methylphenylsilanediylbis(2-methyl-4-phenylindenyl)zirconium
dichloride (7)
[0131] 3.6 ml (8.9 mmol) of a 2.5 M solution of butyllithium in
hexane were added at room temperature under argon to 2.3 g (4.4
mmol) of 6 in 25 ml Of H.sub.2O- and O.sub.2-free toluene, and the
mixture was heated at 80.degree. C. for 3 hours. The suspension of
the dilithio salt was subsequently cooled to -30.degree. C., and
1.1 g (4.5 mmol) of zirconium tetrachloride were added. The mixture
was warmed to room temperature over the course of 1 hour and
stirred for a further 1 hour. After filtration through a G3 frit,
the solvent was removed from the filtrate, and the residue was
crystallized from 10 ml of methylene chloride, giving 0.2 g of the
racemic form of 7 as orange crystals.
[0132] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-8.2 (m, 21H, arom.
H), 6.9 (m, 2H, H--C(3)), 2.4 (s, 3H, CH.sub.3), 2.0 (s, 3H,
CH.sub.3), 1.3 (s, 3H, CH.sub.3Si). Mass spectrum: 690 M.sup.+,
correct decomposition pattern.
EXAMPLE C
rac-Dimethylsilandiylbis(4-phenylindenyl)zirconium dichloride
(12)
[0133] 1. 3-(2-phenylphenyl)propionic acid (8)
[0134] 93 cm.sup.3 (0.61 mmol) of diethyl malonate dissolved in 50
cm.sup.3 of H.sub.2O-free EtOR were added dropwise at room
temperature to 14 g (0.61 mmol) of sodium in 400 cm.sup.3 of
H.sub.2O-free EtOH. 150 g (0.61 mmol) of 2-phenylbenzyl bromide in
200 cm.sup.3 of H.sub.2O-free EtOR were subsequently added
dropwise, and the mixture was refluxed for 3 hours. 102 g (1.83
mol) of KOH dissolved in 150 cm.sup.3 of H.sub.2O were added at
room temperature, and the mixture was refluxed for a further 4
hours. The solvent was removed in vacuo, H.sub.2O was added to the
residue until the latter dissolved completely, and the mixture was
acidified to pH 1 by means of concentrated aqueous HCl. The
precipitate which formed was filtered off with suction, dried and
heated at 130.degree. C. for 1 hour, giving 112 g (81%) of 8 as a
viscous oil.
[0135] .sup.1H-NMR (100 MHz, CDCl.sub.3): 9.1 (s, 1H, COOH),
6.9-7.5 (m, 9H, arom. H), 2.3-3.0 (m, 4H, 2CH.sub.2).
[0136] 2. 4-Phenyl-1-indanone (9)
[0137] A solution of 102 g (0.45 mol) of 8 in 37 cm.sup.3 (0.5 mol)
of thionyl chloride was stirred at room temperature for 18 hours.
Excess thionyl chloride was removed at 10 mbar, and the oily
residue was freed from adhering residues of thionyl chloride by
repeated dissolution in 100 cm.sup.3 of toluene in each case and
stripping off the toluene in vacuo.
[0138] The acid chloride was taken up in 200 cm.sup.3 of toluene
and added dropwise at 10.degree. C. to a suspension of 72 g (0.54
mol) of AlCl.sub.3 in 1000 cm.sup.3 of toluene. The reaction
mixture was heated at 80.degree. C. for 1 hour, poured into 1000 g
of ice and acidified to pH 1 by means of concentrated aqueous
HCl.
[0139] The organic phase was separated off, and the aqueous phase
was then extracted 3 times with 200 cm.sup.3 of Et.sub.2O in each
case. The combined organic phases were washed with saturated
aqueous NaHCO, solution and saturated aqueous NaCl solution and
subsequently dried (MgSO.sub.4), giving 96 g (96%) of 9, which was
reacted further without further purification.
[0140] .sup.1H-NMR (100 MHz, CDCl.sub.3): 6.9-7.5 (m, 8H, arom. H),
2.5-3.4 (m, 4H, 2CH.sub.2).
[0141] 3. 7-Phenylindene (10)
[0142] 23 g (0.62 mol) of NaBH, were added in portions at 0.degree.
C. to a solution of 86 g (0.41 mol) of 9 in 300 cm.sup.3 of
THF/methanol 2:1. The reaction mixture was stirred at room
temperature for 18 hours and poured into 300 g of ice, concentrated
aqueous HCl was added to pH 1, and the mixture was extracted a
number of times with Et.sub.2O. The combined organic phases were
washed with saturated aqueous NaHCO.sub.3 solution and saturated
aqueous NaCl solution, dried (MgSO.sub.4) and freed from solvent in
vacuo.
[0143] The crude product was taken up in 1000 cm.sup.3 of toluene,
4.5 g of p-toluenesulfonic acid were added, the reaction mixture
was refluxed for 2 hours on a water separator and washed three
times with 250 cm.sup.3 of saturated aqueous NaHCO.sub.3 solution,
and the solvent was removed in vacuo. Distillation at 0.1 mbar
gave, at 96-108.degree. C., 33 g (41%) of 10 as a colorless
oil.
[0144] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.1-7.7 (m, 8H, arom. H),
6.9 and 6.5 (2m, 2H, CH), 3.5 (m, 2H, CH.sub.2).
[0145] 4. Dimethylbis(4-phenylindenyl)silane (11)
[0146] 18.7 cm.sup.3 (50 mmol) of a 20% strength solution of
butyllithium in toluene were added at room temperature to a
solution of 10 g (50 mmol) of 10 in 100 cm.sup.3 of H.sub.2O- and
O.sub.2-free toluene and 5 ml of H.sub.2O- and O.sub.2-free THF,
and the mixture was heated at 80.degree. C. for 2 hours. The yellow
suspension was subsequently cooled to 0.degree. C., and 3.2 g (25
mmol) of dimethyldichlorosilane were added. The reaction mixture
was heated at 80.degree. C. for a further 1 hour and subsequently
washed with 50 cm.sup.3 of H.sub.2O. The solvent was removed in
vacuo, and the residue was recrystallized from heptane at
-20.degree. C., giving 6.7 g (62%) of 11 as colorless crystals
(m.p. 109-110.degree. C.).
[0147] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-7.7 (m, 18H, arom. H
and H--C(3)), 6.8 (dd, 2H, H--C(2)), 3.8 (m, 2H, H--C(1)), -0.2,
(8, 6H, CH.sub.3Si).
[0148] 5. rac-Dimethylsilanediylbis(4-phenylindenyl)zirconium
dichloride (12)
[0149] 12 cm.sup.3 (32 mmol) of a 20% strength solution of
butyllithium in toluene were added at room temperature under argon
to a solution of 6.6 g (16 mmol) of 11 in 70 cm.sup.3 of H.sub.2O-
and O.sub.2-free Et.sub.2O, and the mixture was subsequently
refluxed for 3 hours. The solvent was removed in vacuo, the residue
was filtered through a G3 Schlenk frit with 50 ml of H.sub.2O- and
O.sub.2-free hexane, washed with 50 ml of H.sub.2O- and
O.sub.2-free hexane and dried (0.1 mbar, RT).
[0150] The dilithio salt was added at -78.degree. C. to a
suspension of 3.6 g (16 mmol) of zirconium tetrachloride in 80
cm.sup.3 of methylene chloride, and the mixture was warmed to room
temperature over the course of 18 hours with magnetic stirring. The
batch was filtered through a G3 frit, and the residue was then
extracted in portions with a total of 200 cm.sup.3 of methylene
chloride. The combined filtrates were freed from solvent in vacuo
and recrystallized from methylene chloride/hexane (1:1). 5.6 g of
the racemic and meso forms in the ratio 1:1 were obtained. Further
recrystallization from methylene chloride gave the racemic complex
in the form of yellow crystals.
