U.S. patent application number 10/062389 was filed with the patent office on 2002-10-31 for metallocene compositions.
Invention is credited to Burkhardt, Terry J., Hart, James R., Haygood, William T. JR., Kuchta, Matthew C., Li, Robert T., Stehling, Udo M., Vizzini, James C..
Application Number | 20020161143 10/062389 |
Document ID | / |
Family ID | 26910049 |
Filed Date | 2002-10-31 |
United States Patent
Application |
20020161143 |
Kind Code |
A1 |
Burkhardt, Terry J. ; et
al. |
October 31, 2002 |
Metallocene compositions
Abstract
This invention relates to metallocene compositions and their use
in the preparation of catalyst systems for olefin polymerization,
particularly propylene polymerization. The metallocene compositions
may be represented by the formula: 1 wherein M.sup.1 is selected
from the group consisting of titanium, zirconium, hafnium,
vanadium, niobium, tantalum, chromium, molybdenum and tungsten,
preferably zirconium, hafnium or titanium, most preferably
zirconium; R.sup.1 and R.sup.2 are identical or different, and are
one of 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.2-C.sub.40 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, or a conjugated diene which
is optionally substituted with one or more hydrocarbyl,
tri(hydrocarbyl)silyl groups or hydrocarbyl,
tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30
atoms not counting hydrogen; preferably R.sup.1 and R.sup.2 are
identical and are a C.sub.1-C.sub.3 alkyl or alkoxy group, a
C.sub.6-C.sub.8 aryl or aryloxy group, a C.sub.2-C.sub.4 alkenyl
group, a C.sub.7-C.sub.10 arylalkyl group, a C.sub.7-C.sub.12
alkylaryl group, or a halogen atom, preferably chlorine; R.sup.3
are identical or different and are each 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 which may be halogenated, 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, a --NR'.sub.2, --SR'.sup.1, --OR', --OSiR'.sub.3 or
--PR'.sub.2 radical, wherein R' is one of a halogen atom, a
C.sub.1-C.sub.10 alkyl group, or a C.sub.6-C.sub.10 aryl group;
preferably R.sup.3 is not a hydrogen atom; preferably each R.sup.3
is identical and is a fluorine, chlorine or bromine, atom, a
C.sub.1-C.sub.4 alkyl group which may be halogenated, a
C.sub.6-C.sub.8 aryl group which may be halogenated, a --NR'.sub.2,
--SR', --OR', --OSiR'.sub.3 or --PR'.sub.2 radical, wherein R' is
one of a chlorine atom, a C.sub.1-C.sub.4 alkyl group, or a
C.sub.6-C.sub.8 aryl group; more preferably, R.sup.3 are identical
and are each a C.sub.3 alkyl group, most preferably isopropyl
groups; alternatively, R.sup.3 is a C.sub.1 or C.sub.2 alkyl group;
R.sup.4 to R.sup.7 are identical or different and are hydrogen, as
defined for R.sub.3 or two or more adjacent radicals R.sup.5 to
R.sup.7 together with the atoms connecting them form one or more
rings, preferably a 4-8 membered ring , more preferably a
6-membered ring; 2 --B(R.sup.14)--, --Al(R.sup.14)--, --Ge--,
--Sn--, --O--, --S--, --SO--, --SO2-, --N(R.sup.14)--, --CO--,
--P(R.sup.14)--, or --P(O)(R.sup.14)--, or an amidoborane radical;
wherein: R.sup.14, R.sup.15and R.sup.16 are identical or different
and are a hydrogen atom, a halogen atom, a C.sub.1-C.sub.20 alkyl
group, a C.sub.1-C.sub.20 fluoroalkyl or silaalkyl group, a
C.sub.6-C.sub.30 aryl group, a C.sub.6-C.sub.30 fluoroaryl group, a
C.sub.1-C.sub.20 alkoxy group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.7-C.sub.40 arylalkyl group, a C.sub.8-C.sub.40 arylalkenyl
group, a C.sub.7-C.sub.40 alkylaryl group, or R.sup.14 and
R.sup.15, together with the atoms binding them, form a cyclic ring;
preferably, R.sup.14, R.sup.15and R.sup.16 are identical and are a
hydrogen atom, a halogen atom, a C.sub.1-C.sub.4 alkyl group, a
CF.sub.3 group, a C.sub.6-C.sub.8 aryl group, a C.sub.6-C.sub.10
fluoroaryl group, more preferably a pentafluorophenyl group, a
C.sub.1-C.sub.4 alkoxy group, in particular a methoxy group, a
C.sub.2-C.sub.4 alkenyl group, a C.sub.7-C.sub.10 arylalkyl group,
a C.sub.8-C.sub.12 arylalkenyl group, or a
C.sub.7-C.sub.12alkylaryl group; or, R.sup.13 is represented by the
formula: 3 wherein R.sup.17 to R.sup.24 are as defined for R.sup.1
and R.sup.2, or two or more adjacent radicals R.sup.17 to R.sup.24,
including R.sup.20 and R.sup.21, together with the atoms connecting
them form one or more rings; preferably, R.sup.17 to R.sup.24 are
hydrogen. M.sup.2 is one or more carbons, silicon, germanium or
tin, preferably silicon; R.sup.8, R.sup.10 and R.sup.12 are
identical or different and have the meanings stated for R.sup.4 to
R.sup.7; R.sup.9 and R.sup.11 are identical or different and are a
Group IVA radical having from 1 to 20 carbon atoms or are each
primary, secondary or tertiary butyl groups, aryl groups, isopropyl
groups, fluoroalkyl groups, trialkyl silyl groups, or other groups
of similar size, preferably a tertiary butyl group.
Inventors: |
Burkhardt, Terry J.;
(Kingwood, TX) ; Stehling, Udo M.; (Vantaa,
FI) ; Hart, James R.; (Pasadena, TX) ;
Haygood, William T. JR.; (Houston, TX) ; Li, Robert
T.; (Houston, TX) ; Vizzini, James C.;
(Pasadena, TX) ; Kuchta, Matthew C.; (Houston,
TX) |
Correspondence
Address: |
ExxonMobil Chemical Company
P.O. Box 2149
Baytown
TX
77522-2149
US
|
Family ID: |
26910049 |
Appl. No.: |
10/062389 |
Filed: |
January 31, 2002 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10062389 |
Jan 31, 2002 |
|
|
|
09619748 |
Jul 19, 2000 |
|
|
|
6376627 |
|
|
|
|
60215459 |
Jun 30, 2000 |
|
|
|
Current U.S.
Class: |
526/127 ;
526/160; 526/170; 526/348.5; 526/348.6; 526/943 |
Current CPC
Class: |
C07F 17/00 20130101;
C08F 4/65912 20130101; C08F 210/16 20130101; C08F 2420/09 20210101;
C08F 4/65908 20130101; C08F 10/00 20130101; C08F 210/06 20130101;
C08F 110/02 20130101; Y10S 526/943 20130101; C08F 110/06 20130101;
C08F 4/65916 20130101; C08F 10/00 20130101; C08F 4/65927 20130101;
C08F 110/02 20130101; C08F 2500/12 20130101; C08F 2500/03 20130101;
C08F 2500/17 20130101; C08F 110/06 20130101; C08F 2500/03 20130101;
C08F 2500/15 20130101; C08F 2500/12 20130101; C08F 2500/17
20130101; C08F 210/06 20130101; C08F 210/16 20130101; C08F 2500/12
20130101; C08F 2500/17 20130101; C08F 2500/03 20130101; C08F
2500/21 20130101; C08F 210/06 20130101; C08F 210/16 20130101; C08F
2500/12 20130101; C08F 2500/03 20130101; C08F 2500/17 20130101;
C08F 210/16 20130101; C08F 210/06 20130101; C08F 2500/12 20130101;
C08F 2500/03 20130101; C08F 2500/17 20130101 |
Class at
Publication: |
526/127 ;
526/170; 526/943; 526/348.5; 526/348.6; 526/160 |
International
Class: |
C08F 004/44 |
Claims
We claim:
1. A polymerization process comprising contacting under suitable
polymerization conditions one or more monomers and the reaction
product of one or more activators and one ore more compounds
represented by the formula: 23wherein: M.sup.1 is selected from the
group consisting of titanium, zirconium, hafnium, vanadium,
niobium, tantalum, chromium, molybdenum and tungsten; R.sup.1 and
R.sup.2 are identical or different, and are one of 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.2-C.sub.40 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, or a conjugated diene which is optionally substituted
with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or
hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said diene
having up to 30 atoms not counting hydrogen; R.sup.3 are identical
or different and are each a halogen atom, a C.sub.3-C.sub.10 alkyl
5 group which may be halogenated, a C.sub.6-Cl.sub.0 aryl group
which may be halogenated, 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, a --NR'.sub.2, --SR',
--OR:, --OSiR'.sub.3 or --PR'.sub.2 radical, wherein R: is one of 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.7 are identical or different and are
hydrogen, as defined for R.sup.3 or two or more adjacent radicals
R.sup.5 to R.sup.7 together with the atoms connecting them form one
or more rings; 24--B(R.sup.14)--, --Al(R.sup.14)--, --Ge--, --Sn--,
--O--, --S--, --SO--, --SO.sub.2--, --N(R.sup.14)--, --CO--,
--P(R.sup.14)--, or --P(O)(R.sup.14)--, or an amidoborane radical;
wherein: R.sup.14, R.sup.15and R.sup.16 are identical or different
and are a hydrogen atom, a halogen atom, a C.sub.1-C.sub.20 alkyl
group, a C.sub.1-C.sub.20 fluoroalkyl or silaalkyl group, a
C.sub.6-C.sub.30 aryl group, a C.sub.6-C.sub.30 fluoroaryl group, a
C.sub.1-C.sub.20 alkoxy group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.7-C.sub.40 arylalkyl group, a C.sub.8-C.sub.40 arylalkenyl
group, a C.sub.7-C.sub.40 alkylaryl group, or R.sup.14 and
R.sup.15, together with the atoms binding them, form a cyclic ring;
or, R.sup.13 is represented by the formula: 25wherein: R.sup.17 to
R.sup.24 are as defined for R.sup.1 and R.sup.2, or two or more
adjacent radicals R.sup.17 to R.sup.24, including R.sup.20 and
R.sup.21, together with the atoms connecting them form one or more
rings; M.sup.2 is one or more carbons, silicon, germanium or tin;
R.sup.8, R.sup.10 and R.sup.12 are identical or different and have
the meanings stated for R.sup.4to R.sup.7;and R.sup.9 and R.sup.11
are identical or different and are each a Group IVA radical having
from 2 to 20 carbon atoms or are each a primary, secondary or
tertiary butyl group, an aryl group, an isopropyl group, trialkyl
silyl group, or a fluoroalkyl group.
2. The process of claim 1 wherein R.sup.3 are identical
C.sub.3-C.sub.10 alkyl groups.
3. The process of claim 1 wherein R.sup.4 to R.sup.7 are hydrogen
atoms.
4. The process of claim 1 wherein the monomers are selected from
C.sub.2-C.sub.14 olefins.
5. The process of claim 1 wherein the monomers are selected from
ethylene, propylene, 1-butene and 1-hexene.
6. A polymer comprising propylene units prepared by the process of
claim 1.
7. The process of claim 1 wherein the monomers consist essentially
of propylene.
8. The process of claim 1 wherein M.sup.1 is selected from
titanium, zirconium and hafnium.
9. The process of claim 1 wherein M.sup.1 is zirconium.
10. The process of claim 1 wherein R.sup.3 are identical C.sub.3
alkyl groups.
Description
[0001] This application is based on U.S. Provisional Patent
Application Serial No. 60/215,459 filed Jun. 30, 2000.
FIELD
[0002] This invention relates to metallocene compositions and their
use in the preparation of catalyst systems for olefin
polymerization, particularly propylene polymerization.
BACKGROUND
[0003] The use of metallocene compositions in olefin polymerization
is well known. Metallocenes containing substituted, bridged indenyl
derivatives are noted for their ability to produce isotactic
propylene polymers having high isotacticity and narrow molecular
weight distribution. Considerable effort has been made toward
obtaining metallocene produced propylene polymers having
ever-higher molecular weight and melting point, while maintaining
suitable catalyst activity.
[0004] Toward this end researchers have found that there is a
direct relationship between the way in which a metallocene is
substituted, and the molecular structure of the resulting polymer.
For the substituted, bridged indenyl type metallocenes, it is now
well established that the type and arrangement of substituents on
the indenyl groups, as well as the type of bridge connecting the
indenyl groups, determines such polymer attributes as molecular
weight and melting point. Unfortunately, it is impossible at this
time to accurately correlate specific substitution patterns with
specific polymer attributes, though trends may be identified.
[0005] For example, U.S. Pat. No. 5,840,644 describes certain
metallocenes containing aryl-substituted indenyl derivatives as
ligands, which are said to provide propylene polymers having high
isotacticity, narrow molecular weight distribution and very high
molecular weight.
[0006] Likewise, U.S. Pat. No. 5,936,053 describes certain
metallocene compounds said to be useful for producing high
molecular weight propylene polymers. These metallocenes have a
specific hydrocarbon substituent at the 2 position and an
unsubstituted aryl substituent at the 4 position, on each indenyl
group of the metallocene compound.
[0007] WO 98/40419 and WO 99/42497 both describe certain supported
catalyst systems for producing propylene polymers having high
melting point. Metallocene compositions and their activators are
often combined with a support material in order to obtain a
catalyst system that is less likely to cause reactor fouling.
However, it is known that supported metallocene catalyst systems
tend to result in a polymer having lower melting point than would
otherwise be obtained if the metallocene were not supported.
[0008] Much of the current research in this area has been directed
toward using metallocene catalyst systems under commercially
relevant process conditions, to obtain propylene polymers having
melting points higher than known metallocene catalyst systems and
close to, or as high as, propylene polymers obtained using
conventional, Ziegler-Natta catalyst systems, i.e., 160.degree. C.
or higher. The present inventors have discovered metallocene
compounds that not only have this capability, but retain it upon
supportation.
SUMMARY
[0009] The present invention relates to novel metallocene
compositions capable of providing propylene polymers having high
melting point and molecular weight. The present invention further
relates to metallocene catalyst systems comprising one or more of
these compositions and one or more activators or cocatalysts, and
optionally, support material, and to the use of such metallocene
catalyst systems in olefin polymerization, particularly propylene
polymer polymerization.
DESCRIPTION
[0010] The metallocenes of the present invention are represented by
the formula: 4
[0011] wherein: M.sup.1 is selected from the group consisting of
titanium, zirconium, hafnium, vanadium, niobium, tantalum,
chromium, molybdenum and tungsten, preferably zirconium, hafnium or
titanium, most preferably zirconium;
[0012] R.sup.1 and R.sup.2 are identical or different, and are one
of 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.2-C.sub.40 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; R.sup.1 and R.sup.2 may also
be joined together to form an alkanediyl group or a conjugated
C.sub.4-.sub.40 diene ligand which is coordinated to M.sup.1 in a
metallocyclopentene fashion; R.sup.1 and R.sup.2 may also be
identical or different conjugated dienes, optionally substituted
with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or
hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said dienes
having up to 30 atoms not counting hydrogen and forming a .pi.