[0151] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-7.8 (m, 22 H, arom. H
and H--C(3)), 6.1 (d, 2H, H--C(2)), 1.1 (s, 6H, CH.sub.3Si). Mass
spectrum: 598 M.sup.+, correct decomposition pattern.
EXAMPLE D
rac-Dimethylsilanediylbis(2-ethyl-4-phenylindenyl)zirconium
dichloride (17)
[0152] 1. (.+-.)-2-(2-phenylbenzyl)butyric acid (13)
[0153] 188 g (1 mol) of diethyl ethylmalonate dissolved in 100
cm.sup.3 of H.sub.2O-free EtOH are added dropwise at room
temperature to 23 g (1 mol) of sodium in 400 cm.sup.3 of
H.sub.2O-free EtOE. 247 g (1 mol) of 2-phenylbenzyl bromide in 300
cm.sup.3 of H.sub.2O-free EtOH were subsequently added dropwise,
and the mixture was refluxed for 3 hours. 170 g (3 mol) of KOH
dissolved in 300 cm.sup.3 of H.sub.2O were added at room
temperature, and the mixture was refluxed for a further 4 hours.
The solvent was removed in vacuo, H.sub.2O was added to the residue
until the latter had dissolved completely, and the mixture was
subsequently acidified to pH 1 by means of concentrated aqueous
HCl. The precipitate which formed was filtered off with suction,
dried and heated at 130.degree. C. for 1 hour, giving 236 g (93%)
of 13 as a viscous oil.
[0154] .sup.1H-NMR (100 MHz, CDCl.sub.3): 10.3 (s, 1H, COOH),
7.0-7.3 (m, 9H, arom. H), 2.5-3.0 (m, 3H, CH and CH.sub.2), 1.5-1.9
(m, 2H, CH.sub.2), 0.9 (t, 3H, CH.sub.3).
[0155] 2. (.+-.)-2-Ethyl-4-phenyl-1-indanone (14)
[0156] A solution of 236 g (0.93 mol) of 13 in 81 cm.sup.3 (1.2
mol) of thionyl chloride was stirred at room temperature for 18
hours. Excess thionyl chloride was removed at 10 mbar and the oily
residue was freed from adhering residues of thionyl chloride by
repeated dissolution in 200 cm.sup.3 of toluene in each case and
stripping off in vacuo.
[0157] The acid chloride was taken up in 400 cm.sup.3 of toluene
and added dropwise at 10.degree. C. to a suspension of 133 g (1.0
mol) of AlCl.sub.3 in 2000 cm.sup.3 of toluene. The reaction
mixture was heated at 80.degree. C. for 1 hour, poured into 2000 g
of ice and acidified to pH 1 by means of concentrated aqueous HCl.
The organic phase was separated off, and the aqueous phase was then
extracted three times with 200 cm.sup.3 of Et.sub.2O in each case.
The combined organic phases were washed with saturated aqueous
NaHCO.sub.3 solution and saturated aqueous NaCl solution and
subsequently dried (MgSO.sub.4), giving 187 g (85%) of 14, which
was reacted further without further purification.
[0158] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-7.8 (m, 8H, arom. H),
3.1-3.4 (m, 1H, H--C(3)), 2.5-2.9 (m, 2H, H--C(2)) and H--C(3)),
1.3-2.0 (m, 2H, CH.sub.2), 0.9 (t, 3H, CH.sub.3).
[0159] 3. 2-Ethyl-7-phenylindene (15)
[0160] 8 g (0.21 mol) of NaBH, were added in portions at 0.degree.
C. to a solution of 50 g (0.21 mol) of 14 in 600 cm.sup.3 of
THF/methanol 2:1, the reaction mixture was stirred at room
temperature for 18 hours and poured into 600 g of ice, concentrated
aqueous HCl was added to pH 1, and the mixture was extracted a
number of times with Et.sub.2O. The combined organic phases were
washed with saturated aqueous NaHCO.sub.3 solution and saturated
aqueous NaCl solution and subsequently dried (MgSO.sub.4).
[0161] The crude product was taken up in 1000 cm.sup.3 of toluene,
4.5 g of p-toluenesulfonic acid were added, the reaction mixture
was refluxed for 2 hours on a water separator and washed 3 times
with 250 cm.sup.3 of saturated aqueous NaHCO.sub.3 solution, and
the solvent was removed in vacuo. Distillation at 0.1 mbar gave, at
135.degree. C., 33 g (72%) of 15 as a colorless oil.
[0162] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-7.5 (m, 8H, arom. H)
6.5 (m, 1H, CH), 3.2 (m, 2H, CH.sub.2), 2.5 (dq, 2H, CH.sub.2), 1.1
(t, 3H, CH.sub.3).
[0163] 3. Dimethylbis(2-ethyl-4-phenylindenyl)silane (16)
[0164] 29 cm.sup.3 (77 mmol) of a 20% strength solution of
butyllithium in toluene were added at room temperature to a
solution of 17 g (77 mmol) of 15 in 160 cm.sup.3 of H.sub.2O- and
O.sub.2-free toluene and 8 ml of H.sub.2O- and O.sub.2-free THF,
and the mixture was heated at 80.degree. C. for 2 hours. The yellow
suspension was subsequently cooled to 0.degree. C., and 5 g (38
mmol) of dimethylchlorosilane were added. The reaction mixture was
heated at 80.degree. C. for a further 1 hour and subsequently
washed with 100 cm.sup.3 of H.sub.2O. The solvent was removed in
vacuo, and the residue was purified by chromatography on 200 g of
silica gel (hexane/methylene chloride 9:1), giving 9 g (47%) of 16
as a viscous oil.
[0165] .sup.1H-NMR (100 MHz, CDCl.sub.3): 6.97-7.4 (m, 16H, arom.
H), 6.5 (m, 2H, H--C(3)), 3.7 (m, 2H, H--C(1)), 2.4 (m, 4H, CH,),
1.1 (t, 6H, CH.sub.3), -0.1, (s, 6H, CH.sub.3Si).
[0166] 5.
rac-Dimethylsilanediylbis(2-ethyl-4-phenylindenyl)zirconium
dichloride (17)
[0167] 8.4 cm.sup.3 of 20% strength solution of butyllithium in
toluene were added at room temperature under argon to a solution of
5.6 g (11 mmol) of 16 in 50 cm.sup.3 of H.sub.2O- and O.sub.2-free
Et.sub.2O, and the mixture was subsequently refluxed for 3 hours.
The solvent was removed in vacuo, and the residue was filtered
through a G3 Schlenk frit with 50 ml of H.sub.2O- and O.sub.2-free
hexane, then washed with 50 ml Of H.sub.2O- and O.sub.2-free hexane
and dried (0.1 mbar, RT).
[0168] The dilithio salt was added at -78.degree. C. to a
suspension of 2.5 g (11 mmol) of zirconium tetrachloride in 50
cm.sup.3 of methylene chloride, and the mixture was warmed to room
temperature over the course of 18 hours with magnetic stirring. The
batch was filtered through a G3 frit, and the residue was then
extracted in portions with a total of 100 cm.sup.3 of methylene
chloride. The combined filtrates were freed from solvent in vacuo
and recrystallized from toluene/hexane (1:1). 2 g (27%) of the
racemic and meso forms in the ratio 1:1 were obtained. Further
recrystallization from toluene gave the racemic complex 17 in the
form of yellow crystals.
[0169] .sup.1H-NMR (100 MHz, CDCl.sub.3): 6.8-7.7 (m, 16H, arom.
H), 6.6 (m, 2H, H--C(3)), 2.3-3.9 (m, 4H, CH.sub.2) 1.0-1.4 (m,
12H, CH.sub.3 and CH.sub.3Si). Mass spectrum: 654 M.sup.+, correct
decomposition pattern.
EXAMPLE E
rac-Dimethylsilanediylbis(2-methyl-4-(1-naphthyl)indenyl)zirconium
dichloride (24)
[0170] 1. 2-(1-Naphthyl)toluene (18)
[0171] 13.9 g (0.57 mol) of magnesium turnings were covered by 150
ml of H.sub.2O-free Et.sub.2O, and the Grignard reaction was
initiated by means of 5 g of 2-bromotoluene and a few grains of
iodine. 93 g (0.57 mol) of 1-bromotoluene in 450 ml of
H.sub.2O-free Et.sub.2O were subsequently added dropwise at such a
rate that the reaction mixture was kept at the boil. When the
addition was complete, boiling was continued until the magnesium
had reacted fully.
[0172] The Grignard solution was subsequently added dropwise to a
solution of 118 g (0.57 mol) of 1-bromonaphthalene and 3.5 g of
bis(triphenylphosphine)nickel dichloride in 800 cm.sup.3 of toluene
at such a rate that the internal temperature did not exceed
50.degree. C. The mixture was subsequently refluxed for a further 3
hours, 500 ml of 10% strength aqueous HCl were added, the phases
were separated, and the organic phase was freed from solvent in
vacuo. Filtration through silica gel (hexane) gave 115 g (92%) of
18 as a colorless oil.
[0173] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.2-8.0 (m, 11H, arom.
H), 2.0 (s, 3H, CH.sub.3).
[0174] 2. 2-(1-Naphthyl)benzyl bromide (19)
[0175] 114 g (0.52 mol) of 18 and 103 g (0.58 mol) of
N-bromosuccinimide were dissolved in 2000 cm.sup.3 of
tetrachloromethane at room temperature, 3 g of
azobisisobutyronitrile were added, and the mixture was refluxed for
4 hours. The succinimide which precipitated was filtered off, the
solvent was removed in vacuo, and the residue was purified by
filtration through 1000 g of silica gel (hexane/methylene chloride
9:1), giving 141 g (82%) of 19 as a colorless lachrymatory oil.
[0176] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.1-8.0 (m, 11H, arom.
H), 4.2 (q, 2H, CH.sub.2Br).
[0177] 3. (t)-2-(2-(1-naphthyl)benzyl)propionic acid (20)
[0178] 75 g (0.43 mmol) of diethyl methylmalonate dissolved in 50
cm.sup.3 of H.sub.2O-free EtOH were added dropwise at room
temperature to 10 g (0.43 mmol) of sodium in 100 cm.sup.3 of
H.sub.2O-free EtOH. 140 g (0.43 mmol) of 2-phenylbenzyl bromide in
200 cm.sup.3 of H.sub.2O-free EtOH were subsequently added
dropwise, and the mixture was refluxed for 3 hours. 85 g (1.3 mol)
of KOH dissolved in 100 cm.sup.3 Of H.sub.2O were added at room
temperature, and the mixture was refluxed for a further 4 hours.
The solvent was removed in vacuo, H.sub.2O was added to the residue
until the latter had dissolved completely, and the mixture was
acidified to pH 1 by means of concentrated aqueous HCl. The
precipitate which had formed was filtered off with suction, dried
and heated at 130.degree. C. for 1 hour, giving 96 g (77%) of 20 as
a viscous oil.
[0179] .sup.1H-NMR (100 MHz, CDCl.sub.3): 10.1 (s, 1H, COOH),
6.9-8.0 (m, 11H, arom. H) 2.3-3.0 (m, 3H, CH.sub.2 and CH), 0.8 (d,
3H, CH.sub.3).
[0180] 4. (.+-.)-2-Methyl-4-(1-naphthyl)-1-indanone (21)
[0181] A solution of 96 g (0.33 mol) of 20 in 37 cm.sup.3 (0.5 mol)
of thionyl chloride was stirred at room temperature for 18 hours.
Excess thionyl chloride was removed at 10 mbar, and the oily
residue was freed from adhering residues of thionyl chloride by
repeated dissolution in 100 cm.sup.3 toluene in each case and
stripping off in vacuo.
[0182] The acid chloride was taken up in 200 cm.sup.3 of toluene
and added dropwise at 10.degree. C. to a suspension of 44 g (0.33
mol) of AlCl.sub.3 in 1000 cm.sup.3 of toluene, and the reaction
mixture was heated at 80.degree. C. for 3 hours, poured into 1000 g
of ice and acidified to pH 1 by means of concentrated aqueous HCl.
The organic phase was separated off, and the aqueous phase was then
extracted three times with 200 cm.sup.3 of methylene chloride in
each case. The combined organic phases were washed with saturated
aqueous NaCl.sub.3 solution and saturated aqueous NaCl solution and
subsequently dried (MgSO.sub.4). Chromatography on 1000 g of silica
gel (hexane/methylene chloride) gave 12 g (13%) of 21.
[0183] .sup.1H-NMR (100 MHz, CDCl.sub.3); 7.3-8.0 (m, 10H, arom.
H), 2.2-3.2 (m, 3H, CH.sub.2 and CH), 1.2 (d, 3H, Cl.sub.3).
[0184] 5. 2-Methyl-7-(1-naphthyl)indene (22)
[0185] 1.3 g (33 mmol) of NABH, were added at 0.degree. C. to a
solution of 12 g (44 mmol) of 21 in 100 cm.sup.3 of THF/methanol
2:1, the reaction mixture was stirred at room temperature for 18
hours and poured into 100 g of ice, concentrated aqueous HCl was
added to pH 1, and the mixture was extracted a number of times with
Et.sub.2O. The combined organic phases were washed with saturated
aqueous NaHCO.sub.3 solution and saturated aqueous NaCl solution
and subsequently dried (MgSO.sub.4).
[0186] The crude product was taken up in 200 cm.sup.3 of toluene,
0.5 g of p-toluene sulfonic acid was added, the reaction mixture
was refluxed for 2 hours on a water separator and washed 3 times
with 50 cm.sup.3 of saturated aqueous NaHCO.sub.3 solution, and the
solvent was removed in vacuo. Filtration through 200 g of silica
gel (hexane/methylene chloride) gave 10 g (86%) of 22 as a
colorless oil.
[0187] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-8.0 (m, 10H, arom.
H), 6.6 (m, 1H, CH), 3.0 (m, 2H, CH.sub.2), 2.0 (m, 3H,
CH.sub.3).
[0188] 6. Dimethylbis(2-methyl-4-(1-naphthyl)indenyl)silane
(23)
[0189] 14.4 cm.sup.3 (50 mmol) of a 20% strength solution of
butyllithium in toluene were added at room temperature to a
solution of 10 g (38 mmol) of 22 in 100 cm.sup.3 of H.sub.2O- and
O.sub.2-free toluene and 5 ml of H.sub.2O- and O.sub.2-free THF,
and the mixture was heated at 80.degree. C. for 2 hours. The yellow
suspension was subsequently cooled to 0.degree. C., and 2.5 g (19
mmol) of dimethyldichlorosilane were added. The reaction mixture
was heated at 80.degree. C. for a further 1 hour and subsequently
washed with 50 cm.sup.3 of H.sub.2O. The solvent was removed in
vacuo, and the residue was recrystallized from heptane at
-20.degree. C., giving 8.2 g (75%) of 23 as colorless crystals.
[0190] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.2-8.1 (m, 20H, arom.
H), 6.4 (m, 2H, H--C(3)), 4.0 (m, 2H, H--C (1)), -0.1, (8, 6H,
CH.sub.3Si).
[0191] 7. rac-Dimethylsilanediylbis
(2-methyl-4-(1-naphthyl)indenyl)zircon- ium dichloride (24)
[0192] 10.5 cm.sup.3 of a 20% strength solution of butyllithium in
toluene were added at room temperature under argon to a solution of
8.0 g (14 mmol) of 23 in 70 cm.sup.3 of H.sub.2O- and O.sub.2-free
Et.sub.2O, and the mixture was subsequently refluxed for 3 hours.