complex with M, examples include 1,4-diphenyl-1,3-butadiene,
1,3-pentadiene, 2-methyl-1,3-pentadiene, 2,4-hexadiene,
1-phenyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene,
1,4-ditolyl-1,3-butadiene, 1,4-bis(trimethylsilyl)-1,3-butadiene,
and 1,4-dinaphthyl-1,3-butadiene;
[0013] preferably R.sup.1 and R.sup.2 are identical and are a
C.sub.1-C.sub.3 alkyl or alkoxy group, a C.sub.6-Cg aryl or aryloxy
group, a C.sub.2-C.sub.4 alkenyl group, a C.sub.7-C.sub.10
arylalkyl group, a C.sub.7-C.sub.12 alkylaryl group, or a halogen
atom, preferably chlorine;
[0014] R.sup.3 are identical or different and are each 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 which may be
halogenated, 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.8C.sub.40 arylalkenyl group, a --NR'.sub.2,--SR',
--OR, --OSiR'.sub.3 or --PR'.sub.2 radical, wherein R is one of a
halogen atom, a C.sub.1-C.sub.10 alkyl group, or a C.sub.6-C.sub.10
aryl group; preferably R.sup.3 is not a hydrogen atom;
[0015] preferably each R.sup.3 is identical and is a fluorine,
chlorine or bromine, atom, a C.sub.1-C.sub.4 alkyl group which may
be halogenated, a C.sub.6-C.sub.8 aryl group which may be
halogenated, a --NR'.sub.2,--SR', --OR, --OSiR'.sub.3 or
--PR'.sub.2 radical, wherein R' is one of a chlorine atom, a
C.sub.1-C.sub.4 alkyl group, or a C.sub.6-C.sub.8 aryl group;
[0016] more preferably, R.sup.3 are identical and are each a
C.sub.3 alkyl group, most preferably isopropyl groups;
[0017] alternatively, R.sup.3 is a C.sub.1 or C.sub.2 alkyl
group;
[0018] R.sup.4 to R.sup.7 are identical or different and are
hydrogen, or are as defined for R.sup.3 or two or more adjacent
radicals R.sup.5 to R.sup.7 together with the atoms connecting them
form one or more rings, preferably a 6-membered ring, preferably
4-8 membered ring; 5
[0019] --B(R.sup.14)--, --Al(R.sup.14)--, --Ge--, --Sn--, --O--,
--S--, --SO--, --SO.sub.2--, --N(R.sup.14)--, --CO--,
--P(R.sup.14)--, or --P(O)(R.sup.14)--;
[0020] wherein: R.sup.14, R.sup.15 and R.sup.16 are identical or
different and are a hydrogen atom, a halogen atom, a
C.sub.1-C.sub.20 branched or linear alkyl group, a C.sub.1-C.sub.20
fluoroalkyl or silaalkyl group, a C.sub.6-C.sub.30 aryl group, a
C.sub.6-C.sub.30 fluoroaryl group, a C.sub.1-C.sub.20 alkoxy group,
a C.sub.2-C.sub.20 alkenyl group, a C.sub.7-C.sub.40 arylalkyl
group, a C.sub.8-C.sub.40 arylalkenyl group, a C.sub.7-C.sub.40
alkylaryl group, or R.sup.14 and R.sup.15, together with the atoms
binding them, form a cyclic ring;
[0021] preferably, R.sup.14, R.sup.15and R.sup.16 are identical and
are a hydrogen atom, a halogen atom, a C.sub.1-C.sub.4 alkyl group,
a CF.sub.3 group, a C.sub.6-C.sub.8 aryl group, a C.sub.6-C.sub.10
fluoroaryl group, more preferably a pentafluorophenyl group, a
C.sub.1-C.sub.4 alkoxy group, in particular a methoxy group, a
C.sub.2-C.sub.4 alkenyl group, a C.sub.7-C.sub.10 arylalkyl group,
a C.sub.8-C.sub.12 arylalkenyl group, or a C.sub.7-C.sub.14
alkylaryl group;
[0022] or, R.sup.13 is represented by the formula: 6
[0023] wherein: R.sup.17 to R.sup.24 are as defined for R.sup.1 and
R.sup.2, or two or more adjacent radicals R.sup.1 to R.sup.24,
including R.sup.20 and R.sup.21, together with the atoms connecting
them form one or more rings; preferably, R.sup.17 to R.sup.24 are
hydrogen;
[0024] M.sup.2 is one or more carbons, silicon, germanium or tin,
preferably silicon;
[0025] R.sup.13 may also be an amidoborane-type radical such as is
described in WO00/20426 (herein fully incorporated by
reference);
[0026] R.sup.8, R.sup.10 and R.sup.12 are identical or different
and have the meanings stated for R.sup.4to R.sup.7; and
[0027] R.sup.9 and R.sup.11 are identical or different and are a
Group IVA radical having from 1 to 20 carbon atoms or are each
primary, secondary or tertiary butyl groups, aryl groups, isopropyl
groups, fluoroalikyl groups, trialkyl silyl groups, or other groups
of similar size, preferably a tertiary butyl group.
[0028] In another embodiment, the metallocenes of the present
invention are represented by the formula: 7
[0029] wherein: M.sup.1 is selected from the group consisting of
titanium, zirconium, hafnium, vanadium, niobium, tantalum,
chromium, molybdenurn and tungsten;
[0030] R.sup.1 and R.sup.2 are identical or different, and are one
of 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.2-C.sub.40 alkenyl group, a C.sub.7-C.sub.40 arylalkyl group,
a C.sub.7-C.sub.40 atkylaryl group, a C.sub.8-C.sub.40 arylalkenyl
group, an OH group or a halogen atom, or a conjugated diene which
is optionally substituted with one or more hydrocarbyl,
tri(hydrocarbyl)silyl groups or hydrocarbyl,
tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30
atoms not counting hydrogen;
[0031] R.sup.3 are identical or different and are each a halogen
atom, a C.sub.3-C.sub.10 alkyl group which may be halogenated, a
C.sub.6-C.sub.10 aryl group which may be halogenated, 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, a --NR'.sub.2,--SR', --OR', --OSiR'.sub.3 or --PR'.sub.2
radical, wherein R' is one of a halogen atom, a C.sub.1-C.sub.10
alkyl group, or a C.sub.6-C.sub.10 aryl group;
[0032] R.sup.4 to R.sup.7 are identical or different and are
hydrogen, as defined for R.sup.3 or two or more adjacent radicals
R.sup.5 to R.sup.7 together with the atoms connecting them form one
or more rings; 8
[0033] --B(R.sup.14)--, --Al(R.sup.14)--, --Ge--, --Sn--, --O--,
--S--, --SO--, --SO.sub.2--, --N(R.sup.14)--, --CO--,
--P(R.sup.14)--, or --P(O)(R.sup.14)--, or an amidoborane
radical;
[0034] wherein: R.sup.14, R.sup.15and R.sup.16 are identical or
different and are a hydrogen atom, a halogen atom, a
C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 fluoroalkyl or
silaalkyl group, a C.sub.6-C.sub.30 aryl group, a C.sub.6-C.sub.30
fluoroaryl group, a C.sub.1-C.sub.20 alkoxy group, a
C.sub.2-C.sub.20 alkenyl group, a C.sub.7-C.sub.40 arylalkyl group,
a C.sub.8-C.sub.40 arylalkenyl group, a C.sub.7-C.sub.40 alkylaryl
group, or R.sup.14 and R.sup.15, together with the atoms binding
them, form a cyclic ring;
[0035] or, R.sup.13 is represented by the formula: 9
[0036] wherein: R.sup.17 to R.sup.24 are as defined for R.sup.1 and
R.sup.2, or two or more adjacent radicals R.sup.17 to R.sup.24,
including R.sup.20 and R.sup.2 1, together with the atoms
connecting them form one or more rings;
[0037] M.sup.2 is one or more carbons, silicon, germanium or
tin;
[0038] R.sup.8, R.sup.10 and R.sup.12 are identical or different
and have the meanings stated for R.sup.4 to R.sup.7; and
[0039] R.sup.9 and R.sup.11 are identical or different and are each
a Group IVA radical having from 2 to 20 carbon atoms or are each a
primary, secondary or tertiary butyl group, an aryl group, an
isopropyl group, trialkyl sityl group, or a fluoroalkyl group
[0040] In another embodiment the metallocenes of this invention are
represented by the formula: 10
[0041] wherein: M.sup.1 is selected from the group consisting of
titanium, zirconium, hafnium, vanadium, niobium, tantalum,
chromium, molybdenum and tungsten;
[0042] R.sup.1 and R.sup.2 are identical or different, and are one
of 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.2-C.sub.40 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, or a conjugated diene which
is optionally substituted with one or more hydrocarbyl,
tri(hydrocarbyl)silyl groups or hydrocarbyl,
tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30
atoms not counting hydrogen;
[0043] R.sup.3 are identical or different and are each 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 which may be
halogenated, 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.8C.sub.40 arylalkenyl group, a --NR'.sub.2,--SR',
--OR', --OSiR'.sub.3 or --PR'.sub.2 radical, wherein: R' is one of
a halogen atom, a C.sub.1-C.sub.10 alkyl group, or a
C.sub.6-C.sub.10 aryl group;
[0044] R.sup.4 to R.sup.7 are identical or different and are
hydrogen, as defined for R.sup.3 or two or more adjacent radicals
R.sup.5 to R.sup.7 together with the atoms connecting them form one
or more rings; 11
[0045] --B(R.sup.14)--, --Al(R.sup.14)--, --Ge--, --Sn--, --O--,
--S--, --SO--, --SO.sub.2--, --N(R.sup.14)--, --CO--,
--P(R.sup.14)--, or --P(O)(R.sup.14)--, or an amidoborane
radical;
[0046] wherein: R.sup.14, R.sup.15and R.sup.16 are identical or
different and are a hydrogen atom, a halogen atom, a
C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 fluoroalkyl or
silaalkyl group, a C.sub.6-C.sub.30 aryl group, a C.sub.6-C.sub.30
fluoroaryl group, a C.sub.1-C.sub.20 alkoxy group, a
C.sub.2-C.sub.20 alkenyl group, a C.sub.7-C.sub.40 arylalkyl group,
a C.sub.8-C.sub.40 arylalkenyl group, a C.sub.7-C.sub.40 alkylaryl
group, or R.sup.14 and R.sup.15, together with the atoms binding
them, form a cyclic ring;
[0047] or, R.sup.13 is represented by the formula: 12
[0048] wherein: R.sup.17 to R.sup.24 are as defined for R.sup.1 and
R.sup.2, or two or more adjacent radicals R.sup.17 to R.sup.24,
including R.sup.20 and R.sup.21, together with the atoms connecting
them form one or more rings;
[0049] M.sup.2 is one or more carbons, silicon, germanium or
tin;
[0050] R.sup.8, R.sup.10 and R.sup.12 are identical or different
and have the meanings stated for R.sup.4 to R.sup.7; and
[0051] R.sup.9 and R.sup.11 are identical or different and are each
primary, secondary or tertiary butyl groups.
[0052] In another embodiment the metallocenes of this invention are
represented by the formula: 13
[0053] wherein: M.sup.1 is selected from the group consisting of
titanium, zirconium, hafnium, vanadium, niobium, tantalum,
chromium, molybdenum and tungsten;
[0054] R.sup.1 and R.sup.2 are identical or different and are one
of 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.2-C.sub.40 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, or a conjugated diene which
is optionally substituted with one or more hydrocarbyl,
tri(hydrocarbyl)silyl groups or hydrocarbyl,
tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30
atoms not counting hydrogen;
[0055] R.sup.3 are identical and are each a C.sub.1 or C.sub.2
alkyl group, a C.sub.3 alkyl group or a C.sub.4-C.sub.10 alkyl
group;
[0056] R.sup.4 to R.sup.7 are identical or different and are
hydrogen, as defined for R.sup.3 or two or more adjacent radicals
R.sup.5 to R.sup.7 together with the atoms connecting them form one
or more rings; 14
[0057] --B(R.sup.14)--, --Al(.sup.14)--, --Ge--, --Sn--, --O--,
--S--, --SO--, --SO.sub.2--, --N(R.sup.14)--, --CO--,
--P(R.sup.14)--, or --P(O)(R.sup.14)--, or an amidoborane
radical;
[0058] wherein: R.sup.14, R.sup.15 and R.sup.16 are identical or
different and are a hydrogen atom, a halogen atom, a
C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 fluoroalkyl or
silaalkyl group, a C.sub.6-C.sub.30 aryl group, a C.sub.6-C.sub.30
fluoroaryl group, a C.sub.1-C.sub.20 alkoxy group, a
C.sub.2-C.sub.20 alkenyl group, a C.sub.7-C.sub.40 arylalkyl group,
a C.sub.8-C.sub.40 arylalkenyl group, a C.sub.7-C.sub.40 alkylaryl
group, or R.sup.14 and R.sup.15, together with the atoms binding
them, form a cyclic ring;
[0059] or, R.sup.13 is represented by the formula: 15
[0060] wherein: R.sup.17 to R.sup.24 are as defined for R.sup.1 and
R.sup.2, or two or more adjacent radicals R.sup.17 to R.sup.24,
including R.sup.20 and R.sup.21, together with the atoms connecting
them form one or more rings;
[0061] M.sup.2 is one or more carbons, silicon, germanium or
tin;
[0062] R.sup.8, R.sup.10 and R.sup.12 are identical or different
and have the meanings stated for R.sup.4 to R.sup.7; and
[0063] R.sup.9 and R.sup.11 are identical or different and are each
primary, secondary or tertiary butyl groups.
[0064] In another embodiment the metallocenes of this invention are
represented by the formula: 16
[0065] wherein: M.sup.1 is selected from the group consisting of
titanium, zirconium, hafnium, vanadium, niobium, tantalum,
chromium, molybdenum and tungsten;
[0066] R.sup.1 and R.sup.2 are identical or different, and are one
of 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.2-C.sub.40 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, or a conjugated diene which
is optionally substituted with one or more hydrocarbyl,
tri(hydrocarbyl)silyl groups or hydrocarbyl,
tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30
atoms not counting hydrogen;
[0067] R.sup.3 are identical or different and are each 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 which may be
halogenated, 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, a --NR.sub.2.sup.15)
--SR.sup.15, --OR.sup.15, --OSiR.sub.3.sup.15 or --PR.sub.2.sup.15
radical, wherein: R.sup.15 is one of a halogen atom, a
C.sub.1-C.sub.10 alkyl group, or a C.sub.6-C.sub.10 aryl group;
[0068] R.sup.4 to R.sup.7 are identical or different and are
hydrogen, as defined for R.sup.3 or two or more adjacent radicals
R.sup.5 to R.sup.7 together with the atoms connecting them form one
or more rings;
[0069] R.sup.13 is represented by the formula: 17
[0070] wherein: R.sup.17 to R.sup.24 are as defined for R.sup.1 and
R.sup.2, or two or more adjacent radicals R.sup.17 to R.sup.24,
including R.sup.20 and R.sup.21, together with the atoms connecting
them form one or more rings;
[0071] M.sup.2 is one or more carbons, silicon, germanium or
tin;
[0072] R.sup.8, R.sup.10 and R.sup.12 are identical or different
and have the meanings stated for R.sup.4 to R.sup.7; and
[0073] R.sup.9 an d R.sup.24 are identical or different and ar e
each a Group IVA radical having from 1 to 20 carbon atoms, a
primary, secondary or tertiary butyl group, an aryl group, an
isopropyl group, trialkyl silyl group, or a fluoroalkyl group.
[0074] In another embodiment the metallocenes of this invention are
represented by the formula: 18
[0075] wherein: M.sup.1 is selected from the group consisting of
titanium, zirconium, hafnium, vanadium, niobium, tantalum,
chromium, molybdenum and tungsten;
[0076] R.sup.1 and R.sup.2 are identical or different, and are one
of 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 arIloxy group, a C.sub.2-C.sub.10 alkenyl group, a
C.sub.2-C.sub.40 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, or a conjugated diene which
is optionally substituted with one or more hydrocarbyl,
tri(hydrocarbyl)silyl groups or hydrocarbyl,
tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30
atoms not counting hydrogen;
[0077] R.sup.3 are identical and are each a C.sub.1-C.sub.4 alkyl
group;
[0078] R.sup.4 to R.sup.7 are identical or different and are
hydrogen, as defined for R.sup.3 or two or more adjacent radicals
R.sup.5 to R.sup.7 together with the atoms connecting them form one
or more rings;
[0079] R.sup.13 is represented by the formula: 19
[0080] wherein: R.sup.17 to R.sup.24 are as defined for R.sup.1 and
R.sup.2, or two or more adjacent radicals R.sup.17 to R.sup.24,
including R.sup.20 and R.sup.21, together with the atoms connecting
them form one or more rings;
[0081] M.sup.2 is carbon, silicon, germanium or tin;
[0082] R.sup.8, R.sup.10 and R.sup.12 are identical or different
and have the meanings stated for R.sup.4 to R.sup.7; and
[0083] R.sup.9 and R.sup.11 are identical or different and are each
primary, secondary or tertiary butyl groups.
[0084] As utilized herein, the term "alkyl", alone or in
combination, means a straight-chain or branched-chain alkyl
radical. Examples of such radicals include, but are not limited to,
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, pentyl, iso-amyl, hexyl, octyl and the like. The term
"alkenyl" means a straight-chain or branched-chain hydrocarbon
radial having one or more double bonds. Examples of suitable
alkenyl radicals include, but are not limited to, ethenyl,
propenyl, allyl, 1,4-butadienyl and the like. The term "alkoxy"
means an alkyl ether radical wherein the term alkyl is as defined
above. Examples of suitable alkyl ether radicals include, but are
not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
iso-butoxy, sec-butoxy, tert-butoxy and the like. The term "aryl"
means a phenyl, azulenyl, or naphthyl radical and the like which
optionally contains a heteroatom and/or carries one or more
substituents, for example, alkyl, alkoxy, halogen, hydroxy, amino,
nitro, etc.