The solvent was removed in vacuo, and the residue was filtered
through a G3 Schlenk frit with 50 ml of H.sub.2O- and O.sub.2-free
hexane, then washed with 50 ml of H.sub.2O- and O.sub.2-free hexane
and dried (0.1 mbar, RT).
[0193] The dilithio salt was added at -78.degree. C. to a
suspension of 3.2 g (14 mmol) of zirconium tetrachloride in 80
cm.sup.3 of methylene chloride, and the mixture was warmed to room
temperature over the course of 18 hours with magnetic stirring. The
batch was filtered through a G3 frit, and the residue was then
extracted in portions with a total of 400 cm.sup.3 of methylene
chloride. The combined filtrates were freed from solvent in vacuo
and recrystallized from methylene chloride. 1.5 g (15%) of the
racemic and meso forms in the ratio 1:1 were obtained. Further
recrystallization from methylene chloride gave the racemic complex
in the form of yellow crystals.
[0194] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-8.0 (m, 22H, arom.
H), 6.5 (s, 2H, H--C(3)), 2.2 (s, 6H, CH.sub.3), 1.3 (s, 6H,
CH.sub.3Si). Mass spectrum: 729 M.sup.+, correct decomposition
pattern.
EXAMPLE F
rac-Dimethylsilanediylbis(2-methyl-4-(2-naphthyl)indenyl)zirconium
dichloride (31)
[0195] 1. 2-(2-Naphthyl)toluene (25)
[0196] 14 g (0.57 mol) of magnesium turnings were covered by 150 ml
of H.sub.2O-free Et.sub.2O, and the Grignard reaction was initiated
by means of 5 g of 2-bromotoluene and a few grains of iodine. 95 g
(0.58 mol) of 1-bromotoluene in 450 ml of H.sub.2O-free Et.sub.2O
were subsequently added dropwise at such a rate that the reaction
mixture was kept at the boil. When the addition was complete,
boiling was continued until the magnesium had reacted fully.
[0197] The Grignard solution was subsequently added dropwise to a
solution of 120 g (0.57 mol) of 2-bromonaphthalene and 3.5 g of
bis(triphenylphosphine)nickel dichloride in 800 cm.sup.3 of toluene
at such a rate that the internal temperature did not exceed
50.degree. C. The mixture was subsequently refluxed for a further 3
hours, 500 ml of 10% strength aqueous HCl were added, the phases
were separated, and the organic phase was freed from solvents in
vacuo. Filtration through silica gel (hexane) gave 107 g (87%) of
25 as a colorless oil.
[0198] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-7.9 (m, 11H, arom.
H), 1.9 (s, 3H, CH.sub.3).
[0199] 2. 2-(2-Naphthyl)benzyl bromide (26)
[0200] 105 g (0.48 mol) of 25 and 90 g (0.5 mol) of
N-bromosuccinimide were dissolved in 2000 cm.sup.3 of
tetrachloromethane at room temperature, 3 g of
azobisisobutyronitrile were added, and the mixture was refluxed for
4 hours. The succinimide which precipitated was filtered off, the
solvent was removed in vacuo, and the residue was purified by
filtration through 1000 g of silica gel (hexane/methylene chloride
9:1), giving 112 g (79%) of 26 as a colorless lachrymatory oil.
[0201] .sup.1H-NMR (100 MHz, CDCl.sub.3): 6.9-8.0 (m, 11H, arom.
H), 4.1 (s, 2H, CH.sub.2Br).
[0202] 3. (.+-.)-2-(2-(2-naphthyl)benzyl)propionic acid (27)
[0203] 70 g (0.37 mmol) of diethyl methylmalonate dissolved in 50
cm.sup.3 of H.sub.2O-free EtOH were added dropwise at room
temperature to 8.5 g (0.37 mmol) of sodium in 100 cm.sup.3 of
H.sub.2O-free EtOH. 110 g (0.37 mmol) of 26 in 200 cm.sup.3 of
H.sub.2O-free EtOH were subsequently added dropwise, and the
mixture was refluxed for 3 hours. 62 g (1.1 mol) of KOH dissolved
in 100 cm.sup.3 of H.sub.2O were added at room temperature, and the
mixture was refluxed for a further 4 hours. The solvent was removed
in vacuo, H.sub.2O was added to the residue until the latter had
dissolved completely, and the mixture was acidified to pH 1 by
means of concentrated aqueous HCl. The precipitate which had formed
was filtered off with suction, dried and heated at 130.degree. C.
for 1 hour, giving 90 g (84%) of 27 as a viscous oil.
[0204] .sup.1H-NMR (100 MHz, CDCl.sub.3): 10.9 (s, 1H, COOH),
7.0-8.1 (m, 11H, arom. H) 2.3-3.0 (m, 3H, CH.sub.2 and CH), 1.0 (d,
3H, CH.sub.3).
[0205] 4. (.+-.)-2-Methyl-4-(2-naphthyl)-1-indanone (28)
[0206] A solution of 89 g (0.31 mol) of 27 in 37 cm.sup.3 (0.5 mol)
of thionyl chloride was stirred at room temperature for 18 hours.
Excess thionyl chloride was removed at 10 mbar, and the oily
residue was freed from adhering residues of thionyl chloride by
repeated dissolution in 100 cm.sup.3 of toluene in each case and
stripping off in vacuo. The acid chloride was taken up in 200
cm.sup.3 of toluene and added dropwise at 10.degree. C. to a
suspension of 44 g (0.33 mol) of AlCl.sub.3 in 1000 cm.sup.3 of
toluene, and the reaction mixture was heated at 80.degree. C. for 3
hours, poured into 1000 g of ice and acidified to pH 1 by means of
concentrated aqueous HCl. The organic phase was separated off, and
the aqueous phase was then extracted three times with 200 cm.sup.3
of methylene chloride in each case. The combined organic phases
were washed with saturated aqueous NaHCO.sub.3 solution and
saturated aqueous NaCl solution and subsequently dried
(MgSO.sub.4). Chromatography on 1000 g of silica gel (hexane/AeOEt)
gave 27 g (33%) of 28.
[0207] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.1-8.0 (m, 10H, arom.
H), 2.2-3.3 (m, 3H, CH.sub.2 and CH), 1.1 (d, 3H, CH.sub.3).
[0208] 5. 2-Methyl-7-2-naphthyl)indene (29)
[0209] 3.8 g (100 mmol) of NaBH.sub.4 were added at 0.degree. C. to
a solution of 27 g (100 mmol) of 28 in 200 cm.sup.3 of THF/methanol
2:1, the reaction mixture was stirred at room temperature for 18
hours and poured into 100 g of ice, concentrated aqueous HCl was
added to pH 1, and the mixture was extracted a number of times with
Et.sub.2O. The combined organic phases were washed with saturated
aqueous NaHCO.sub.3 solution and saturated aqueous NaCl solution
and subsequently dried (MgSO.sub.4).
[0210] The crude product was taken up in 500 cm.sup.3 of toluene,
1.5 g of p-toluene sulfonic acid was added, the reaction mixture
was refluxed for 2 hours on a water separator and washed 3 times
with 50 cm.sup.3 of saturated aqueous NaHCO.sub.3 solution, and the
solvent was removed in vacuo. Filtration through 200 g of silica
gel (hexane/methylene chloride) gave 18.4 g (72%) of 29 as a
colorless oil.
[0211] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-8.0 (m, 10H, arom.
H), 6.6 (m, 1H, CH), 3.0 (m, 2H, CH.sub.2), 2.0 (m, 3H,
CH.sub.3).