[0085] The following are particularly preferred metallocenes:
[0086]
rac-dimethylsiladiyl(2-methyl,4-[3',5'-di-tbutylphenyl]indenyl).sub-
.2zirconium dichloride;
[0087]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl).sub.-
2zirconium dichloride;
[0088]
rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-di-tbutylphenyl]indenyl).s-
ub.2zirconium dichloride;
[0089]
rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2zirconium dichloride;
[0090]
rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-di-tbutylphenyl]indenyl).su-
b.2zirconium dichloride;
[0091]
rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2zirconium dichloride;
[0092]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2zirconium dichloride;
[0093]
rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2zirconium dichloride;
[0094]
rac-dimethylsiladiyl(2-methyl,4-[3',5'-di-tbutylphenyl]indenyl).sub-
.2hafnium dichloride;
[0095]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl).sub.-
2hafnium dichloride;
[0096] rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-di-tbutylphenyl]
indenyl).sub.2haffnium
[0097]
rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2hafnium dichloride;
[0098]
rac-dimethylsiladiyl(2-butyl,4-[3',5'-di-tbutylphenyl]indenyl).sub.-
2hafnium dichloride;
[0099]
rac-9-silafluorendiyl(2-methyl,4-[3',5'-di-tbutylphenyl]indenyl).su-
b.2zirconium dichloride;
[0100]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl).sub-
.2zirconium dichloride;
[0101]
rac-9-sitafluorendiyl(2-n-propyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2zirconium dichloride;
[0102]
rac-9-sitafluorendiyl(2-iso-propyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2zirconium dichloride;
[0103]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-di-tbutylphenyl]indenyl).s-
ub.2zirconium dichloride;
[0104] rac-9-silafluorendiyl(2-iso-butyl,4-[3',5
'-di-tbutylphenyl]indenyl- ).sub.2zirconium dichloride;
[0105]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2zirconium dichloride;
[0106]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2zirconium dichloride;
[0107]
rac-9-silafluorendiyl(2-methyl,4-[3',5'-di-tbutylphenyl]indenyl).su-
b.2hafnium dichloride;
[0108]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl).sub-
.2hafnium dichloride;
[0109]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2hafnium dichloride;
[0110]
rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-di-tbutylpheny]indenyl)-
.sub.2hafnium dichloride;
[0111]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-di-tbutylphenyl]indenyl).s-
ub.2hafnium dichloride;
[0112]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2hafnium dichloride;
[0113]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2hafnium dichloride;
[0114]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2hafnium dichloride;
[0115]
rac-dimethylsiladiyl(2-methyl,4-[3',5'-di-tbutylphenyl]indenyl).sub-
.2zirconium dimethyl;
[0116]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl).sub.-
2zirconium dimethyl;
[0117]
rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-di-tbutylphenyl]indenyl).s-
ub.2zirconium dimethyl;
[0118]
rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2zirconium dimethyl;
[0119] rac-dimethylsiladiyl(2-n-butyl,4-[3',5
'-di-tbutylphenyl]indenyl).s- ub.2zirconium dimethyl;
[0120]
rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2zirconium dimethyl;
[0121]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2zirconium dimethyl;
[0122] rac-dimethylsiladivl(2-teft-but 1,
4-[3',5'-di-tbutylphenyl]indenyl- ).sub.2zirconium dimethyl;
[0123]
rac-dimethylsiladiyl(2-methyl,4-[3',5'-di-tbutylphenlyl]indenyl).su-
b.2hafnium dimethyl,
[0124]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-di-butylhenyl]indenyl).sub.2h-
afnium dimethyl;
[0125]
rac-dimethylsiladiyl(2n-propyl,4-[3',5'-di-tbutylphenyl]indenyl).su-
b.2hafnium dimethyl
[0126]
rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2hafnium dimethyl;
[0127]
rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-di-tbutylpheny]indenyl).sub-
.2hafnium dimethyl;
[0128]
rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2hafnium dimethyl;
[0129]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2hafnium dimethyl;
[0130]
rac-dimethylsiladiyl(2-teit-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2hafnium dimethyl;
[0131]
rac-9-silafluorendiyl(2-methyl,4-[3',5'-di-tbutylphenyl]indenyl).su-
b.2zirconium dimethyl;
[0132]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl).sub-
.2zirconium dimethyl;
[0133]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2zirconium dimethyl,
[0134]
rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2zirconium dimethyl;
[0135]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-di-tbutylphenyl]indenyl).s-
ub.2zirconium dimethyl;
[0136]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2zirconium dimethyl;
[0137]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2zirconium dimethyl;
[0138]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2zirconium dimethyl;
[0139]
rac-9-silafluorendiyl(2-methyl,4-[3',5'-di-tbutylphenyl]indenyl).su-
b.2hafnium dimethyl;
[0140]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl).sub-
.2hafnium dimethyl;
[0141]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2hafnium dimethyl;
[0142]
rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2hafnium dimethyl;
[0143]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-di-tbutylphenyl]indenyl).s-
ub.2hafnium dimethyl;
[0144]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2hafnium dimethyl;
[0145]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2hafnium dimethyl;
[0146]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2hafnium dimethyl;
[0147]
rac-dimethylsiladiyl(2-methyl,4-[3',5'-bis-trifluoromethylphenyl]in-
denyl).sub.2zirconium dichloride;
[0148] rac-dimethylsiladiyl(2-ethyl,4-[3',5'-bis
-trifluoromethylphenyl]in- denyl).sub.2zirconium dichloride;
[0149] rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0150] rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0151] rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]- indenyl).sub.2zirconium dichloride;
[0152] rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0153] rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0154] rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-bis
-tri'fluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0155]
rac-dimethylsiladiyl(2-methyl,4-[3',5'-bis-trifluoromethylphenyl]in-
denyl) .sub.2hafnium dichloride;
[0156] rac-dimethylsiladiyl(2-ethyl,4-[3',5
'-bis-trifluoromethylphenyl]in- denyl).sub.2hafnium dichloride;
[0157] rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dichloride;
[0158] rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dichloride;
[0159] rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]- indenyl).sub.2hafnium dichloride;
[0160] rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dichloride;
[0161] rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dichloride;
[0162] rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dichloride;
[0163] rac-9-silafluorendiyl(2-methyl,4-[3',5'-bis
-trifluoromethylphenyl]- indenyl).sub.2zirconium dichloride;
[0164] rac-dimethylsiladiyl(2-ethyl,4[3',5'-bis-
trifluoromethylphenyl]ind- enyl).sub.2hafnium dichloride;
[0165] rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0166] rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0167] rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0168] rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0169] rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0170] rac-9-sitafluorendiyl(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0171]
rac-9-silafluorendiyl(2-methyl,4-[3',5'-bis-trifluoromethylphenyl]i-
ndenyl) .sub.2hafnium dichloride;
[0172]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-bis-trifuoromethylphenyl]ind-
enyl).sub.2hafnium dichloride;
[0173] rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-bis-
trifluoromethylphenyl]indenyl).sub.2hafnium dichloride;
[0174] rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-bis-
trifluoromethylphenyl]indenyl).sub.2hafnium dichloride;
[0175] rac-9-silafluorendiyl(2-n-butyl,4[3',5'-bis
-trifluoromethylphenyl]- indenyl).sub.2hafnium dichloride;
[0176] rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dichloride;
[0177] rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dichloride;
[0178] rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dichloride;
[0179] rac-dimethylsiladiyl(2-methyl,4-[3',5'-bis
-trifluoromethylphenyl]i- ndenyl).sub.2zirconium dimethyl;
[0180] rac-dimethylsiladiyl(2-ethyl,4-[3',5'-bis
-trifluoromethylphenyl]in- denyl).sub.2zirconium dimethyl;
[0181] rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0182] rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0183] rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]- indenyl).sub.2zirconium dimethyl;
[0184] rac-dimethylsiladiyl(2-iso-butyL 4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0185] rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0186] rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0187]
rac-dimethylsiladiyl(2-methyl,4-[3',5'-bis-trifluoromethylphenyl]in-
denyl) .sub.2hafnium dimethyl;
[0188]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-bis-trifluoromethylphenyl]ind-
enyl).sub.2hafnium dimethyl;
[0189] rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dimethyl;
[0190] rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dimethyl;
[0191] rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]- indenyl).sub.2hafnium dimethyl;
[0192] rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dimethyl;
[0193] rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dimethyl;
[0194] rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dimethyl;
[0195] rac-9-silafluorendiyl(2-methyl,4-[3',5'-bis
-trifluoromethylphenyl]- indenyl).sub.2zirconium dimethyl;
[0196] rac-dimethylsiladiyl(2-ethyl,4-[3',5'-bis-
trifluoromethylphenyl]in- denyl).sub.2hafnium dimethyl;
[0197] rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0198] rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0199] rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0200] rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0201] rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0202] rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0203]
rac-9-silafluorendiyl(2-methyl,4-[3',5'-bis-trifluoromethylphenyl]i-
ndenyl) .sub.2hafnium dimethyl;
[0204]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-bis-trifluoromethylphenyl]in-
denyl).sub.2hafnium dimethyl;
[0205] rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-bis-
trifluoromethylphenyl]indenyl).sub.2 hafnium dimethyl;
[0206] rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-bis-
trifluoromethylphenyl]indenyl).sub.2hafnium dimethyl;
[0207] rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dimethyl;
[0208] rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dimethyl;
[0209] rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dimethyl;
[0210] rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2hafnium dimethyl;
[0211]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-di-iso-propylphenyl]indenyl).-
sub.2zirconium dichloride;
[0212]
rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-di-iso-propylphenyl]indeny-
l).sub.2zirconium dichloride
[0213]
rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2zirconium dichloride;
[0214]
rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-di-iso-propylphenyl]indenyl-
).sub.2zirconium dichloride;
[0215]
rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-di-iso-propylphenyl]inden-
yl).sub.2zirconium dichloride;
[0216]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-di-iso-propylphenyl]inden-
yl).sub.2zirconium dichloride;
[0217]
rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2zirconium dichloride;
[0218]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-di-iso-propylphenyl]indenyl).-
sub.2hafnium dichloride;
[0219]
rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-di-iso-propylphenyl]indeny-
l).sub.2hafnium dichloride;
[0220] rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-
iso-propylphenyl]indenyl).sub.2hafnium dichloride;
[0221] rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-di-
iso-propylphenyl]indeny- l).sub.2hafnium dichloride;
[0222] rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-di-
iso-propylphenyl]indenyl).sub.2hafnium dichloride;
[0223] rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-di-
iso-propylphenyl]indenyl).sub.2hafnium dichloride;
[0224] rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-di-
iso-propylphenyl]indenyl).sub.2hafnium dichloride;
[0225]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-iso-propylphenyl]indenyl)-
.sub.2zirconium dichloride;
[0226]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-di-iso-propylphenyl]inden-
yl).sub.2zirconium dichloride;
[0227]
rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-di-iso-propylphenyl]ind-
enyl).sub.2zirconium dichloride;
[0228]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-di-iso-propylphenyl]indeny-
l).sub.2zirconium dichloride;
[0229]
rac-9-silafluorendiyl(2-isobutyl,4-[3',5'-di-iso-propylphenyl]inden-
yl).sub.2zirconium dichloride;
[0230]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2zirconium dichloride;
[0231]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-di-iso-propylphenyl]ind-
enyl).sub.2zirconium dichloride;
[0232]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-iso-propylphenyl]indenyl)-
.sub.2hafnium dichiloride-,
[0233]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-di-iso-propylphenyl]inden-
yl).sub.2hafnium dichloride;
[0234]
rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-di-iso-propylphenyl]ind-
enyl).sub.2hafnium dichlorde;
[0235] rac-9-silafluorendiyl(2-n-buty,
4-[3')5'-di-iso-propylphenyl]indeny- l).sub.2hafnium
dichloride;
[0236]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2hafnium dichloride;
[0237]
rac-9-silafluorendiy.(2-sec-butyl,4-3',5'-di-iso-propylphenyl]inden-
yl).sub.2hafrnum dichloride;
[0238]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-di-iso-propylphenyl]ind-
enyl).sub.2hafnium dichloride;
[0239]
rac-dimethylsihldiyl(2-ethyl,4-[3',5'-di-iso-propylphenyl]indenyl).-
sub.2zirconium dimethyl;
[0240]
rac-dimethylsildiyl(2-ni-propyl,4-[3',5'-di-iso-propylphenyl]indeny-
l).sub.2zirconium dimethyl
[0241]
rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2Zirconium dimethyl;
[0242]
rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-di-iso-propylphenyl]indenyl-
).sub.2zirconium dimethyl;
[0243]
rac-dimethylsiladiyl(2-isobutyl,4-[3',5'-di-iso-propylphenyl]indeny-
l).sub.2zirconium dimethyl;
[0244]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-di-iso-propylphenyl]inden-
yl).sub.2zirconium dimethyl;
[0245] rac-dimethylsiladiyl(2-tert-buty
4-[3',5'-di-iso-propylphenyl]inden- yl).sub.2zirconium
dimethyl;
[0246]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-di-iso-propylphenyl]indenyl).-
sub.2hafnium dimethyl;
[0247] rac-dimethylsiladiyl(2-n-propyl,4-[3',5 '-di- iso-propy
lphenyl] indenyl).sub.2hafnium dimethyl;
[0248] rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-
iso-propylphenyl]indenyl).sub.2hafnium dimethyl;
[0249] rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-di-
iso-propylphenyl]indeny- l).sub.2hafnium dimethyl;
[0250]
rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-di-iso-propylphenyl]inden-
yl).sub.2zirconium dimethyl;
[0251]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-di-iso-propylphenyl]inden-
yl).sub.2zirconium dimethyl;
[0252]
rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2zirconium dimethyl;
[0253]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-iso-propylphenyl]indenyl)-
.sub.2zirconium dimethyl;
[0254]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-di-iso-propylphenyl]inden-
yl).sub.2zirconium dimethyl;
[0255]
rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-di-iso-propylphenyl]ind-
enyl).sub.2zirconium dimethyl;
[0256]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-di-iso-propylphenyl]indeny-
l).sub.2zirconium dimethyl;
[0257]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2zirconium dimethyl;
[0258]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2zirconium dimethyl;
[0259]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-di-iso-propylphenyl]ind-
enyl).sub.2zirconium dimethyl;
[0260]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-iso-propylphenyl]indenyl)-
.sub.2hafnium dimethyl;
[0261]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-di-iso-propylphenyl]inden-
yl).sub.2hafnium dimethyl;
[0262]
rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-di-iso-propylphenyl]ind-
enyl).sub.2hafnium dimethyl;
[0263] rac-9-silafluorendiyl(2-n-butyl,4-[3
','-di-iso-propylphenyl]indeny- l).sub.2hafnium dimethyl;
[0264]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-di-iso-propylphenyli]nde-
nyl).sub.2hafnium dimethyl;
[0265]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2hafnium dimethyl;
[0266]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-di-iso-propylphenyl]ind-
enyl)hafnium dimethyl;
[0267] rac-dimethylsiladiyl(2-methyt,
4-[3',5'-di-phenylphenyl]indenyl).su- b.2zirconium dichloride;
[0268]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-di-phenylphenyl]indenyl).sub.-
2zirconium dichloride;
[0269]
rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-di-phenylphenyl]indenyl).s-
ub.2zirconium dichloride;
[0270]
rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2zirconium dichloride;
[0271]
rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-di-phenylphenyl]indenyl).su-
b.2zirconium dichloride;
[0272]
rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2zirconium dichloride;
[0273]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2zirconium dichloride;
[0274]
rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2zirconium dichloride;
[0275]
rac-dimethylsiladiyl(2-methyl,4-[3',5'-di-phenylphenyl]indenyl).sub-
.2hafnium dichloride;
[0276]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-di-phenylphenyl]indenyl).sub.-
2hafnium dichloride;
[0277]
rac-dimethylsiladiyl(2-n-propyl,4-[3',.sup.5'-di-phenylphenyl]inden-
yl).sub.2hafnium dichloride;
[0278]
rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2hafnium dichloride;
[0279]
rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-di-phenylphenyl]indenyl).su-
b.2hafnium dichloride;
[0280]
rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2hafnium dichloride;
[0281]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',.sup.5'-di-phenylphenyl]inde-
nyl).sub.2hafnium dichloride;
[0282]
rac-dimethylsiladiyl(2-tert-butyl,4-[3',.sup.5'-di-phenylphenyl]ind-
enyl).sub.2hafnium dichloride;
[0283]
rac-9-silafluorendiyl(2-methyl,4-[3',5'-di-phenylphenyl]indenyl).su-
b.2zirconium dichloride;
[0284]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-phenylphenyl]indenyl).sub-
.2zirconium dichloride;
[0285]
rac-9-silafluorendiyl(2-n-propyl,4-[3',.sup.5'-di-phenylphenyl]inde-
nyl).sub.2zirconium dichloride;
[0286] rac-9-silafluorendiyl(2-iso-propyl,
.sup.4-[.sup.3',.sup.5'-di-phen- ylphenyl]indenyl).sub.2zirconium
dichloride;
[0287]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-di-phenylphenyl]indenyl).s-
ub.2zirconium dichloride;
[0288]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2zirconium dichloride;
[0289]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2zirconium dichloride;
[0290]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',.sup.5'-di-phenylphenyl]in-
denyl).sub.2zirconium dichloride;
[0291]
rac-9-silafluorendiyl(2-methyl,4-[3',.sup.5'-di-phenylphenyl]indeny-
l).sub.2hafnium dichloride;
[0292]
rac-9-silafluorendiyl(2-ethyl,4-[3',.sup.5'-di-phenylphenyl]indenyl-
).sub.2hafnium dichloride;
[0293]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2hafnium dichloride;
[0294]
rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-di-phenylphenyl]indenyl-
).sub.2hafnium dichloride;
[0295]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-di-phenylphenyl]indenyl).s-
ub.2hafnium dichloride;
[0296]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2hafnium dichloride;
[0297]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2hafnium dichloride;
[0298]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-di-phenylphenyl]indenyl-
).sub.2hafnium dichloride;
[0299]
rac-dimethylsiladiyl(2-methyl,4-[3',.sup.5'-di-phenylphenyl]indenyl-
).sub.2zirconium dimethyl;
[0300]
rac-dimethylsiladiyl(2-ethyl,4-[3',.sup.5'-di-phenylphenyl]indenyl)-
.sub.2zirconium dimethyl;
[0301]
rac-dimethylsiladiyl(2-n-propyl,4-[3',.sup.5'-di-phenylphenyl]inden-
yl).sub.2zirconium dimethyl;
[0302]
rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2zirconium dimethyl;
[0303] rac-dimethylsiladiyl(2-n-butyl,
.sup.4-[.sup.3',.sup.5'-di-phenylph- enyl]indenyl).sub.2zirconium
dimethyl;
[0304]
rac-dimethylsiladiyl(2-iso-butyl,4-[3',.sup.5'-di-phenylphenyl]inde-
nyl).sub.2zirconium dimethyl;
[0305]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2zirconium dimethyl;
[0306]
rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2zirconium dimethyl;
[0307]
rac-dimethylsiladiyl(2-methyl,4-[3',5'-di-phenylphenyl]indenyl).sub-
.2hafnium dimethyl;
[0308]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-di-phenylphenyl]indenyl).sub.-
2hafnium dimethyl;
[0309]
rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-di-phenylphenyl]indenyl).s-
ub.2hafnium dimethyl;
[0310]
rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2hafnium dimethyl;
[0311]
rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-di-phenylphenyl]indenyl).su-
b.2hafnium dimethyl;
[0312]
rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2hafnium dimethyl;
[0313]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2hafnium dimethyl;
[0314] rac-dimethylsiladiyl(2-tert-butyl,4-[3',5
'-di-phenylphenyl]indenyl- ).sub.2hafnium dimethyl;
[0315]
rac-9-silafluorendiyl(2-methyl,4-[3',5'-di-phenylphenyl]indenyl).su-
b.2zirconium dimethyl;
[0316]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-phenylphenyl]indenyl).sub-
.2zirconium dimethyl;
[0317]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2zirconium dimethyl;
[0318] rac-9-si1afluorendiyl(2-iso-propy1,
4-[3',5'-di-phenylphenyl] indenyl).sub.2zirconium dimethyl;
[0319]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-di-phenylphenyl]indenyl).s-
ub.2zirconium dimethyl;
[0320]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2zirconium dimethyl;
[0321]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2zirconium dimethyl;
[0322]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-di-phenylphenyl]indenyl-
).sub.2zirconium dimethyl;
[0323]
rac-9-silafluorendiyl(2-methyl,4-[3',5'-di-phenylphenyl]indenyl).su-
b.2hafnium dimethyl;
[0324]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-phenylphenyl]indenyl).sub-
.2hafnium dichloride;
[0325]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2hafnium dimethyl;
[0326]
rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-di-phenylphenyl]indenyl-
).sub.2hafnium dimethyl;
[0327]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-di-phenylphenyl]indenyl).s-
ub.2hafnium dimethyl;
[0328]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2hafnium dimethyl;
[0329]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2haffium dimethyl;
[0330] rac-9-silafluorendiyl(2-tert-butyl,4-[3 ',
.sup.5'-di-phenylphenyl]- indenyl).sub.2hafnium dimethyl;
[0331]
rac-dimethylsiladiyl(2-methyl,4-[3',5'-di-tbutylphenyl]indenyl).sub-
.2.eta..sup.4-1,4-diphenyl -1,3-butadiene;
[0332]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl).sub.-
2.eta..sup.4-1,4-diphenyl -1,3-butadiene;
[0333]
rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-di-tbutylphenyl]indenyl).s-
ub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0334]
rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0335]
rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-di-tbutylphenyl]indenyl).su-
b.2.eta..sup.4-1,4-diphenyl -1,3-butadiene;
[0336]
rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0337]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0338]
rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0339]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-bis-trifluoromethylphenyl]ind-
enyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0340]
rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-bis-trifluoromethylphenyl]-
indenyl).sub.2.eta..sup.4-1,4-1,4-diphenyl-1,3-butadiene;
[0341] rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-bis-
trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadien-
e;
[0342]
rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-bis-trifluoromethylphenyl]i-
ndenyl).sub.2.eta..sup.4-1,4-diphenyl-1 ,3-butadiene;
[0343]
rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-bis-trifluoromethylphenyl-
]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0344]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',.sup.5'-bis-trifluoromethylp-
henyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0345]
rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-bis-trifluoromethylpheny-
l]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0346]
rac-dimethylsiladiyl(2-ethyl,4-[3',5'-di-iso-propylphenyl]indenyl).-
sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0347]
rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-di-iso-propylphenyl]indeny-
l).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0348]
rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2.eta..sup.4-1,4-diphenyl-1 ,3-butadiene;
[0349]
rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-di-iso-propylphenyl]indenyl-
).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0350]
rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-di-iso-propylphenyl]inden-
Yl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0351]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',S'-di-iso-propylphenyl]inden-
yl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0352]
rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0353]
rac-dimethylsiladiyl(2-methyl,4-[3',5'-di-phenylphenyl]indenyl).sub-
.2.eta..sup.4-1,4-diphenyl -1,3-butadiene;
[0354]
rac-dimethylsiladiyl(2-ethyl,4-[3',5.sup.t-di-phenylphenyl]indeny
).sub.2'.sup.4-1,4-diphenyl -1,3-butadiene;
[0355]
rac-dimethylsiladiyl(2-n-propyl,4-[3',5'-di-phenylphenyl]indenyl).s-
ub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0356]
rac-dimethylsiladiyl(2-iso-propyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0357]
rac-dimethylsiladiyl(2-n-butyl,4-[3',5'-di-phenylphenyl]indenyl).su-
b.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0358]
rac-dimethylsiladiyl(2-iso-butyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0359]
rac-dimethylsiladiyl(2-sec-butyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0360]
rac-dimethylsiladiyl(2-tert-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0361]
rac-9-silafluorendiyl(2-methyl,4-[3',5'-di-tbutylphenyl]indenyl).su-
b.2.eta..sup.4-1,4-diphenyl -1,3-butadiene;
[0362]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl).sub-
.2.eta..sup.4-1,4-diphenyl -1,3-butadiene;
[0363]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0364]
rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0365]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-di-tbutylphenyt]indenyl).s-
ub.2.eta..sup.4-1,4-diphenyl -1,3-butadiene;
[0366]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0367]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0368]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0369] rac-9-silafluorendiyl(2-ethyl,4-[3',5
'-bis-trifluoromethylphenyl]i-
ndenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0370]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-bis-trifluoromethylphenyl-
]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0371] rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-bis-
trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadien-
e;
[0372]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-bis-trifluoromethylphenyl]-
indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0373]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-bis-trifluoromethylpheny-
l]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0374]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-bis-trifluoromethylpheny-
l]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0375]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-bis-trifluoromethylphen-
yl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0376]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-iso-propylphenyl]indenyl)-
.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0377]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-di-iso-propylphenyl]inden-
yl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0378]
rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-di-iso-propylphenyl]ind-
enyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0379]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-di-iso-propylphenyl]indeny-
l).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0380]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0381]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0382]
rac-9-silafluorendiyl(2-tert-butyl,4-[3',5'-di-iso-propylphenyl]ind-
enyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0383] rac-9-silafluorendiyl(2-methyl,4-[3',5'-di- phen
ylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0384]
rac-9-silafluorendiyl(2-ethyl,4-[3',5'-di-phenylphenyl]indenyl).sub-
.2.eta..sup.4-1,4-diphenyl -1,3-butadiene;
[0385]
rac-9-silafluorendiyl(2-n-propyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0386]
rac-9-silafluorendiyl(2-iso-propyl,4-[3',5'-di-phenylphenyl]indenyl-
).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadienee;
[0387]
rac-9-silafluorendiyl(2-n-butyl,4-[3',5'-di-phenylphenyl]indenyl).s-
ub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0388]
rac-9-silafluorendiyl(2-iso-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0389]
rac-9-silafluorendiyl(2-sec-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0390] rac-9-silafluorendiyl(2-tert-butyl,4-[3',5
'-di-phenylphenyl]indeny-
l).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0391]
rac-dimethylamidoborane(2-methyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2zirconium dichloride;
[0392]
rac-dimethylamidoborane(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl).s-
ub.2zirconium dichloride;
[0393]
rac-dimethylamidoborane(2-n-propyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2zirconium dichloride;
[0394] rac-dimethylamidoborane(2-iso-propyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0395]
rac-dimethylamidoborane(2-n-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2zirconium dichloride;
[0396]
rac-dimethylamidoborane(2-iso-butyl,4-[3',5'-di-tbutylphenyl]indeny-
l).sub.2zirconium dichloride;
[0397]
rac-dimethylamidoborane(2-sec-butyl,4-[3',5'-di-tbutylphenyl]indeny-
l).sub.2zirconium dichloride;
[0398]
rac-dimethylamidoborane(2-tert-butyl,4-[3',5'-di-tbutylphenyl]inden-
yl).sub.2zirconium dichloride;
[0399] rac-dimethylamidoborane(2-ethyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0400] rac-dimethylamidoborane(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0401] rac-dimethylamidoborane(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0402] rac-dimethylamidoborane(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0403] rac-dimethylamidoborane(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0404] rac-dimethylamidoborane(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0405] rac-dimethylamidoborane(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0406]
rac-dimethylamidoborane(2-ethyl,4-[3',5'-di-iso-propylphenyl]indeny-
l).sub.2zirconium dichloride;
[0407] rac-dimethylamidoborane(2-n-propyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride
[0408] rac-dimethylamidoborane(2-iso-propyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0409] rac-dimethylamidoborane(2-n-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0410] rac-dimethylamidoborane(2-iso-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0411] rac-dimethylamidoborane(2-sec-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0412] rac-dimethylamidoborane(2-tert-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0413]
rac-dimethylamidoborane(2-methyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2zirconium dichloride;
[0414]
rac-dimethylamidoborane(2-ethyl,4-[3',5'-di-phenylphenyl]indenyl).s-
ub.2zirconium dichloride;
[0415] rac-dimethylamidoborane(2-n-propyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0416] rac-dimethylamidoborane(2-iso-propyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0417]
rac-dimethylamidoborane(2-n-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2zirconium dichloride;
[0418] rac-dimethylamidoborane(2-iso-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0419] rac-dimethylamidoborane(2-sec-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0420] rac-dimethylamidoborane(2-tert-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0421]
rac-dimethylamidoborane(2-methyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0422]
rac-dimethylamidoborane(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl).s-
ub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0423]
rac-dimethylamidoborane(2-n-propyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0424]
rac-dimethylamidoborane(2-iso-propyl,4-[3',5'-di-tbutylphenyl]inden-
yl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0425] rac-dirmethylamidoborane(2-n-buty1,
4-[3',5'-di-tbutylphenyl]indeny-
l).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0426]
rac-dimethylamidoborane(2-iso-butyl,4-[3',5'-di-tbutylphenyl]indeny-
l).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0427]
rac-dimethylamidoborane(2-sec-butyl,4-[3',5'-di-tbutylphenyl]indeny-
l).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0428] rac-dimethylamidoborane(2-tert-butyl,4-[3',5
'-di-tbutylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0429] rac-dimethylamidoborane(2-ethyl,4-[3',5'-b
is-ttifluoromethylphenyl-
]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0430]
rac-dimethylamidoborane(2-n-propyl,4-[3',5'-bis-trifluoromethylphen-
yl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0431] rac-dimethylamidoborane(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0432]
rac-dimethylamidoborane(2-n-butyl,4-[3',5'-bis-trifluoromethylpheny-
l]indenyl) .sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0433]
rac-dimethylamidoborane(2-iso-butyl,4-[3',5'-bis-trifluoromethylphe-
nyl]indenyl).sub.2.eta..sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0434]
rac-dimethylamidoborane(2-sec-butyl,4-[3',5'-bis-trifluoromethylphe-
nyl]indenyl).sub.2.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0435] rac-dimethylamidoborane(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0436]
rac-dimethylamidoborane(2-ethyl,4-[3',5'-di-iso-propylphenyl]indeny-
l).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0437]
rac-dimethylamidoborane(2-n-propyl,4-[3',5'-di-iso-propylphenyl]ind-
enyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene,
[0438] rac-dimethylamidoborane(2-iso-propyl,4-[3',5'-di-iso
propylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0439]
rac-dimethylamidoborane(2-n-butyl,4-[3',5'-di-iso-propylphenyl]inde-
nyl).sub.2.theta..sup.4-1,4-diphenyl-1,3-butadiene;
[0440]
rac-dimethylamidoborane(2-iso-butyl,4-[3',5'-di-iso-propylphenyl]in-
denyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0441]
rac-dimethylamidoborane(2-sec-butyl,4-[3',5'-di-iso-propylphenyt]in-
denyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0442]
rac-dimethylamidoborane(2-tert-butyl,4-[3',5'-di-iso-propylphenyl]i-
ndenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0443]
rac-dimethylamidoborane(2-methyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2.eta..sup.4-1,4-diphenyl 1,3-butadiene;
[0444]
rac-dimethylamidoborane(2-ethyl,4-[3',5'-di-phenylphenyl]indeny
).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0445]
rac-dimethylamidoborane(2-n-propyl,4-[3',5'-di-phenylphenyl]indenyl-
).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0446]
rac-dimethylamidoborane(2-iso-propyl,4-[3',5'-di-phenylphenyl]inden-
yl).sub.2 114_ 1,4-diphenyl-1,3-butadiene;
[0447]
rac-dimethylamidoborane(2-n-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0448] rac-dimethylamidoborane(2-iso-butyl,4-[
3',5'-di-phenylphenyl]inden-
yl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0449]
rac-dimethylamidoborane(2-sec-butyl,4-[3',5'-di-phenylphenyl]indeny-
l).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0450]
rac-dimethylamidoborane(2-tert-butyl,4-[3',5'-di-phenylphenyl]inden-
yl ).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0451]
rac-dimethylamidoborane(2-methyl,4-[3',5'-di-tbutylphenyl]indenyl).-
sub.2zirconium dimethyl.