[0212] 6. Dimethylbis(2-methyl-4-(2-naphthyl)indenyl)silane
(30)
[0213] 26 cm.sup.3 (70 mmol) of a 20% strength solution of
butyllithium in toluene were added at room temperature to a
solution of 18 g (70 mmol) of 29 in 70 cm.sup.3 of H.sub.2O- and
O.sub.2-free toluene and 4 ml of H.sub.2O- and O.sub.2-free THF,
and the mixture was heated at 80.degree. C. for 2 hours. The yellow
suspension was subsequently cooled to 0.degree. C., and 4.5 g (35
mmol) of dimethyldichlorosilane were added. The reaction mixture
was heated at 80.degree. C. for a further 1 hour and subsequently
washed with 50 cm.sup.3 of H.sub.2O. The solvent was removed in
vacuo, and the residue was recrystallized from heptane at
-20.degree. C., giving 10.8 g (54%) of 30 as colorless
crystals.
[0214] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-8.1 (m, 20H, arom.
H), 6.4 (m, 2H, H--C(3)), 4.0 (m, 2H, H--C (1)), -0.1, (s, 6H,
CH.sub.3Si).
[0215] 7. rac-Dimethylsilanediylbis
(2-methyl-4-(2-naphthyl)indenyl)zircon- ium dichloride (31)
[0216] 13.6 cm.sup.3 of a 20% strength solution of butyllithium in
toluene were added at room temperature under argon to a solution of
10.5 g (18 mmol) of 30 in 70 cm.sup.3 of H.sub.2O- and O.sub.2-free
Et.sub.2O, and the mixture was subsequently refluxed for 3 hours.
The solvent was removed in vacuo, and the residue was filtered
through a G3 Schlenk frit with 50 ml of H.sub.2O- and O.sub.2-free
hexane, then washed with 50 ml of H.sub.2O- and O.sub.2-free hexane
and dried (0.1 mbar, RT).
[0217] The dilithio salt was added at -78.degree. C. to a
suspension of 4.2 g (18 mmol) of zirconium tetrachloride in 80
cm.sup.3 of methylene chloride, and the mixture was warmed to room
temperature over the course of 18 hours with magnetic stirring. The
batch was filtered through a G3 frit, and the residue was then
extracted in portions with a total of 400 cm.sup.3 of methylene
chloride. The combined filtrates were freed from solvent in vacuo
and recrystallized from methylene chloride. 3.1 g (23%) of the
racemic and meso forms in the ratio 1:1 were obtained. Further
recrystallization from methylene chloride gave the racemic complex
in the form of yellow crystals.
[0218] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-8.0 (m, 22H, arom.
H), 6.9 (s, 2H, H--C(3)), 2.2 (s, 6H, CH.sub.3), 1.3 (s, 6H,
CH.sub.3Si). Mass spectrum: 729 M.sup.+, correct decomposition
pattern.
EXAMPLE G
rac-Ethanediylbis(2-methyl-4-phenylindenyl)zirconium dichloride
(33)
[0219] 1. 1,2-Bis(2-methyl-4-phenylindenyl)ethane (32)
[0220] 90 cm.sup.3 (0.24 mol) of a 20% strength solution of
butyllithium in toluene were added at room temperature under argon
to a solution of 50 g (0.24 mol) of 3 in 500 ml of THF. The mixture
was stirred at 60.degree. C. for 2 hours, and cooled to -78.degree.
C., 22.5 g (0.12 mol) of dibromoethane were added, and the mixture
was warmed to room temperature over the course of 18 hours. The
reaction mixture was washed with 50 cm.sup.3 of H.sub.2O, the
solvent was removed in vacuo, and the residue was chromatographed
on 500 g of silica gel (hexane/methylene chloride 9:1), giving 2.5
g (5%) of 32 as a yellow oil which solidified slowly at -20.degree.
C.
[0221] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-8.1 (m, 20H, arom.
H), 6.4 (m, 2H, H--C(3)), 4.0 (m, 2H, H--C (1)), -0.1, (s, 6H,
CH.sub.3Si).
[0222] 2. rac-Ethanediylbis(2-methyl-4-phenylindenyl)zirconium
dichloride (33)
[0223] 4 cm.sup.3 (10 mmol) of a 20% strength solution of
butyllithium in toluene were added at room temperature under argon
to a solution of 2.3 g (5 mmol) of 32 in 20 ml of H.sub.2O- and
O.sub.2-free Et.sub.2O, and the mixture was refluxed for 3 hours.
The solvent was removed in vacuo, the residue was filtered through
a G3 Schlenk frit with 30 ml of H.sub.2O- and O.sub.2-free hexane,
then washed with 30 ml of H.sub.2O- and O.sub.2-free hexane and
dried (0.1 mbar, RT).
[0224] The dilithio salt was added at -78.degree. C. to a
suspension of 1.2 g (5 mmol) of zirconium tetrachloride in 30
cm.sup.3 of methylene chloride, and the mixture was warmed to a
temperature over the course of 18 hours with magnetic stirring. The
batch was filtered through a G3 frit, and the residue was then
extracted in portions with a total of 100 cm.sup.3 of methylene
chloride. The combined filtrates were freed from solvent in vacuo
and recrystallized from methylene chloride/hexane. 0.5 g (18%) of
the racemic and meso forms in the ratio 1:1 was obtained. Further
recrystallization from toluene gave the racemic complex in the form
of yellow crystals.
[0225] .sup.1H-NMR (100 MHz, CDCl.sub.3): 7.0-7.7 (m, 16H, arom.
H), 6.6 (m, 2H, H--C(3)), 3.4-4.1 (m, 4H, H.sub.2C--CH.sub.2), 2.1
(s, 6H, CH.sub.3). Mass spectrum : 598 M.sup.+, correct
decomposition pattern.
EXAMPLE E
Me.sub.2Si(2-Me-4-Ph-indenyl).sub.2ZrMe[BPh.sub.4] (35)
[0226] 1.
rac-Dimethylsilanediylbis(2-Methyl-4-phenyl-indenyl)dimethylzirc-
onium (34)
[0227] 1 cm.sup.3 of a 1.6 M (1.6 mmol) solution of methyllithium
in Et.sub.2O were added at -30.degree. C. to 0.5 g (0.8 mmol) of
rac-5 in 10 cm.sup.3 of H.sub.2O- and O.sub.2-free Et.sub.2O, and
the mixture was stirred at 0.degree. C. for 1 hour. The solvent was
subsequently removed in vacuo, and the residue was taken up in 20
cm.sup.3 of H.sub.2O- and O.sub.2-free hexane and filtered off
through a G3 frit, giving 0.34 g (72%) of 34. Mass spectrum : 588
M.sup.+, correct decomposition pattern.
[0228] 2. Me.sub.2Si(2-Me-4-Ph-Indenyl).sub.2ZrMe[BPh.sub.4]
(35)
[0229] 0.2 g (0.3 mmol) of 34 were added at 0.degree. C. to 0.25 g
(mmol) of tributylammonium tetraphenylborate in 0 cm.sup.3 of
toluene. The mixture was warmed to 50.degree. C. with stirring and
stirred at this temperature for 15 minutes. An aliquot portion of
the solution was used for the polymerization.
EXAMPLE 1
[0230] A dry 16 dm.sup.3 reactor was first flushed with nitrogen
and subsequently with propylene and filled with 10 dm.sup.3 of
liquid propylene. 30 cm.sup.3 of a toluene solution of
methylaluminoxane were then added, and the batch was stirred at
30.degree. C. for 15 minutes.
[0231] In parallel, 1.1 mg of rac-5 were dissolved in 20 cm.sup.3
of a toluene solution of methylaluminoxane (27 mmol of Al) and
reacted by standing for 15 minutes. The solution was then
introduced into the reactor and heated to the polymerization
temperature of 50.degree. C. (4.degree. C./min) by supply of heat,
and the polymerization system was kept at 50.degree. C. for 1 hour
by cooling. The polymerization was terminated by addition of 20
cm.sup.3 of isopropanol. The excess monomer was removed in gas
form, and the polymer was dried in vacuo, giving 0.9 kg of
polypropylene. The reactor exhibited thin deposits on the internal
wall and stirrer. The catalyst activity was 818 kg of PP/g of
metallocene.times.h. VI=905 cm.sup.3/g; m.p. 159.4.degree. C.;
II=98.8%; mmmm=95.4%; M.sub.w=1,100,000 g/mol;
M.sub.w/M.sub.n=2.5.