[0452]
rac-dimethylamidoborane(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl).s-
ub.2zirconium dimethyl;
[0453]
rac-dimethylamidoborane(2-n-propyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2zirconium dimethyl;
[0454] rac-dimethylamidoborane(2-iso-propyl,4-[3',5'-di
-tbutylphenyl]indenyl2zirconium dimethyl;
[0455]
rac-dimethylamidoborane(2-n-butyl,4-[3',5'-di-tbutylphenyl]indenyl)-
.sub.2zirconium dimethyl;
[0456]
rac-dimethylamidoborane(2-iso-butyl,4-[3',5'-di-tbutylphenyl]indeny-
l).sub.2zirconium dimethyl;
[0457]
rac-dimethylamidoborane(2-sec-butyl,4-[3',5'-di-tbutylphenyl]indeny-
l).sub.2zirconium dimethyl;
[0458]
rac-dimethylamidoborane(2-tert-butyl,4-[3',5'-di-tbutylphenyl]inden-
yl).sub.2zirconium dimethyl;
[0459] rac-dimethylamidoborane(2-ethyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0460] rac-dimethylamidoborane(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0461] rac-dimethylamidoborane(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0462] rac-dimethylamidoborane(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0463] rac-dimethylamidoborane(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0464] rac-dimethylamidoborane(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0465] rac-dimethylamidoborane(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0466]
rac-dimethylamidoborane(2-ethyl,4-[3',5'-di-iso-propylphenyl]indeny-
l).sub.2zirconium dimethyl;
[0467] rac-dimethylamidoborane(2-n-propyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl
[0468] rac-dimethylamnidoborane(2-iso-propyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0469] rac-dimethylamidoborane(2-n-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0470] rac-dimethylamidoborane(2-iso-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0471] rac-dimethylamidoborane(2-sec-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0472] rac-dimethylamidoborane(2-tert-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0473]
rac-dimethylamidoborane(2-methyl,4-[3',5'-di-phenylphenyl]indenyl).-
sub.2zirconium dimethyl;
[0474]
rac-dimethylamidoborane(2-ethyl,4-[3',5'-di-phenylphenyl]indenyl).s-
ub.2zirconium dimethyl;
[0475] rac-dimethylamidoborane(2-n-propyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0476] rac-dimethylamidoborane(2-iso-propyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0477]
rac-dimethylamidoborane(2-n-butyl,4-[3',5'-di-phenylphenyl]indenyl)-
.sub.2zirconium dimethyl;
[0478] 5
[0479] rac-dimethylamidoborane(2-iso-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0480] rac-dimethylamidoborane(2-sec-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0481] rac-dimethylamidoborane(2-tert-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0482]
rac-diisopropylamidoborane(2-methyl,4-[3',5'-di-tbutylphenyl]indeny-
l).sub.2zirconium dichloride;
[0483]
rac-diisopropylamidoborane(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2zirconium dichloride;
[0484] rac-diisopropylamidoborane(2-n-propyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0485] rac-diisopropylamidoborane(2-iso-propyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0486] rac-diisopropylamidoborane(2-n-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0487] rac-diisopropylamidoborane(2-iso-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0488] rac-diisopropylamidoborane(2-sec-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride; 25
[0489] rac-diisopropylamidoborane(2-tert-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0490] rac-diisopropylamidoborane(2-ethyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0491] rac-diisopropylamidoborane(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0492] rac-diisopropylamidoborane(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0493] rac-diisopropylamidoborane(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0494] rac-diisopropylamidoborane(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0495] rac-diisopropylamidoborane(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0496] rac-diisopropylamidoborane(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0497] rac-diisopropylamidoborane(2-ethyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0498] rac-diisopropylamidoborane(2-n-propyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride
[0499] rac-diisopropylamidoborane(2-iso-propyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0500] rac-diisopropylamidoborane(2-n-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0501] rac-diisopropylamidoborane(2-iso-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0502] rac-diisopropylamidoborane(2-sec-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0503] rac-diisopropylamidoborane(2-tert-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0504] rac-diisopropylamidoborane(2-methyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0505]
rac-diisopropylamidoborane(2-ethyl,4-[3',5'-di-phenylphenyl]indenyl-
).sub.2zirconium dichloride;
[0506] rac-diisopropylamidoborane(2-n-propyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0507] rac-diisopropylamidoborane(2-iso-propyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0508] rac-diisopropylamidoborane(2-n-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0509] rac-diisopropylamidoborane(2-iso-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0510] rac-diisopropylamidoborane(2-sec-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0511] rac-diisopropylamidoborane(2-tert-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0512]
rac-diisopropylamidoborane(2-methyl,4-[3',5'-di-tbutylphenyl]indeny-
l).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0513] rac-diisopropylamidoborane(2-ethyl,4-[3',5'-di-tbutylphenyl]
indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0514]
rac-diisopropylamidoborane(2-n-propyl,4-[3',5'-di-tbutylphenyl]inde-
nyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0515]
rac-diisopropylamidoborane(2-iso-propyl,4-[3',5'-di-tbutylphenyl]in-
denyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0516]
rac-diisopropylamidoborane(2-n-butyl,4-[3',5'-di-tbutylphenyl]inden-
yl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0517]
rac-diisopropylamidoborane(2-iso-butyl,4-[3',5'-di-tbutylphenyl]ind-
eny).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0518]
rac-diisopropylamidoborane(2-sec-butyl,4-[3',5'-di-tbutylphenyl]ind-
enyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0519]
rac-diisopropylamidoborane(2-tert-butyl,4-[3',5'-di-tbutylphenyl]in-
denyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0520]
rac-diisopropylamidoborane(2-ethyl,4-[3',5'-bis-trifluoromethylphen-
yl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0521] rac-diisopropylamidoborane(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0522] rac-diisopropylamidoborane(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0523] rac-diisopropylamidoborane(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0524] rac-diisopropylamidoborane(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0525] rac-diisopropylamidoborane(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0526] rac-diisopropylamidoborane(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0527]
rac-diisopropylamidoborane(2-ethyl,4-[3',5'-di-iso-propylphenyl]ind-
enyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0528]
rac-diisopropylamidoborane(2-n-propyl,4-[3',5'-di-iso-propylphenyl]-
indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0529]
rac-diisopropylamidoborane(2-iso-propyl,4-[3',5'-di-iso-propylpheny-
l]indenyl) .eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0530]
rac-diisopropylamidoborane(2-n-butyl,4-[3',5'-di-iso-propylphenyl]i-
ndenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0531]
rac-diisopropylamidoborane(2-iso-butyl,4-[3',5'-di-iso-propylphenyl-
]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0532]
rac-diisopropylamidoborane(2-sec-butyl,4-[3',5'-di-iso-propylphenyl-
]indenyl).sub.2.eta..sup.4-1,4-dipheny[-1,3-butadiene;
[0533]
rac-diisopropylamidoborane(2-tert-butyl,4-[3',5'-di-iso-propylpheny-
l]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0534]
rac-diisopropylamidoborane(2-methyl,4-[3',5'-di-phenylphenyl]indeny-
l).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0535]
rac-diisopropylamidoborane(2-ethyl,4-[3',5'-di-phenylphenyl]indenyl-
).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0536]
rac-diisopropylamidoborane(2-n-propyl,4-[3',5'-di-phenylphenyl]inde-
nyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0537]
rac-diisopropylamidoborane(2-iso-propyl,4-[3',5'-di-phenylphenyl]in-
denyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0538]
rac-diisopropylamidoborane(2-n-butyl,4-[3',5'-di-phenylphenyl]inden-
yl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0539]
rac-diisopropylamidoborane(2-iso-butyl,4-[3',5'-di-phenylphenyl]ind-
enyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0540]
rac-diisopropylamidoborane(2-sec-butyl,4-[3',5'-di-phenylphenyl]ind-
enyl).sub.2.theta..sup.4-1,4-diphenyl-1,3-butadiene;
[0541]
rac-diisopropylamidoborane(2-tert-butyl,4-[3',5'-di-phenylphenyl]in-
denyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0542]
rac-diisopropylamidoborane(2-methyl,4-[3',5'-di-tbutylphenyl]indeny-
l).sub.2zirconium dimethyl;
[0543]
rac-diisopropylamidoborane(2-ethyl,4-[3',5'-di-tbutylphenyl]indenyl-
).sub.2zirconium dimethyl;
[0544] rac-diisopropylamidoborane(2-n-propyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dimethyl;
[0545] rac-diisopropylamidoborane(2-iso-propyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dimethyl;
[0546] rac-diisopropylamidoborane(2-n-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dimethyl;
[0547] rac-diisopropylamidoborane(2-iso-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dimethyl,
[0548] rac-diisopropylamidoborane(2-sec-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dimethyl;
[0549] rac-diisopropylamiidoborane(2-tert-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dimethyl;
[0550] rac-diisopropylamidoborane(2-ethyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0551] rac-diisopropylamidoborane(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0552] rac-diisopropylamidoborane(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0553] rac-diisopropylamidoborane(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0554] rac-diisopropylamidoborane(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0555] rac-diisopropylamidoborane(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0556] rac-diisopropylamidoborane(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0557] rac-diisopropylamidoborane(2-ethyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0558] rac-diisopropylamidoborane(2-n-propyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl
[0559] rac-diisopropylamidoborane(2-iso-propyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0560] rac-diisopropylamidoborane(2-n-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0561] rac-diisopropylamidoborane(2-iso-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0562] rac-diisopropylamidoborane(2-sec-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0563] rac-diisopropylamidoborane(2-tert-butyl 4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0564] rac-diisopropylamidoborane(2-methyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0565]
rac-diisopropylamidoborane(2-ethyl,4-[3',5'-di-phenylphenyl]indenyl-
).sub.2zirconium dimethyl;
[0566] rac-diisopropylamidoborane(2-n-propyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0567] rac-diisopropylamidoborane(2-iso-propyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0568] rac-diisopropylamidoborane(2-n-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0569] rac-diisopropylamidoborane(2-iso-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0570] rac-diisopropylamidoborane(2-sec-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0571] rac-diisopropylamidoborane(2-tert-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0572] rac-bis(trimethylsilyl)amidoborane(2-methyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0573] rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0574] rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0575] rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0576] rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3',5 '-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0577] rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0578] rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0579] rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dichloride;
[0580] rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0581] rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0582] rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0583] rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0584] rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0585] rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-p3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0586] rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dichloride;
[0587] rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0588]
rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride
[0589]
rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0590] rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0591]
rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0592]
rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0593]
rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dichloride;
[0594] rac-bis(trimethylsilyl)amidoborane(2-methyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0595] rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0596] rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0597] rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0598] rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0599] rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3',55'di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0600] rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0601] rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dichloride;
[0602]
rac-bis(trimethylsilyl)amidoborane(2-methyl,4-[3',5'-di-tbutylpheny-
l]indenyl).sub.2.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0603]
rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3',5'-di-tbutylphenyl-
]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0604]
rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3',5'-di-tbutylphe-
nyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0605]
rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3',5'-di-tbutylp-
henyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0606] rac-bis(t4methykillamidoborane(2-n-butyI,
4-[3',5'-di-butylphenyl]i-
ndenyl).sub.2.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0607]
rac-bis(trimethylsilyl)amidoborane(2-so-butyl,4-[3',5'-di-tbutylphe-
nyl]indenyl).sub.2.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0608]
rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3',5'-di-tbutylph-
enyl]indenyl).sub.2.sub.2.eta..sup.4-1,4-diplieny-1,3-butadiene;
[0609]
rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3',5'-di-tbutylph-
enyl]indenyl).sub.2.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0610]
rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3',5'-di-tbutylp-
henyl]indenyl).sub.2.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0611] rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0612] rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0613] rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0614] rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0615] rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0616] rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0617]
rac-bis(trimethylsilyl)atnidoborane(2-tert-butyl,4-[3',5'-bis
-trifluoromethytphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadie-
ne;
[0618]
rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3',5'-di-iso-propylph-
enyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0619]
rac-bis(trimethytsilyl)amidoborane(2-n-propyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0620]
rac-bis(trimethylsityt)amidoborane(2-iso-propyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0621] rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0622]
rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0623]
rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0624]
rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0625]
rac-bis(trimethylsilyl)amidoborane(2-methyl,4-[3',5'-di-phenylpheny-
l]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0626]
rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3',5'-di-phenylphenyl-
]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0627]
rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3',5'-di-phenylphe-
nyl]indenyl).sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0628] rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2.eta..sup.4-1,4diphenyl-1,3-butadiene;
[0629]
rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3',5'-di-phenytphen-
yl]indenyl).sub.2.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0630]
rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3',5'-di-phenylph-
enyl]indenyt).sub.2.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0631]
rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3',5'-di-phenylph-
enyl]indenyl).sub.2.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0632]
rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3',5'-di-phenylp-
henyl]indenyl).sub.2.sub.2.eta..sup.4-1,4-diphenyl-1,3-butadiene;
[0633] rac-bis(trimethylsilyl)amidoborane(2-methyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dimethyl;
[0634] rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dimethyl;
[0635] rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dimethyl;
[0636] rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dimethyl;
[0637] rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dimethyl;
[0638] rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dimethyl;
[0639] rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3',5'-di
-tbutylphenyl]indenyl).sub.2zirconium dimethyl;
[0640] rac-bis (trimethylsilyl)amidoborane(2-tert-butyl,4-[3, 5-di
-tbutytphenyl]indenyl).sub.2zirconium dimethyl;
[0641] rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0642] rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0643] rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0644] rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0645] rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3',5'-bis
-trifluoromethylphenyl]ihdenyl).sub.2zirconium dimethyl;
[0646] rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3',5'-bis
-trifluoromethylphenyl]indenyl).sub.2zirconium dimethyl;
[0647] rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3',5'-bis
-trifluoromethylphenyl]ihdenyl).sub.2zirconium dimethyl;
[0648] rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0649]
rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3',5'-di-iso
-propylphenyl]indenyt).sub.2zirconium dimethyl
[0650]
rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0651] rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl; 5
[0652]
rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0653]
rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0654]
rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3',5'-di-iso
-propylphenyl]indenyl).sub.2zirconium dimethyl;
[0655] rac-bis(trimethylsilyl)amidoborane(2-methyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0656] rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3',5'-di
-phenylphenyl]indenyt).sub.2zirconium dimethyl;
[0657] rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0658] rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0659] rac-bis(trimethylsilyl)amidoborane(2-n-butyt, 4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium ditnethyl;
[0660] rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl;
[0661] rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl- and
[0662] rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3',5'-di
-phenylphenyl]indenyl).sub.2zirconium dimethyl.
[0663] "9-silafluorendiyl-" refers to the substituent: 20
[0664] The metallocenes of this invention are prepared according to
general techniques known from the literature, for example U.S. Pat.
Nos. 5,789,634 and 5,840 ,644 (both entirely incorporated herein by
reference).
[0665] Generally, metallocenes of this type are synthesized as
shown below (R.sup.4.dbd.H) where (a) is an aryl-coupling reaction
between a 4-halosubstituted indene and an aryl Grignard reagent
catalyzed by NiCl2(PPh3)in ether-type solvents at room temperature
to reflux. Product is usually purified by column chromatography or
distillation. (b) is a deprotonation via a metal salt of an alkyl
anion (e.g. n--BuLi) to form an indenide followed by reaction with
an appropriate bridging precursor (e.g. Me.sub.2SiCl.sub.2).
Reactions are usually done in ether-type solvents at ambient
temperatures. The fmal product is purified by column chromatography
or distillation; and (c) is double deprotonation via an alkyl anion
(e.g. n--BuLi) to form a dianion followed by reaction with a metal
halide (e.g. ZrCl.sub.4). The reactions are usually done in
ether-type or aromatic solvents at ambient temperatures. The final
products are obtained by recrystallization of the crude solids.
21
[0666] The metallocenes of this invention are highly active
catalyst components for the polymerization of olefins. The
metallocenes are preferably employed as chiral 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 this may be entirely desirable.
[0667] Rac/meso metallocene isomer separation is facilitated when
metallocenes containing certain bridging groups are prepared. We
have found this to be true when the bridging group, R.sup.13, is
represented by the formula: 22
[0668] wherein M.sup.2 and R.sup.17 to R.sup.24 are as defined
above.
[0669] Metallocenes are generally used in combination with some
form of activator in order to create an active catalyst system. The
terms "activator" and "cocatalyst" are used interchangeably and are
defined herein to mean any compound or component, or combination of
compounds or components, capable of enhancing the ability of one or
more metallocenes to polymerize olefins. Alklyalumoxanes such as
methylalumoxane (MAO) are commonly used as metallocene activators.
Generally alkylalumoxanes contain 5 to 40 of the repeating
units:
[0670] R(AlRO).sub.xAlR.sub.2 for linear species and
[0671] (AlRO).sub.xfor cyclic species
[0672] where R is a C.sub.1-C.sub.8 alkyl including mixed alkyls.
Compounds in which R is methyl are particularly preferred.
Alumoxane solutions, particularly methylalumoxane solutions, may be
obtained from commercial vendors as solutions having various
concentrations. There are a variety of methods for preparing
alumoxane, non-limiting examples of which are described in U.S.
Pat. Nos. 4,665,208, 4,952,540 , 5,091,352, 5,206,199, 5,204,419,
4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,
5,248,801, 5,235,081, 5,103,031 and EP-A-0 561 476, EP-B1-0 279
586, EP-A-0 594-218 and WO 94/10180, each fully incorporated herein
by reference.
[0673] Ionizing activators may also be used to activate
metallocenes. These activators are neutral or ionic, or are
compounds such as tri(n-butyl)ammonium
tetrakis(pentaflurophenyl)borate, which ionize the neutral
metallocene compound. Such ionizing compounds may contain an active
proton, or some other cation associated with, but not coordinated
or only loosely coordinated to, the remaining ion of the ionizing
compound. Combinations of activators may also be used, for example,
alumoxane and ionizing activator combination, see for example, WO
94/07928.
[0674] Descriptions of ionic catalysts for coordination
polymerization comprised of metallocene cations activated by
non-coordinating anions appear in the early work in EP-A-0 277 003,
EP-A-0 277 004 and U.S. Pat. No. 5,198,401 and WO-A-92/00333 (each
incorporated herein by reference). These teach desirable methods of
preparation wherein metallocenes are protonated by an anion
precursor such that an alkyl/hydride group is abstracted from a
transition metal to make it both cationic and charge-balanced by
the non-coordinating anion. Suitable ionic salts include
tetrakis-substituted borate or aluminum salts having fluorided
aryl-constituents such as phenyl, biphenyl and napthyl.
[0675] The term "non-coordinating anion" (NCA) means an anion which
either does not coordinate to said cation or which is only weakly
coordinated to said cation thereby remaining sufficiently labile to
be displaced by a neutral Lewis base. "Compatible" non-coordinating
anions are those which are not degraded to neutrality when the
initially formed complex decomposes. Further, the anion will not
transfer an anionic substituent or fragment to the cation so as to
cause it to form a neutral four coordinate metallocene compound and
a neutral by-product from the anion. Non-coordinating anions useful
in accordance with this invention are those which are compatible,
stabilize the metallocene cation in the sense of balancing its
ionic charge at +1, yet retain sufficient lability to permit
displacement by an ethylenically or acetylenically unsaturated
monomer during polymerization.
[0676] The use of ionizing ionic compounds not containing an active
proton but capable of producing both the active metallocene cation
and a non-coordinating anion is also known. See, for example,
EP-A-0 426 637 and EP-A-0 573 403 (each incorporated herein by
reference). An additional method of making the ionic catalysts uses
ionizing anion precursors which are initially neutral Lewis acids
but form the cation and anion upon ionizing reaction with the
metallocene compounds, for example the use of
tris(pentafluorophenyl) borane. See EP-A-0 520 732 (incorporated
herein by reference). Ionic catalysts for addition polymerization
can also be prepared by oxidation of the metal centers of
transition metal compounds by anion precursors containing metallic
oxidizing groups along with the anion groups, see EP-A-0 495 375
(incorporated herein by reference).
[0677] Where the metal ligands include halogen moieties (for
example, bis-cyclopentadienyl zirconium dichloride) which are not
capable of ionizing abstraction under standard conditions, they can
be converted via known alkylation reactions with organometallic
compounds such as lithium or aluminum hydrides or alkyls,
alkylalumoxanes, Grignard reagents, etc. See EP-A-0 500 944 and
EP-A1-0 570 982 (each incorporated herein by reference) for in situ
processes describing the reaction of alkyl aluminum compounds with
dihalo-substituted metallocene compounds prior to or with the
addition of activating anionic compounds.
[0678] Methods for supporting ionic catalysts comprising
metallocene cations and NCA are described in WO 9950311, U.S. Pat.
Nos. 5,643,847 and 5,972,823, U.S. patent application Ser. No.
09184358, filed Nov. 2, 1998 and U.S. patent application Ser. No.
09184389, filed Nov. 2, 1998 (each fully incorporated herein by
reference).
[0679] When the activator for the metallocene supported catalyst
composition is a NCA, preferably the NCA is first added to the
support composition followed by the addition of the metallocene
catalyst. When the activator is MAO, preferably the MAO and
metallocene catalyst are dissolved together in solution. The
support is then contacted with the MAO/metallocene catalyst
solution. Other methods and order of addition will be apparent to
those skilled in the art.
[0680] The catalyst systems used to prepare the compositions
of-this invention are preferably supported using a porous
particulate material, such as for example, talc, inorganic oxides,
inorganic chlorides such as magnesium chloride, and resinous
materials such as polyolefin or polymeric compounds.
[0681] Preferably, the support materials are porous inorganic oxide
materials, which include those from the Periodic Table of Elements
of Groups 2, 3, 4, 5, 13 or 14 metal/metalloid oxides. Silica,
alumina, silica-alumina, and mixtures thereof are particularly
preferable. Other inorganic oxides that may be employed either
alone or in combination with the silica, alumina or silica-alumina
are magnesia, titania, zirconia, and the like.
[0682] Preferably the support material is porous silica which has a
surface area in the range of from 10 to 700 m.sup.2/g, a total pore
volume in the range of from 0.1 to 4.0 cc/g and an average particle
size in the range of from 10 to 500 Mm. More preferably, the
surface area is in the range of from 50 to 500 m.sup.2/g, the pore
volume is in the range of from 0.5 to 3.5 cc/g and the average
particle size is in the range of from 20 to 200 .mu.m. Most
desirably the surface area is in the range of from 100 to 400
m.sup.2/g, the pore volume is in the range of from 0.8 to 3.0 cc/g
and the average particle size is in the range of from 30 to 100
.mu.m. The average pore size of typical porous support materials is
in the range of from 10 to 1000 .ANG.. Preferably, a support
material is used that has an average pore diameter of from 50 to
500 .ANG., and most desirably from 75 to 350 .ANG.. It may be
particularly desirable to dehydrate the silica at a temperature of
from 100.degree. C. to 800.degree. C. anywhere from 3 to 24
hours.
[0683] The metallocene, activator and support material may be
combined in any number of ways. More than one metallocene may also
be used. Examples of suitable support techniques are described in
U.S. Pat. Nos. 4,808,561 and 4,701,432 (each fully incorporated
herein by reference.). Preferably the metallocenes and activator
are combined and their reaction product supported on the porous
support material as described in U.S. Pat. No. 5,240 ,894 and WO
94/28034, WO 96/00243, and WO 96/00245 (each fully incorporated
herein by reference.) Alternatively, the metallocenes may be
preactivated separately and then combined with the support material
either separately or together. If the metallocenes are separately
supported, then preferably, they are dried then combined as a
powder before use in polymerization.
[0684] Regardless of whether the metallocene(s) and their activator
are separately precontacted or whether the metallocene(s) and
activator are combined at once, in some instances it may be
preferred that the total volume of reaction solution applied to
porous support is less than 4 times the total pore volume of the
porous support, more preferably less than 3 times the total pore
volume of the porous support and even more preferably in the range
of from more than I to less than 2.5 times the total pore volume of
the porous support. Procedures for measuring the total pore volume
of porous support are well known in the art. One such method is
described in Volume 1, Experimental Methods in Catalyst Research,
Academic Press, 1968, pages 67-96.
[0685] The supported catalyst system may be used directly in
polymerization or the catalyst system may be prepolymerized using
methods well known in the art. For details regarding
prepolymerization, see U.S. Pat. Nos. 4,923,833 and 4,921,825, and
EP 0 279 863 and EP 0 354 893 (each fully incorporated herein by
reference).
[0686] The metallocene catalyst systems described herein are useful
in the polymerization of all types of olefins. This includes
polymerization processes which produce homopolymers, copolymers,
terpolymers and the like as well as block copolymers and impact
copolymers. These polymerization processes may be carried out in
solution, in suspension or in the gas phase, continuously or
batchwise, or any combination thereof, in one or more steps,
preferably at a temperature of from 60.degree. C. to 200.degree. C,
more preferably from 30.degree. C. to 80.degree. C., particularly
preferably from 50.degree. C. to 80.degree. C. The polymerization
or copolymerization is carried out using olefins of the formula
RaCH.dbd.CH--Rb . In this formula, Ra and Rb 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, l-octene, norbomene and
norbornadiene. In particular, propylene and ethylene are
polymerized. The metallocenes and metallocenes catalyst systems of
this invention are most suitable for the polymerization of
propylene based polymers.
[0687] 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.
[0688] Typically, the metallocene is used in the polymerization in
a concentration, based on the transition metal, of from 10.sup.-3
to 10.sup.-8 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. When alumoxane is used as the cocatalyst, it 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.
[0689] 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 typically used for example, the
polymerization is carried out in an aliphatic or cycloaliphatic
hydrocarbon; examples of which are propane, butane, hexane,
heptane, isooctane, cyclohexane and methylcyclohexane. It is also
possible to use a benzene or hydrogenated diesel oil fraction.
Toluene can also be used. The polymerization is preferably carried
out in the liquid monomer. If inert solvents are used, the monomers
are metered in gas or liquid form.
[0690] Before addition of the catalyst, in particular of the
supported catalyst system, 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.
[0691] 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.
[0692] The process according to the invention is distinguished by
the fact that the metallocenes described can give propylene
polymers of very high molecular weight, melting point, and very
high stereotacticity, with high catalyst activities in the
industrially particularly interesting polymerization temperature
range of from 50.degree. C. to 80.degree. C.
[0693] The catalyst systems of this invention are capable of
providing polymers, particularly propylene homopolymers and
copolymers, of exceptionally high molecular weight and melting
point even when used in processes under commercially relevant
conditions of temperature, pressure and catalyst activity.
Preferred melting points are at least as high as 155.degree. C.,
more preferably at least 157.degree. C., even more preferably at
least 157.degree. C., and most preferably 1 60.degree. C. or
more.
[0694] The catalyst systems of this invention are also capable of
providing propylene polymers having high stereospecificity and
regiospecificity. Isotactic propylene polymers prepared according
to the processes of this invention may have a proportion of
2,1-inserted propene units of less than 0.5%, at a triad tacticity
of greater than 98%. Preferably there is no measurable proportion
of 2,1-inserted propene units. Triad tacticity is determined using
.sup.13C-NMR according to J. C. Randall, Polymer Sequence
Determination: Carbon-13 NMR Method, Academic Press New York 1978.
Polymers prepared using the processes of described herein find uses
in all applications including fibers, injection-molded parts,
films, pipes etc.
[0695] While the present invention has been described and
illustrated by reference to particular embodiments, it will be
appreciated by those of ordinary skill in the art, that the
invention lends itself to many different variations not illustrated
herein. For these reasons, then, reference should be made solely to
the appended claims for purposes of determining the true scope of
the present invention.
[0696] Although the appendant claims have single appendencies in
accordance with U.S. patent practice, each of the features in any
of the appendant claims can be combined with each of the features
of other appendant claims or the main claim.
EXAMPLES
[0697] All air sensitive experiments are carried out in nitrogen
purged dry boxes. All solvents were purchased from commercial
sources. 4-Bromo-2-methyl indene, 4-chloro-2-methyl-indene and tris
(perfluorophenyl) borane in toluene were purchased from commercial
sources. Aluminum alkyls were purchased as hydrocarbon solutions
from commercial sources. The commercial methylalumoxane ("MAO") was
purchased from Albemarle as a 30 wt % solution in toluene. The
metallocenes racemic
dimethylsiladiyl(2-methyl4-phenylindenyl).sub.2zirconium dichloride
and racemic
dimethylsiladiyl(4-[1-naphthy]-2-methylindenyl).sub.2zirconium
dichloride were obtained from commercial sources.
Comparative Example 1
racemic dimethylsiladiyl(2-methyl-4phenylindenyl).sub.2zirconium
dichloride
Supported Comparison Metallocene Catalyst System 1
racemic dimethylsiladiyl(2-methyl-4phenylindenyl).sub.2zirconium
dichloride/MAO
[0698] In a 100 mL round bottom flask racemic
dimethylsiladiyl(2-methyl4-p- henylindenyl).sub.2zirconium
dichloride (Comparison metallocene 1, 0.055 g) was added to a MAO
solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was
filtered through a medium glass frit funnel and washed with toluene
(14 mL). To the combined filtrates was added dehydrated silica (4.0
g, Davison 948 Regular, 600.degree. C. dehydration). This slurry
was stirred for twenty minutes then dried at 40.degree. C. for two
minutes under vacuum on a rotary evaporator until the liquid
evaporated, and then the solid was further dried a total of about
two hours and twenty two minutes. The supported catalyst was
recovered as a light orange, free flowing solid (5.63 g).
Comparative Example 2
racemic dimethylsiladiyl(2-
methyl-4-[l-naphthy]indenyl).sub.2zirconium dichloride
Supported Comparison Metallocene Catalyst System 2
racemic dimethylsiladiyl(2-
methyl-4-[1-naphthy]indenyl).sub.2zirconium dichloride/MO
[0699] In a 100 mL round bottom flask racemic dimethylsiladiyl(2-
methyl-4-[1-naphthy]indenyl).sub.2zirconium dichloride (Comparison
metallocene 2, 0.064 g) was added to a MAO solution (6.74 g, 7.2
mL) and stirred twenty minutes. This was filtered through a medium
glass frit funnel and washed with toluene (14 mL). To the combined
filtrates was added dehydrated silica (4.0 g, Davison 948 Regular,
600.degree. C. dehydration). This slurry was stirred for twenty
minutes then dried at 40.degree. C. for two minutes under vacuum on
a rotary evaporator until the liquid evaporated, and then the solid
was further dried a total of about two hours. The supported
catalyst was recovered as an orange, free flowing solid (4.72
g).
Example 3
racemic dimethylsiladiyl-bis-(
4-(3',5'-di-tertbutylphenyl).sub.2-methylin- denyl)zirconium
dichloride
1-bromo-3,5-di-tertbutylbenzene
[0700] A 1000 mL three-neck, round-bottom flask was equipped with a
mechanical stirrer, a pressure-compensating dropping funnel, and a
reflux condenser. A nitrogen gas flow adapter with overpressure
valve was attached on top of the reflux condenser. A slight
nitrogen flow guaranteed an inert gas atmosphere in the apparatus.
The flask was charged with 181 g triphenylphosphine (690 mmol) and
160 mL acetonitrile (BPLC grade). The white suspension was cooled
in an ice bath for 15 minutes. While stirring, dropwise addition of
101.5 g bromine (635 mmol) took place within 40 minutes. After
bromine addition, the ice bath was removed. 124 g of
3,5-di-tertbutylphenol (601 mmol) and 140 mL acetonitrile were
added in one portion. The orange/white suspension converted into an
orange solution upon heating. The mechanical stirrer was replaced
by an egg-shape stir bar. The solution was stirred at gentle reflux
temperature for three hours.
[0701] The flask was then fitted for a simple distillation and the
acetonitrile was distilled under water aspirator pressure. After
all the acetonitrile had been removed, the condenser was replaced
with a short, large-diameter glass tube connected to a 500 niL
glass washing bottle half filled with water. The liquid mixture was
stirred for 80 minutes at a temperature of 280-3 10C. The reaction
mixture was cooled to approximately 100.degree. C. and poured into
a 1000 mL beaker. A slight flow of nitrogen into the beaker kept
the product mixture dry. At room temperature the solid was brought
into a dry box, broken into fine pieces, and ground in a mortar.
The ground material was stirred four times with 200 mL of pentane.
The liquid phases were decanted, combined, washed with saturated
NaHCO.sub.3 solution (200 nLL), dried with MgSO.sub.4, and the
solvent evaporated. Column chromatography (silica/pentane) gave
41.6 g (25.7%) of a white, crystalline product.
[0702] .sup.1H-NMR (CHCl.sub.3=7.24ppm): .delta. 7.30 (s, 3H), 1.28
(s, 18H).
4-(3',5'-Di-tertbutylphenyl)-2-methylindene
[0703] Preparation of the Grignard salt:A 100 ml flask was charged
with 1.88 g Mg (77.3 mmol) and 10 mL THF. 13.36 g
3,5-di-tertbutyl-bromobenzen- e (49.6 mmol) were dissolved in 45
niL THF and slowly added to the Mg-turnings. The flask was heated
to 50.degree. C. in an oil bath as soon as the reaction started,
and this temperature was kept for one hour after addition of the
bromobenzene was complete. The oil bath temperature was raised and
a gentle reflux maintained for four hours.
[0704] Coupling reaction: A 100 mL flask was charged with 7.42 g
4-chloro-2-methylindene (45.1 mmol), 0.723 g
1,3-bis(diphenylphosphino)pr- opane nickel(ll)chloride, (1.334
mmol) and 30 mL Et.sub.2O. The red suspension was cooled to
-20.degree. C., and the Grignard-salt suspension from above added
within 20 minutes. The suspension was heated in an oil bath to
50.degree. C., and stirred for 40 hours at this temperature. The
flask was cooled in an ice bath. While stirring, 4 ml water and 15
ml 10% aqueous HCI were added. The THF phase was separated, the
water phase washed with Et.sub.2O, and the combined organic phases
dried with MgSO.sub.4. A purification by column chromatography
followed after evaporation of the solvent. Silica was used as the
stationary phase and pentane as the solvent. Later the solvent was
changed to a pentane/Et.sub.2O mixture (98:2). All fractions
containing product were combined, the solvent completely
evaporated. The product was recrystallized in the smallest possible
amount of pentane, stored at 4.degree. C., the solvent decanted,
and the solid dried under vacuum. Yield was 3.14 g (9.96 mmol,
21.9%). The product is a mixture of two isomers
[0705] .sup.1H-NMR (CHCl.sub.3=7.24ppm): .delta. 7.40-7.12 (m,
2x6H), 6.64 (s, 1H), 6.53 (t, 1H), 3.36 (s, 2.times.2H), 2.13 (s,
2.times.3H), 1.36 (s, 2.times.18H).
dimethylsiladiyl-bis-(4-(3',5'-di-tertbutylphenyl)-2-methylindene)
[0706] 3.12 g 4-(3',5'-Di-tertbutylphenyl)-2-methyl-indene (9.8
mmol) was dissolved in 20 mL TMF. A 100 mL flask was charged with
0.65 g KH and 25 mL TMF. At a temperature of -75.degree. C. the
indene solution was added within 8 minutes to the KH suspension.
The suspension was allowed to warm up within 40 minutes to
-50.degree. C., and then within 75 minutes to -35.degree. C. After
stirring at room temperature for 90 minutes the solid was allowed
to settle, and the orange solution transferred to a second flask.
0.6 mL Dichlorodimethylsitane (4.95 mmol) was added to the K-salt
solution at -35.degree. C. The solution was stirred overnight at
room temperature. Addition of 3 mL saturated NH.sub.4Cl solution
stopped the reaction. The solution was filtered from a white
precipitate and dried with MgSO.sub.4. Addition of 5 g silica and
complete evaporation of solvent gave a silica/raw product mixture.