EXAMPLE 2
[0232] The polymerization of Example 1 was repeated with the
difference that the catalyst used was 0.9 mg of rac-5 and the
polymerization temperature was 70.degree. C. 1.4 kg of
polypropylene were obtained. The reactor exhibited thick deposits
on the internal wall and stirrer. Catalyst activity was 1,555 kg of
PP/g of metallocene.times.h. VI=719 cm.sup.3/g; m.p.=157.7.degree.
C.
EXAMPLE 3
[0233] 22 cm.sup.3 of the suspension of "MAO on SiO.sub.2" (49 mmol
of Al) was introduced under argon into a G3 Schlenk frit, and a
solution of 4.5 mg of rac-5 in 10 cm.sup.3 of toluene (7.2 .mu.mol
of Zr) was added. The reaction mixture was stirred at room
temperature for 30 minutes, with a spontaneous color change to red
gradually fading. The mixture was subsequently filtered, and the
solid was washed 3 times with 10 cm.sup.3 of hexane. The
hexane-moist filter residue which remained was resuspended in 20
cm.sup.3 of hexane for the polymerization.
[0234] In parallel, a dry 16 dm.sup.3 reactor was flushed first
with nitrogen and subsequently with propylene and filled with 10
dm.sup.3 of liquid propylene. 3 cm.sup.3 of triisobutylaluminum
(pure, 12 mmol) were then diluted with 30 cm.sup.3 of hexane and
introduced into the reactor and the batch was stirred at 30.degree.
C. for 15 minutes. A catalyst suspension was subsequently
introduced into the reactor and heated to the polymerization
temperature of 50.degree. C. (4.degree. C./min), and the
polymerization system was kept at 50.degree. C. for 1 hour by
cooling. Polymerization was terminated by addition of 20 cm.sup.3
of isopropanol. The excess monomer was removed in gas form, and the
polymer was dried in vacuo. 300 g of polypropylene powder were
obtained. The reactor exhibited no deposits on the internal wall or
stirrer. The catalyst activity was 67 kg of PP/g of
metallocene.times.h. VI=1380 cm.sup.3/g; m.p.=156.degree. C.
EXAMPLE 4
[0235] The synthesis of the supported catalyst system from Example
3 was repeated with the difference that 13 cm.sup.3 (29 mmol of Al)
of the suspension "MAO on SiO.sub.2" and 1.8 mg of rac-5 (2.9
.mu.mol of Zr) were used.
[0236] The polymerization was carried out analogously to Example 3
at 70.degree. C. 420 g of polypropylene powder were obtained. The
reactor exhibited no deposits on the internal wall or stirrer. The
catalyst activity was 233 kg of PP/g of metallocene.times.h. VI=787
cm.sup.3/g; m.p.=149.5.degree. C.
EXAMPLE 5
[0237] The synthesis of the supported catalyst system from Example
3 was repeated with the difference that 150 cm.sup.3 (335 mmol of
Al) of the suspension "MAO on SiO.sub.2" and 44.2 mg of rac-5 (70.3
.mu.mol of Zr) were used and the reaction mixture was stirred at
room temperature for 60 minutes. The solid was subsequently
filtered off and washed 3 times with 50 cm.sup.3 of hexane. The
hexane-moist filter residue which remained was dried in vacuo to
give a free-flowing, pale pink powder. 33.3 g of supported, dry
catalyst were obtained.
[0238] For the polymerization, 2.98 g of this dry catalyst (4
mg=6.3 .mu.mol of Zr) were resuspended in 20 cm.sup.3 of
hexane.
[0239] The polymerization was carried out analogously to Example 3
at 70.degree. C. 1.05 kg of polypropylene powder were obtained. The
reactor exhibited no deposits on the internal wall or stirrer. The
catalyst activity was 263 kg of PP/g of metallocene.times.h. VI=944
cm.sup.3/g; m.p.=156.degree. C.
EXAMPLE 6
[0240] A dry 1.5 dm.sup.3 reactor was flushed with N.sub.2 and
filled at 20.degree. C. with 750 cm.sup.3 of a benzine cut with the
boiling range 100-120.degree. C. from which the aromatic compounds
had been removed (".RTM.Exxsol 100/120"). The gas space of the
reactor was then flushed free of nitrogen by injecting 8 bar of
propylene and releasing the pressure, and repeating this procedure
four times. 3.75 cm.sup.3 of a toluene solution of
methylaluminoxane (10% by weight of MAO) were then added. The
reactor contents were then heated to 30.degree. C. over the course
of 15 minutes with stirring, and the overall pressure was set at 8
bar by addition of propylene at a stirring rate of 500 rpm.
[0241] In parallel, 0.1 mg of rac-5 were dissolved in 1.25 cm.sup.3
of a toluene solution of methylaluminoxane and reacted fully by
standing for 15 minutes. The solution was then introduced into the
reactor, and the polymerization system was heated to a temperature
of 50.degree. C. and kept at this temperature for 1 hour by
appropriate cooling. The pressure was kept at 8 bar during this
time by appropriate supply of propylene, the reaction was then
terminated by addition of 2 cm.sup.3 of isopropanol, and the
polymer was filtered off and dried in vacuo.
[0242] 16 g of polypropylene were obtained. The reactor exhibited
deposits on the internal wall and stirrer. The catalyst activity
(CTY.sub.red) was 20 kg of PP/g of metallocene.times.h.times.bar.
VI=833 cm.sup.3/g; m.p. =159.degree. C.
EXAMPLE 7
[0243] The polymerization of Example 6 was repeated with the
difference that the polymerization temperature was 60.degree.
C.
[0244] 35 g of polypropylene were obtained. The reactor exhibited
deposits on the internal wall and stirrer. The catalyst activity
(CTY.sub.red) was 44 kg of PP/g of metallocene.times.h.times.bar.
VI=484 cm.sup.3/g; m.p.=159.degree. C.
EXAMPLE 8
[0245] The polymerization from Example 6 was repeated with the
difference that the polymerization temperature was 70.degree.
C.
[0246] 88 g of polypropylene were obtained. The reactor exhibited
deposits on the internal wall and stirrer. The catalyst activity
(CTY.sub.red) was 110 kg of PP/g of metallocene.times.h.times.bar.
VI=414 cm.sup.3/g; m.p.=159.degree. C.
EXAMPLES 9-12
[0247] The procedure was as in Example 2. However, hydrogen was
metered in before the filling with liquid propylene:
1 Dm.sup.2(s.t.) Metallocene activity VI Example of H.sub.2 [kg of
PP/g of Met .times. h] [cm.sup.3/g] 9 1.5 1640 495 10 3 1590 212 11
4.5 1720 142 12 200 1580 17
[0248] Examples 9-12 demonstrate the good hydrogen utilization of
the metallocene according to the invention. Molecular weight
regulation into the wax region (see Example 12) is possible.
EXAMPLE 13
[0249] The procedure was as in Example 3. However, 0.2 bar of
hydrogen was injected into the reactor before addition of the
catalyst, and the polymerization temperature was 60.degree. C.
However, ethylene was metered in at a uniform rate during the
polymerization. In total. 12 g of ethylene were introduced into the
reactor. 0.4 kg of ethylene-copolymer were obtained. The
metallocene activity was 88 kg of copolymer/g of
metallocene.times.h. The ethylene content of the polymer was 2.4%
by weight, and the ethylene was predominantly incorporated as
isolated units. VI=200 cm.sup.3/g; melting point 143.degree. C.