Column chromatography over 125 g silica and pentane/Et.sub.2O=99:1
(500 mL) and then 98:2 (500 mL). A quantitative yield with a slight
contamination of indene starting material was recovered. The
product is a mixture of two isomers. .sup.1H-NMR
(CHCl.sub.3=7.24ppm): .delta.7.48-7.13 (m, 2.times.12H), 6.80 (m,
2.times.2H), 3.85 (s, 2H), 3.80 (s, 2H, 2.24 (s, 6H), 2.23 (s, 6H),
1.38+1.37 (2s, 2.times.36H), -0.20 (s, 3H), -0.22 (s, 2.times.3H),
-0.26 (s, 3H).
racemic dimethylsiladiyt-bis-(4-3',5'-di-tertbutylphenyl)-2-methyl
-indenyl)zirconium dichloride
[0707] 4 g of the above silane (5.77 mmol) were dissolved in 6 ml
pentane and 43 mL TBF. At -85.degree. C. 4.6 mL n-BuLi (2.5M in
hexanes, 11.5 mmol) were added within 11 minutes. The color of the
solution turned from yellow to red-brown. The solution was warmed
to -60.degree. C. within 30 minutes and stirred at room temperature
for one hour. The solvent was completely evaporated, 10 mL toluene
were added, followed again by complete evaporation of the solvent.
The red-brown residue was dissolved in 45 ml toluene and cooled to
-85.degree. C. Addition of 1.32 g ZrCl.sub.4 (5.66 mmol) gave a
brown suspension. Within two hours the suspension was warmed to
room temperature, and then refluxed for 6.5 hours. This gave a
bright orange suspension. Toluene was completely evaporated, 60 mL
pentane were added to stir the suspension overnight. Filtration
over celite and washing of the orange residue with 45 mL pentane
gave a clear orange filtrate. By slow evaporation of the pentate
solution to the dry box atmosphere, the racemic zirconocene
crystallized out of solution. The solution was decanted from the
solid; the solid washed with a few mL cold pentane and dried. By
washing the orange residue on celite above with toluene, a clear
orange toluene solution can be obtained. Evaporation of half of the
toluene and adding at least half the volume of pentane gives
crystalline meso zirconocene. Yield of racemic zirconocene was 1.5
g (1.76 mmol, 30.5%). 0.51 g (0.60 mmol, 10.4%) meso zirconocene
could be isolated. .sup.1H-NMR (CHCl.sub.3=7.24ppm): .delta. 7.64
(d, 2x 1H), 7.51 (s, 41), 7.40 (d, 2.times.1H), 7.39 (s, 2H), 7.10
(t) 2.times.1H), 6.95 (s, 2.times.1H), 2.24 (s, 2.times.3H), 1.33
(s, 2.times.3H), 1.30 (s, 12.times.3H) for the racemic zirconocene,
and 6 7.62 (d, 2.times.1H), 7.45 (s, 4H), 7.37 (t) 2.times.1H),
7.11 (d, 2.times.1H), 6.86 (m, 2.times.1H), 6.78 (s, 2.times.1H),
2.44 (s, 2.times.3H), 1.46 (s, 3H), 1.31 (s, 12.times.3H), 1.23 (s,
3H) for the meso zirconocene.
Supported Metallocene Catalyst System 3A
racemic dimethylsiladiyl-bis-(
4-(3',5'-di-tertbutylphenyl)-2-methylindeny- l)zirconium
dichloride/MAO
[0708] In a 100 mL round bottom flask racemic
dimethylsiladiyl-bis-(4-(3',- 5'-di
-tertbutylphenyl)-2-methylindenyl) zirconium dichloride (0.075 g)
was added to a MAO solution (6.74 g, 7.4 mL) and stirred twenty
minutes. This was filtered through a medium glass frit funnel and
washed with toluene (14 mL). To the combined filtrates was added
dehydrated silica (4.0 g, Davison 948 Regular, 600.degree. C.
dehydration). This slurry was stirred for twenty minutes, then
dried at 40.degree. C. for one minutes under vacuum on a rotary
evaporator until the liquid evaporated, and then the solid was
further dried a total of about two hours and twenty minutes. The
supported catalyst was recovered as a reddish pink, free flowing
solid (5.4 g).
dimethylsiladiylbis[4-(3',5
'-di-tert-butylphenyl)-2-methylindenyl]zirconi- um dimethyl
[0709]
Dimethylsiladiylbis[4-3',5'-di-tert-butylphenyl)-2-methylindenyl]Zr-
Cl.sub.2 (488 mgs, 0.57 mmol) was dissolved in 30 mL of toluene to
give a clear orange solution. 3.OM MeMgBr solution in Et.sub.2O
(0.76 mL, 2.28 mmol) was added at room temperature via syringe and
the reaction was stirred at reflux overnight. After this time, the
reaction was cooled and 0.5 mL of 1,4-dioxane and 0.5mL of
Me.sub.3SiCl was added to the solution. This solution was filtered
through a celite-packed frit and the toluene was removed in vacuo.
The remaining yellow solid was washed with pentane and dried in
vacuo to yield 257 mgs (55.3%) of the desired metallocene.
Supported Metallocene Catalyst System 3B
racemic dimethylsiladiyl-bis-(
4-(3',5'-di-tertbutylphenyl)-2-methylindeny- l)zirconium
dimethyl/NCA
[0710] In a 50-ml beaker, 1.07 g (0.232 mmol) of an 11.05 wt %
solution of tris (perfluorophenyl) borane in toluene was massed.
0.035 g (0.232 mmol) of N, N -diethylaniline (Aldrich, 98+%) was
added followed by 4.5 g of toluene. A pink solution resulted. This
solution was pipetted into a 50 ml round bottom flask containing
2.0 g of silica (Grace Davison, calcined at 500.degree. C. with
3-wt % H.sub.4).sub.2SiF.sub.6) and a magnetic stir bar. 4.5 g of
toluene was used to rinse the beaker, pipette, and the sides of the
flask. The flask was heated to 50.degree. C. in an oil bath. The
mixture was stirred for 30 minutes. 0.023 g (0.028 mmol) of the
dimethylsiladiyl-bis-(4-(3',5'-di-tertbutylphenyl)-2-methylindenyl)
zirconium dimethyl was added as a solid to produce a red slurry.
Stirring was continued for 1 hour at 50.degree. C. After this time,
the stirring and heating were discontinued. The solvent was
stripped overnight in vacuo to give 2.13 g of a flesh colored
powder. Composition by mass balance: Zirconium: 0.013 mmol/g
catalyst, Boron: 0.11 mmol/g catalyst.
Supported Metallocene Catalyst System 3C
racemic dimethylsiladiyl-bis-(
4-(3',5'-di-tertbutylphenyl).sub.2-methylin- denyl)zirconium
dimethyl/NCA
[0711] This catalyst preparation used the same raw materials as
above. In a 50 mL beaker, 2.68 g (0.58 mmol) of an 11.05-wt %
solution of tris (perfluorophenyl) borane in toluene was massed.
0.088 g (0.59 mmol) of N, N-diethylaniline was added followed by 15
g of toluene. A pink solution resulted. This solution was pipetted
into a 100 mL round bottom flask containing 5.0 g of silica and a
magnetic stir bar. 1.0 g of toluene was used to rinse the beaker,
pipette, and the sides of the flask. The flask was heated to
50.degree. C. in an oil bath. The mixture was stirred for 30
minutes. 0.0061 g (0.075 mmol) of the
dimethylsiladiyl-bis-(4-(3',5'-d-
i-tertbutylphenyl)-2-methylindenyl) zirconium dimethyl was added as
a solid to produce a red slurry. Stirring was continued for 30
minutes at 50.degree. C. After this time, the stirring and heating
were discontinued. The solvent was stripped overnight in vacuo to
give 5.36 g of a flesh colored powder. Composition by mass balance:
Zr: 0.013 mmol/g catalyst, B: 0.11 mmol/g catalyst.
Example 4
racemic
[9-Silafluorenebis(4-(3',5'-di-t-butylphenyl)-2-methylindene]zirco-
nium dichloride
[0712] 4-[3',5'-di-t-butylphenyl]-2-methylindene
[0713] 4-Chloro-2-methylindene (6.1 g, 37 mmol) and
NiCl.sub.2(PPh.sub.3).sub.2 (1.8 g, 2.8 mmol) were dissolved in 150
mL of Et.sub.2O. 3,5-Di-t-butylphenylmagnesium bromide (10 g, 37
mmol) as a Et.sub.2O solution was added to the solution and the
reaction was stirred overnight at room temperature. After overnight
stirring, the reaction was slowly quenched with H.sub.2O to
neutralize unreacted Grignard. The solution was subsequently
treated with 100 mL of 10% HCl(aq), neutralized with saturated
sodium bicarbonate aqueous solution. The organic layer was dried
with magnesium sulfate and the solvent was removed by rotary
evaporation. The remaining residue was loaded onto a silica gel
column and eluted with hexane.
[0714] Yield was 4.6 g (40%).
lithium 4-[3',5'-di-t-butylphenyl]-2-methylindene
[0715] 4-[3'.sup.t,S-Di-t-butylphenyl]-2-methylindene (4.7 g, 15
mmol) was dissolved in 80 mL of pentane. To this solution was added
5.9 mL of n-BuLi (2.5M in hexane) and the reaction is allowed to
stir 4 hours at room temperature. A white solid precipitated from
solution and was collected by frit filtration and washed with
additional pentane. Yield was 3.6 g (78%).
9-silafluorenebis [4-(3',5'-di-t-butylphenyl)-2-methylindene
[0716] 9,9-Dichloro-9-silafluorene (1.2 g, 9.2 mmol) was dissolved
in 80 mL of THF. To this solution was slowly added lithium
4-(3',5'-di-t-butylphenyl)-2-methylindene (3.0 g, 9.2 mmol) as a
dry powder and the solution was stirred overnight. After this time,
the solvent was removed in vacuo and the residue was taken up in
diethyl ether. The solution was filtered through a frit to remove
LiCl and the solvent was removed in vacuo and used as a crude
product (4.1 g) for the next step.
[9-silafluorenebis(4-(3',5'-di-t-butylphenyl)-2-methylindene]ZrCl.sub.2
[0717] The crude solid from the previous step (4.1 g, 5.5 mmol) was
taken up in 50 mL of diethyl ether. To this solution was slowly
added n-BuLi (4.4 mL, 2.5 M in hexane) and stirred for 3 hours at
room temperature. The solution was cooled to -30.degree. C. and
ZrCl.sub.4 (1.28 g, 4.6 mmol) was added as a dry powder and stirred
at room temperature for two hours. The solvent was removed in vacuo
and toluene as added to the crude residue. The solution was
filtered to remove LiCl. The filtrate was concentrated and pentane
is added under heating. The solution was cooled to induce
crystallization. Yield of pure racemic isomer was 187 mgs
(3.7%).
Supported Metallocene Catalyst System 4
racemic
[9-silafluorenebis(4-(3',5'-di-t-butylphenyl)-2-methylindene]zirco-
nium dichloride
[0718] In a 100 mL round bottom flask racemic
[9-Silafluorenebis(4-(3',5'-- di-t
-butylphenyl)-2-methylindene]zirconium dichloride (0.085 g) was
added to a MAO solution (6.74 g, 7.2 mL) and stirred twenty
minutes. This was filtered through a medium glass frit funnel and
washed with toluene (14 mL). To the combined filtrates was added
dehydrated silica (4.0 g, Davison 948 Regular, 600.degree. C.
dehydration). This slurry was stirred for twenty minutes, then
dried at 40.degree. C. for two minutes under vacuum on a rotary
evaporator until the liquid evaporated, and then the solid was
further dried a total of about two hours and twenty minutes. The
supported catalyst was recovered as a pink reddish, free flowing
solid (5.24 g).
Example 5
racemic
[9-silafluorenebis(4-(3',5'-di-t-butylphenyl)-2-isopropylindene]zi-
rconium dichloride
[0719] 4-[3',5'-di-t-butylphenyl]-2-isopropylindene
[0720] 4-Chloro-2-isopropylindene (7.2 g, 37 mmol) and
NiCl.sub.2(PPh.sub.3).sub.2 (1.8 g, 2.8 mmol) were dissolved in 150
mL of Et.sub.2O. 3,5-Di-di-t-butylphenylmagnesium bromide (10 g, 37
mmol) as a Et.sub.2O solution was added to the solution and the
reaction was stirred overnight at room temperature. After overnight
stirring, the reaction was slowly quenched with H.sub.2O to
neutralize unreacted Grignard. The solution was subsequently
treated with 100 mL of 10% HCl(aq), neutralized with saturated
sodium bicarbonate aqueous solution. The organic layer was dried
with magnesium sulfate and the solvent was removed by rotary
evaporation. The remaining residue was loaded onto a silica gel
column and eluted with hexane. Yield is 5.8 g (45%).
lithium 4-[3',5'-di-t-butylphenyl]-2-isopropylindene
[0721] 4-[3',5'-di-t-butylphenyl]-2-isopropylindene (5.8 g, 17
mmol) was dissolved in 80 mL of pentane. To this solution was added
6.6 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to
stir 4 hours at room temperature. A white solid precipitated from
solution and was collected by frit funnel filtration and washed
with additional pentane. Yield is 5.0 g (87%).
silafluorenebis[4-(3',5'-bis[t-butyl]phenyl)-2-isopropylindene
[0722] 9,9-Dichloro-9-silafluorene (1.1 g, 8.5 mmol) was dissolved
in 80 mL of THF. To this solution was slowly added lithium
4-(3',5'-di-t-butylphenyl)-2-isopropylindene (3.0 g, 8.5 mmol) as a
dry powder and the solution was stirred overnight. After this time,
the solvent was removed in vacuo and the residue was taken up in
diethyl ether. The solution as filtered through frit to remove LiCl
and the solvent was removed in vacuo and used as a crude product
(3.9 g) for the next step.
9-silafluorenebis(4-(3',5'-di-t-butylphenyl)-2-isopropylindene]ZrCl.sub.2
[0723] The crude solid from the previous step (3.9 g, 4.6 mmol) was
taken up in 50 mL of diethyl ether. To this solution was slowly
added n-BuLi (3.7 mL, 2.5 M in hexane) and stirred for 3 hours at
room temperature. The solution was cooled to -30.degree. C. and
ZrCl.sub.4 (1.1 g, 4.6 mmol) was added as a dry powder and stirred
at room temperature for two hours. The solvent was removed in vacuo
and toluene was added to the crude residue. The solution was
filtered to remove LiCl. The filtrate was concentrated and pentane
added under heating. The solution was cooled to induce
crystallization. Yield of pure racemic isomer was 280 mgs (6.0
Supported Metallocene Catalyst System 5
racemic
[9-silafluorenebis(4(3',5'-di-t-butylphenyl)-2-isopropylindene]zir-
conium dichloride
[0724] In a 100 mL round bottom flask racemic
[[9-Silafluorenebis(4-(3',5'- -di-t
-butylphenyl)-2-isopropylindene]zirconium dichloride (0.090 g) was
added to a MAO solution (6.74 g, 7.2 mL) and stirred twenty
minutes. This was filtered through a medium glass frit funnel and
washed with toluene (14 mL). To the combined filtrates was added
dehydrated silica (4.0 g, Davison 948 Regular, 600.degree. C.
dehydration). This slurry was stirred for twenty minutes, then
dried at 40.degree. C. for two minutes under vacuum on a rotary
evaporator until the liquid evaporated and then the solid was
fuirther dried a total of about two hours and twenty minutes. The
supported catalyst was recovered as a light purple, free flowing
solid (5.17 g).
Example 6
dimethylsiladiyl-bis-(2-methyl-4-(3',5'-di-methylphenyl)indenyl)zirconium
dichloride
[0725] 4-(3',5'-dimethylphenyl)-2-methylindene
[0726] 4-Chloro-2-methylindene (8.9 g, 54 mmol) and
NiCl.sub.2(PPh.sub.3).sub.2 (1.8 g, 2.8 mmol) were dissolved in 150
mL of Et.sub.2O. 3,5-Dimethylphenylmagnesium bromide (log, 54 mmol)
as a Et.sub.2O solution was added to the solution and the reaction
was stirred overnight at room temperature. After overnight
stirring, the reaction was slowly quenched with H.sub.2O to
neutralize unreacted Grignard- The solution was subsequently
treated with 100 mL of 10% HCl(aq), neutralized with saturated
sodium bicarbonate aqueous solution. The organic layer was dried
with magnesium sulfate and the solvent was removed by rotary
evaporation. The remaining residue was loaded onto a silica gel
column and eluted with hexane. Yield was 5.6 g (44%).
lithium 4-3',5'-dimethylphenyl).sub.2-methylindene
[0727] 4-(3',5'-dimethylphenyl)-2-methylindene (5.6 g, 23.9 mmol)
was dissolved in 80 ImL of pentane. To this solution was added 9.6
mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir
4 hours at room temperature. A white solid precipitated from
solution and was collected by frit filtration and washed with
additional pentane. Yield was 4.5 g (80%).
dimethylsilylbis[4-(3',5'-dimethylphenyl).sub.2-methylindene
[0728] SiMe.sub.2Cl.sub.2 (1.2 g, 9.4 mmol) was dissolved in 80 mL
of THF. While stirring, lithium
4-(3,5-dimethylphenyl)-2-methylindenide (4.5 g, 18.7 mmol) was
added as a dry powder and the contents were allowed to stir
overnight at room temperature. The solvent was removed in vacuo and
the residue was taken up in pentane and filtered to remove LiCl
salts. The pentane was removed in vacuo to yield a flaky white
solid (4.23 g, 87%).
dimethylsiladiylbis[4-(3',5'-dimethylphenyl).sub.2-methylindene]ZrCl.sub.2
[0729]
Dimethylsilylbis[4-(3',5'-dimethylphenyl).sub.2-methylindene] (4.23
g, 8.0 mmol) was dissolved in 60 mL of Et.sub.2O. While stirring,
6.4 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at
room temperature for two hours. After this time, the solution was
cooled to -35.degree. C. and ZrCl.sub.4 (1.58 g, 8.0 mmol) was
added and allowed to stir at room temperature for 3 hours. The
solvent was then removed in vacuo and the residue was taken up in a
mixture of methylene chloride and pentane and filtered to remove
LiCl salts. The filtrate was then concentrated and chilled to
-35.degree. C. to induce crystallization. 0.23 g (5.0%) of pure
racemic compound was obtained.