EXAMPLE 14
[0250] The procedure was as in Example 13. However, a total of 34 g
of ethylene were metered in during polymerization. 0.38 kg of
ethylene-propylene copolymer containing 7% by weight of ethylene
was obtained. VI=120 cm.sup.3; melting point 121.degree. C.
EXAMPLE 15
[0251] The procedure was as in Example 4. However, 4 g of ethylene
were metered in during the polymerization and 0.1 bar of hydrogen
was injected before the polymerization. 0.52 kg of
ethylene-propylene copolymer were obtained. The metallocene
activity was 286 kg of copolymer/g of metallocene.times.h. The
ethylene content of the polymer was 6.1% by weight, and the
majority of the ethylene was incorporated as isolated units. VI=150
cm.sup.3/g; melting point 116.degree. C.
EXAMPLE 16
[0252] A dry 150 dm.sup.3 reactor was flushed with nitrogen and
filled at 20.degree. C. with 80 dm.sup.3 of a benzine cut having
the boiling range of 100-120.degree. C. from which the aromatic
compounds had been removed. The gas space was then flushed free of
nitrogen by injecting 2 bar of propylene and releasing the
pressure, and repeating this procedure four times. After 50 l of
liquid propylene had been added, 64 cm.sup.3 of a toluene solution
of methylaluminoxane (corresponding to 100 mmol of Al, molecular
weight 1080 g/mol according to cryoscopic determination) were
added, and the reactor contents were heated to 50.degree. C. A
hydrogen content of 2.0% was established in the gas space of the
reactor by metering in hydrogen and was later kept constant during
the 1st polymerization step by subsequent metering in.
[0253] 9.8 mg of rac-7 were dissolved in 32 ml of the toluene
solution of methylaluminoxane (corresponding to 50 mmol of Al) and
were introduced into the reactor after 15 minutes. The
polymerization was then carried out in a 1st polymerization step
for 5 hours at 50.degree. C. The gaseous components were then
removed at a reactor pressure of 3 bar, and 2000 g of ethylene gas
were fed in. The reactor pressure increased to 8 bar during this
operation, and the polymerization was continued for a further 14
hours at 40.degree. C. before the reaction was terminated by means
of CO.sub.2 gas.
[0254] 18.6 kg of block copolymer were obtained, corresponding to a
metallocene activity of 99.9 kg of copolymer/g of
metallocene.times.h. VI=230 cm.sup.3/g; MFI (230/5)=11 dg/min, MFI
(230/2.16)=3.7 dg/min; melting point of the polymer in the 1st
polymerization step: 159.degree. C., glass transition temperature
of the polymer in the 2nd polymerization step: -38.degree. C. The
block copolymer contained 5% of ethylene. Fractionation of the
product gave the following composition: 69% by weight of
homopolymer, 31% by weight of copolymer, the copolymer having an
ethylene content of 15% by weight, and the mean C.sub.2 block
length was 2.2.
EXAMPLE 16a
[0255] The procedure was as in Example 16.
[0256] 3 mg of rac-24 were dissolved in 32 ml of the toluene
solution of methylaluminoxane (corresponding to 50 mmol of Al) and
were introduced into the reactor after 15 minutes. The
polymerization was then carried out in a 1st polymerization step
for 2.5 hours at 50.degree. C. The gaseous components were then
removed at a reactor pressure of 3 bar, and 3000 g of ethylene gas
were fed in. The reactor pressure increased to 8 bar during this
operation, and the polymerization was continued for a further 8
hours at 40.degree. C. before the reaction was terminated by means
of CO.sub.2 gas.
[0257] 16.5 kg of block copolymer were obtained, corresponding to a
metallocene activity of 524 kg of copolymer/g of
metallocene.times.h. VI=480 cm.sup.3/g; MFI (230/5)=2 dg/min,
melting point of the polymer in the 1st polymerization step:
162.degree. C., glass transition temperature of the polymer in the
2nd polymerization step: -54.degree. C. The block copolymer
contained 15% of ethylene.
EXAMPLE 17
[0258] The procedure was as in Example 1, but 12.5 mg of
metallocene rac-7 were used. 1.5 kg of polypropylene were obtained;
the metallocene activity was 120 kg of PP/g of metallocene.times.h.
VI=1050 cm.sup.3/g; melting point 159.degree. C.
EXAMPLE 18
[0259] The procedure was as in Example 2, but 4.1 mg of metallocene
rac-7 were used. 1.3 kg of polypropylene were obtained; the
metallocene activity was 317 kg of PP/g of metallocene.times.h.
VI=555 cm.sup.3/g; melting point 157.degree. C.
COMPARATIVE EXAMPLE A
[0260] The procedure was as in Example 1, but 12.5 mg of
rac-phenyl(methyl)silanediylbis(2-methyl-1-indenyl)zirconium
dichloride were used. 1.35 kg of polypropylene were obtained; the
metallocene activity was 108 kg of PP/g of metallocene.times.h.
VI=1050 cm.sup.3/gl; melting point 149.degree. C.
COMPARATIVE EXAMPLE B
[0261] The procedure was as in Example 1, but 12.5 mg of rac-phenyl
(methyl) silanediylbis (1-indenyl) zirconium dichloride were used.
0.28 kg of polypropylene were obtained; the metallocene activity
was 22.4 kg of PP/g of metallocene.times.h. VI=74 cm.sup.3/gl;
melting point 141.degree. C.
EXAMPLE 19
[0262] The procedure was as in Example 1, but 3.3 mg of 24 were
used. 0.78 kg of polypropylene were obtained; metallocene activity
was 237 kg of PP/g of metallocene.times.h. VI=1700 cm.sup.3/g;
melting point 163.degree. C., M.sub.w=2.1.times.10.sup.6 g/mol, MFI
230/21.6 1 dg/min; M.sub.w/M.sub.n=2.1.
EXAMPLE 19a
[0263] The procedure was as in Example 2, but 1.0 mg of rac-24 were
used. 1.2 kg of polypropylene were obtained. The metallocene
activity was 1200 kg of PP/g of metallocene.times.h. VI=1100
cm.sup.3/g. Melting point=161.degree. C.
EXAMPLE 20
[0264] The procedure was as in Example 1; however the
polymerization temperature was 40.degree. C. 6.0 mg of 17 were
used. 1.95 kg of polypropylene were obtained; the metallocene
activity was 325 kg of PP/g of metallocene.times.h. VI=1320
cm.sup.3/g; melting point 162.degree. C.,
M.sub.w=1.79.times.10.sup.6 g/mol, M.sub.w/M.sub.n2.3.
COMPARATIVE EXAMPLE C
[0265] The procedure was as in Example 20, but the conventional
metallocene rac-dimethylsilanediylbis(2-ethyl-1-indenyl)zirconium
dichloride was used. 0.374 kg of polypropylene were obtained; the
metallocene activity was 62.3 kg of PP/g of metallocene.times.h.
VI=398 cm.sup.3/g; melting point 147.degree. C., M.sub.w=450,000
g/mol, M.sub.w/M.sub.n=2.5.
EXAMPLE 21
[0266] The procedure was as in Example 1, but 5.2 mg of 31 were
used. 1.67 kg of polypropylene were obtained; the metallocene
activity was 321 kg of PP/g of metallocene.times.h. VI=980
cm.sup.3/g; melting point 158.degree. C.
EXAMPLE 22
[0267] The procedure was as in Example 1, but the polymerization
was carried out at 30.degree. C. and 3.7 mg of 33 were used. 0.35
kg of polypropylene were obtained; the metallocene activity was 94
kg of PP/g of metallocene.times.h. VI=440 cm.sup.3/g; melting point
153.degree. C.
EXAMPLE 23
[0268] A dry 16 dm.sup.3 reactor was flushed with propylene and
filled with 10 dm.sup.3 of liquid propylene. 1.1 cm.sup.3 of the
reaction product from H.2 (corresponding to 7.5 mg of 34) were then
dissolved in 20 cm.sup.3 of toluene and introduced into the reactor
at 30.degree. C. The reactor was heated to 50.degree. C.
(10.degree. C./min) and the polymerization system was kept at this
temperature for 1 hour by cooling. The polymerization was
terminated by addition of CO.sub.2 gas. The excess monomer was
removed in gas form, and the polymer was dried in vacuo at
80.degree. C. 2.45 kg of polypropylene were obtained. VI=875
cm.sup.3/g; melting point 160.degree. C.
EXAMPLE 24
[0269] A dry 16 dm.sup.3 reactor was flushed with nitrogen and
filled at 20.degree. C. with 10 dm.sup.3 of a benzine cut having
the boiling range 100-120.degree. C. from which the aromatic
compounds had been removed. The gas space of the reactor was then
flushed free of nitrogen by injecting 2 bar of ethylene and
releasing the pressure and repeating this operation 4 times. 30
cm.sup.3 of a toluene solution of methylaluminoxane (corresponding
to 45 mmol of Al, molecular weight 700 g/mol according to
cryoscopic determination) were then added. The reactor contents
were heated to 30.degree. C. over the course of 15 minutes with
stirring, and the overall pressure was set at 5 bar by addition of
ethylene at a stirring rate of 250 rpm.
[0270] In parallel, 3.2 g of 12 were dissolved in 20 cm.sup.3 of a
toluene solution of methylaluminoxane and were preactivated by
standing for 15 minutes. The solution was then introduced into the
reactor, and the polymerization system was heated to a temperature
of 50.degree. C. and kept at this temperature for 4 hours by
appropriate cooling. The overall pressure was kept at 5 bar during
this time by a appropriate supply of ethylene.
[0271] The polymerization was terminated by addition of 20 ml of
isopropanol, and the polymer was filtered off and dried in vacuo.
0.7 kg of polyethylene were obtained. VI=690 cm.sup.3/g.
EXAMPLE 25
[0272] The procedure of Example 24 was followed. In contrast to
Example 23, 1.8 mg of rac-7 were employed, and the polymerization
system was heated to 70.degree. C. and kept at this temperature for
1 hour. 0.9 kg of polyethylene were obtained. VI=730
cm.sup.3/g.
EXAMPLE 26
[0273] 15 g of "F-MAO on SiO.sub.2" (111 mmol of Al) were suspended
in 100 cm.sup.3 of toluene in a stirrable vessel and cooled to
-20.degree. C. At the same time, 155 mg (0.246 mmol) of rac-5 were
dissolved in 75 cm.sup.3 of toluene and added dropwise to this
suspension over the course of 30 minutes. The mixture was slowly
warmed to room temperature with stirring, the suspension taking on
a red color. The mixture was subsequently stirred at 80.degree. C.
for 1 hour, cooled to room temperature and filtered, and the solid
was washed 3 times with 100 cm.sup.3 of toluene in each case and
once with 100 cm.sup.3 of hexane. The filtrate was red. The
hexane-moist filter residue which remained was dried in vacuo,
giving 13.2 g of free-flowing, pale red, supported catalyst.
Analysis gave a content of 3.2 mg of zirconocene per gram of
catalyst.
[0274] Polymerization: For the polymerization, 2.08 g of the
catalyst were suspended in 50 cm.sup.3 of a benzine cut having the
boiling range of 100-120.degree. C. from which the aromatic
compounds had been removed. The polymerization was carried out
analogously to Example 3 at 60.degree. C. 1100 g of polypropylene
powder were obtained. The reactor exhibited no deposits on the
internal wall or stirrer. Activity=165 kg of PP/(g of
metallocene.times.h). VI=1100 cm.sup.3/g. Melting point=153.degree.
C.; M.sub.w=1,485,000; M.sub.w/M.sub.n=3.2; MFI 230/5=0.1 dg/min;
BD=440 g/dm.sup.3.
EXAMPLE 27
[0275] 1.31 g of the catalyst from Example 26 were suspended in 50
cm.sup.3 of a benzine cut having the boiling range of
100-120.degree. C. from which the aromatic compounds had been
removed. The polymerization was carried out analogously to Example
3 at 70.degree. C. 1300 g of polypropylene powder were obtained.
The reactor exhibited no deposits on the internal wall or stirrer.
Activity=310 kg of PP/(g of metallocene.times.h). VI=892
cm.sup.3/g; melting point=150.degree. C., M.sub.w=1,290,000;
M.sub.w/M.sub.n=3.0; BD=410 g/dm.sup.3.
EXAMPLE 28
[0276] The supporting procedure from Example 26 was repeated with
the difference that 0.845 g of rac-5 dissolved in 500 cm.sup.3 of
toluene were reacted with 90 g of "F-MAO on SiO.sub.2" and
suspended in 500 cm.sup.3 of toluene. 84 g of red, pulverulent
catalyst were obtained. Analysis gave a content of 9 mg of
metallocene per gram of solid, and the red filtrate contained 13 mg
of zirconium.
[0277] Polymerization: 1.1 g of the supported catalyst were
suspended in 50 ml of a benzine cut having a boiling range of
100-120.degree. C. from which the aromatic compounds had been
removed. The polymerization was carried out analogously to Example
3 at 70.degree. C. 2850 g of polypropylene powder were obtained.
The reactor exhibited no deposits on the internal wall or stirrer.
Activity=288 kg of PP/(g of metallocene.times.h); VI=638
cm.sup.3/g; melting point=150.degree. C.; MFI 230/5=0.5 dg/min;
BD=410 g/dm.sup.3.
EXAMPLE 29
[0278] A microporous polypropylene powder (AKZO) having a particle
size of smaller than 100 .mu.m was freed from impurities by
extraction with toluene in a Soxhlet extractor under inert
conditions and subsequently washed with 20% strength by weight of
trimethylaluminum solution in toluene and dried in vacuo. In
parallel, 51.1 mg of rac-5 were dissolved in 40 cm.sup.3 of a
toluene solution of methylaluminoxane and reacted fully by standing
for 15 minutes. 16.5 g of the PP powder were metered in, and the
gas in the pores of the support and some of the solvent were
removed by briefly applying a vacuum, and the catalyst solution was
absorbed fully. Vigorous shaking of the reaction vessel gave 46 g
of homogeneous, finely divided and free-flowing red powder. 10 g of
the supported catalyst powder were prepolymerized for 30 minutes
with ethylene under inert conditions in a rotary evaporator. The
ethylene excess pressure was kept constant at 0.1 bar by means of a
pressure-regulation valve, and the mixing of the catalyst powder
was achieved by continuous rotation of the reaction vessel with
cooling at 0.degree. C. 12 g of prepolymerized catalyst were
obtained.
[0279] Polymerization: 4.6 g of the supported, prepolymerized
catalyst were suspended in 50 cm.sup.3 of a benzine cut having the
boiling range 100-120.degree. C. from which the aromatic compounds
had been removed. Polymerization was carried out analogously to
Example 3 at 70.degree. C. 250 g of polypropylene powder were
obtained. The reactor exhibited no deposits on the internal wall or
stirrer, and the mean particle size was 1,000 .mu.m. Activity=59 kg
of PP/(g of metallocene.times.h); VI=734 cm.sup.3/g. Melting
point=152.degree. C.; BD=390 g/dm.sup.3.
EXAMPLE 30
[0280] 1 g of the supported, non-prepolymerized catalyst from
Example 29 was suspended in 50 cm.sup.3 of n-decane for the
polymerization. The polymerization was carried out analogously to
Example 3 at 70.degree. C. 600 g of polypropylene were obtained.
The reactor exhibited thin deposits on the internal wall and
stirrer, and the mean particle diameter was>2000 .mu.m.
Activity=540 kg of PP/(g of metallocene.times.h); VI=1400
cm.sup.3/g; melting point=157.7.degree. C.; BD=280 g/dm.sup.3.
* * * * *