Supported Metallocene Catalyst System 6
dimethylsiladiyl-bis-(2-methyl-4-(3',5'-di-methylphenyl)indenyl)zirconium
dichloride/MAO
[0730] In a 100 mL round bottom flask
Dimethylsiladiyl-bis-(2-methyl-4-(3'- ,5'-di -methylphenyl)indenyl)
zirconium dichloride (0.061 g) was added to a MAO solution (6.74 g,
7.4 mL) and stirred twenty minutes. This was filtered through a
medium glass frit funnel and washed with toluene (14 mL). To the
combined filtrates was added dehydrated silica (4.0 g, Davison 948
Regular, 600.degree. C. dehydration). This slurry was stirred for
twenty minutes, then dried at 40.degree. C. for two minutes under
vacuum on a rotary evaporator until the liquid evaporated, and then
the solid was dried a total of about two hours and thirty four
minutes. The supported catalyst was recovered as a light orange,
free flowing solid (5.36 g).
Example 7
dimethylsiladiyl-bis-(4-(3',5'-bistrifluoromethylphenyl).sub.2-methyl
-indenyl)zirconium dichloride
[0731] 4-[3',5'-bis(trifluoromethyl)phenyl]-2-methylindene
[0732] 4-Bromo-2-methylindene (10.7 g, 51 mmol) and
NiCl.sub.2(PPh.sub.3).sub.2 (1.8 g, 2.8 mmol) were dissolved in 150
mL of Et.sub.2O. 3,5-bis(trifluoromethyl)phenylmagnesium bromide
(51 mmol) as a Et.sub.2O solution was added under vigorous stirring
and the reaction stirred overnight at room temperature. After
overnight stirring, the reaction was slowly quenched with H.sub.2O
to neutralize unreacted Grignard. The solution was subsequently
treated with 100 mL of 10% HCl(aq), and neutralized with saturated
sodium bicarbonate aqueous solution. The organic layer was dried
with magnesium sulfate and the solvent was removed by rotary
evaporation. The remaining residue was loaded onto a silica gel
column and eluted with hexane. Yield was 2.2 g (13%).
lithium 4-[3',5'-bis(trifluoromethyl)phenyl]-2-methylindenide
[0733] 4-[3',5'-bis(trifluoromethyl)phenyl]-2-methylindene (2.2 g,
6.5 mmol) was dissolved in 50 mL of pentane. To this solution was
added 2.6 mL of n-BuLi (2.5M in hexane) and the reaction was
allowed to stir 4 hours at room temperature. A yellow-white solid
precipitated from solution and was collected by frit filtration and
washed with additional pentane. Yield was 1.6 g (73%).
dimethylsiladiylbis[4-(3',5'-bis[trifluoromethyl]phenyl)-2-methylindene
[0734] SiMe.sub.2Cl.sub.2 (0.48 g, 3.7 mmol) was dissolved in 80 mL
of THF. While stirring, lithium
4-[3',5'-bis(trifluoromethylphenyl]-2-methyl- indenide (2.6 g, 7.5
mmol) was added as a dry powder and the contents were allowed to
stir overnight at room temperature. The solvent was removed in
vacuo and the residue taken up in pentane and filtered to remove
LiCl salts. The pentane was removed iii vacuo, and the crude
product is loaded onto a silica gel column and eluted with hexane.
Yield was 2.2 g (80%)
dimethylsiladiylbis[4-(3',5'-bis[trifluoromethyl]phenyl)-2-methylindene]Zr-
Cl.sub.2
[0735]
Dimethylsiladiylbis[4-(3',5'-bis[trifluoromethylphenyl])-2-methylin-
dene](2.2 g, 3.0 mmol) was dissolved in 50 mL of Et.sub.2O. While
stirring, 2.4 mL of n -BuLi (2.5M in hexane) was added and allowed
to stir at room temperature for two hours. After this time, the
solution was cooled to -35.degree. C. and ZFCl.sub.4 (0.69 g, 3.0
mmol) was added and allowed to stir at room temperature for 3
hours. The solvent was then removed in vacuo and the residue taken
up in toluene and filtered to remove LiCl salts. The filtrate was
then concentrated and chilled to -35.degree. C. to induce
crystallization. 90 mg (3.3%) of pure racemic compound was
obtained.
Supported Metallocene Catalyst System 7
dimethylsiladiyl-bis-(4(3',5'-bistrifluoromethylphenyl)-2-methyl
-indenyl)zirconium dichloride/MAO
[0736] In a 100 mL round bottom flask
dimethylsiladiyl-bis-(4-(3',5'-bistr-
ifluoromethylphenyl)-2-methyl-indenyl)zirconium dichloride ( 0.075
g) was added to a MAO solution (6.32 g, 6.75 mL) and stirred twenty
minutes. This was filtered through a medium glass frit funnel and
washed with toluene (13 mL). To the combined filtrates was added
dehydrated silica (3.75 g, Davison 948 Regular, 600.degree. C.
dehydration). This slurry was stirred for thirty minutes then dried
at 40.degree. C. for two minutes under vacuum on a rotary
evaporator until the liquid evaporated and then the solid was
further dried a total of about two hours and twenty minutes. The
supported catalyst was recovered as a dull red pink, free flowing
solid (5.03
Example 8
dimethylsiladiylbis(4-(3',5'-bis-trimethylsilyl-phenyl)-2-methylindenyl)zi-
rconium dichloride
[0737] 3,5-Dibromo-trimethylsilyl-benzene
[0738] 42.4 g of Tribromobenzene (134.6 mmol) was dissolved in 600
mL Et.sub.2O. The solution was chilled to -55.degree. C., at which
temperature starting material precipitated. 54 mL of n-BuLi (2.5 M
in hexanes, 135 mmol) were added within 20 minutes. After stirring
for 35 minutes at -52.degree. C., 20 ml TMSCl (158 mmol) and 20 mL
Et.sub.2O were added within 7 minutes. The suspension turned into a
solution at -42.degree. C., and a fine precipitate appeared at
-30.degree. C. The suspension was stirred overnight at room
temperature. 100 mL 2M HCl were used to hydrolyze the mixture.
After stirring for 30 minutes, the Et.sub.2O-phase was dried with
MgSO.sub.4, filtered, and solvent evaporated until compound
crystallized out of solution. The flask was stored overnight at
+4.degree. C. The crystalline compound was filtered, washed with a
small amount cold pentane, and dried under vacuo. A second fraction
of crystalline compound was obtained from the filtrate. Yield: 31.9
g (103.5 mmol, 77%). .sup.1H-NMR (CHCl.sub.3=7.24ppm): .delta. 7.62
(t, 1H), 7.49 (d, 2H), 0.25 (s, 3.times.3H).
3,5--Bis-trimethylsilyl-bromobenzene
[0739] 17.18 g of 3,5-Dibromo-trimethylsilyl-benzene, 55.8 mmol,
was dissolved in 380 ml Et.sub.2O. The solution was chilled to
-68.degree. C., and 22.3 mL of n-BuLi (2.5 M in hexanes), 55.8
mmol, were added within 18 minutes. The solution changed its color
from clear to yellow, and was stirred for 45 minutes at -68.degree.
C. 7.5 mL TMSCl, 59 mmol, were added within six minutes. The
temperature of solution rose within one hour to -33.degree. C., and
after another 30 minutes to -18.degree. C. The solution was stirred
overnight at room temperature. 60 mL of 2M HCl were added to the
white suspension. Stirring for 30 minutes resulted in two clear
phases. Et.sub.2O-phase was dried with MgSO.sub.4, filtered, and
solvent evaporated. Raw product was distilled at a temperature of
70-76.degree. C. and 0.1-0.2 mbar. All pure fractions were combined
and gave 15.8 g of product (52.4 mmol, 94%). .sup.1H-NMR
(CHCl.sub.3=7.24ppm): .delta. 7.56 (s, 2H), 7.50 (t, 1H), 0.25 (s,
6.times.3H).
4-(3',5 '--Bis-trimethylsilyl-phenyl)-2-methylindene
[0740] Preparation of the Grignard salt: A 100 miL flask was
charged with 2.9 g Mg (119 mmol) and 10 ml THE. 15.8 g
3,5--Bis-trimethylsilyl-bromobe- nzene (52.4 mmol) were dissolved
in 45 mL THF and slowly added to the Mg-turnings at room
temperature. The reaction started after 5 minutes resulting in a
black -brown, hot solution. The mixture was stirred overnight
maintaining a gentle reflux temperature.
[0741] Coupling reaction: A 100 mL flask was charged with 8.2 g
4-chloro-2-methylindene (49.8 mmol) and 1.14 g
1,2-bis(diphenylphosphino)- ethane nickel(II)chloride (2.16 mmol).
At room temperature the Grignard-salt suspension from above was
poured to the indene/nickel catalyst suspension. The suspension was
stirred for 16 hours at gentle reflux temperature. While stirring,
5 ml water and 10 mL 10% aqueous HCl were added. The THF phase was
separated, the water phase washed with Et.sub.2O, and the combined
organic phases dried with MgSO.sub.4. Purification by column
chromatography followed after evaporation of the solvent. Silica
was used as the stationary phase and pentane as the solvent. Later
the solvent was changed to a pentane/Et.sub.2O mixture (98:2). All
fractions containing product were combined, the solvent completely
evaporated. Yield was 15.35 g, 43.8 mmol (83.5%). The product is a
mixture of two diastereomers. .sup.1H-NMR (CHCl.sub.3=7.24ppm):
.delta. 7.67-7.63 (m, 2.times.3H), 7.37-7.10 (m, 2.times.3H), 6.61
(s, 1H), 6.53 (d, 1H), 3.36 (s, 2H), 3.34 (s, 2H), 2.13 (s,
2.times.3H), 0.29 (s, 2.times.18H).
Dimethylsiladiylbis(4-(3',5'-bis-trimethylsilyl-phenyl)-2-methylindene)
[0742] 15.35 g 4-(3',5'--Bis-trimethylsilyl-phenyl)-2-methyl-indene
(43.8 mmol) were dissolved in 70 mL THF. A second flask was charged
with 2.6 g KH, and 70 mL THF. At a temperature of -65.degree. C.
the indene solution was added within 20 minutes to the KU
suspension. After stirring at room temperature for two hours the
solid was allowed to settle for 30 minutes, and the red solution
transferred to a new flask. A few ml THF were added to the KH
suspension, let stir and settle, and transferred also this solution
to the new flask. 2.6 mL Dimethyldichlorosilane (21.4 mmol) were
added to the K-salt solution at -35.degree. C. The solution was
stirred over night at room temperature. Addition of 10 ml sat.
NH.sub.4Cl solution stopped the reaction. The solution was filtered
from a white precipitate, and dried with MgSO.sub.4. Addition of 22
g silica and complete evaporation of solvent gave a silica/raw
product mixture. Column chromatography was done over 250 g silica
with pentane/Et.sub.2O mixtures of 99:1 to 96:4. Obtained were 11.2
g product (14.79 mmol, 67.5%), and 2.7 g of a less pure fraction.
The product is a mixture of two isomers. .sup.1H-NMR
(CHCl.sub.3=7.24ppm): 6 7.68-7.14 (m, 2.times.12H), 6.78 (m,
2.times.2H), 3.85 (s, 2H), 3.81 (s, 2H), 2.24 (s, 6H), 2.23 (s,
6H), 0.31 (2s, 2.times.36H), -0.19 (s, 3H), -0.23 (s, 3H), -0.26
(s, 6H).
Dimethylsiladiytbis(4-(3',5'-bis-trimethylsilyl-phenyl)-2-methylindenyl)
zirconium dichloride
[0743] 4.1 g Silane from above (5.4 mmol) were dissolved in 50 mL
THF. At a cooling bath temperature of -83.degree. C., 4.3 mL n-BuLi
(2.5M in hexanes, 10.8 mmol) were added within one minute. The
color of the solution turned from yellow to red-brown. The solution
was warmed to -30.degree. C. within 100 minutes and then stirred at
room temperature for 100 minutes. The solvent was completely
evaporated, 13 mL toluene were added following again complete
evaporation of the solvent. The residue was dissolved in 50 ml
toluene and cooled to -82.degree. C. lo Addition of 1.26 g
ZrCl.sub.2 (5.41 mmol) resulted in a light brown suspension. The
suspension was stirred overnight at room temperature, refluxed for
5.5 hours, and again stirred overnight at room temperature. This
resulted in an orange suspension. Filtration over celite and
complete evaporation of toluene gave an orange solid. 40 mL Pentane
was added to the solid, and the suspension stirred. Filtration,
using a frit, washing with 3 mL cold pentane, and drying under
vacuo gave fraction 1 (1.56 g). Rac/meso ratio of fraction 1 is
8:92. All solvent was evaporated from the filtrate, and exactly 8
mL pentane were added to dissolve the residue. The solution was
placed in a freezer at -35.degree. C. which initiated the
crystallization of a solid compound. Filtration, using a frit,
washing with a few mL cold pentane, and drying under vacuo gave
fraction 2 (0.63 g). Rac/meso ratio of fraction 2 is 85:15. All
solvent was evaporated from the filtrate, and the solid kept as
fraction 3 (1.77 g). Racimeso ratio of fraction 3 is 73:27. .sup.1
H-NMR (CHCl.sub.3=7.24ppm): .delta. 7.78 (s, 2.times.2H), 7.70 (d,
2.times.1H), 7.64 (s, 2.times.1H), 7.41 (d, 2.times.1H), 7.12 (m,
2.times.1H), 6.91 (s, 2.times.1H), 2.25 (s, 2.times.3ff), 1.32 (s,
2.times.3H), 0.24 (s, 12.times.3H) for the racemic zirconocene, and
6 7.72 (s, 2.times.2H), 7.66 (s, 2.times.1H), 7.62 (s, 2.times.1H),
7.12 (d, 2.times.1H), 6.88 (m, 2.times.1H), 6.75 (s, 2.times.1H),
2.43 (s, 2.times.3H), 1.46 (s, 3H), 1.23 (s, 3H), 0.25 (s,
12.times.3H) for the meso zirconocene.
Supported Metallocene Catalyst System 8
dimethylsiladiylbis(4-(3',5'-bis-trimethylsilyl-phenyl)-2-methylindenyl)zi-
rconium dichloride/MAO
[0744] In a 100 mL round bottom flask
Dimethylsiladiylbis(4-(3',5'-bis
-trimethylsilyl-phenyl).sub.2-methylindenyl) zirconium dichloride
(0.080 g) was added to a MAO solution (6.74 g, 7.3 mL) and stirred
twenty minutes. This was filtered through a medium glass frit
funnel and washed with toluene (14 mL). To the combined filtrates
was added dehydrated silica (4.0 g, Davison 948 Regular,
600.degree. C. dehydration). This slurry was stirred for twenty
minutes, then dried at 40.degree. C. for two minutes under vacuum
on a rotary evaporator until the liquid evaporated, and then the
solid was further dried a total of about 4 hours and thirty
minutes. The supported catalyst was recovered as a pink red, free
flowing solid (5.15 g).
Example 9
dimethylsiladiylbis[4-(3',5'-dimethylphenyl)-2-isopropylindene]zirconium
dichloride
4-(3',5'-dimethylphenyl)-2-isopropylindene
[0745] 4-chloro-2-isopropylindene (10.0 g, 54 mmol) and
NiCl.sub.2(PPh.sub.3).sub.2 (1.8 g, 2.8 mmol) were dissolved in 150
mL of Et.sub.2O. 3,5-dimethylphenylmagnesium bromide (54 mmol) as a
Et.sub.2O solution was added under vigorous stirring and the
reaction was stirred overnight at room temperature. After overnight
stirring, the reaction was slowly quenched with H.sub.2O to
neutralize unreacted Grignard. The solution was subsequently
treated with 100 mL of 10% HCl(aq), neutralized with saturated
sodium bicarbonate aqueous solution. The organic layer was dried
with magnesium sulfate and the solvent was removed by rotary
evaporation. The remaining residue was loaded onto a silica gel
column and eluted with hexane. Yield was 5.5 g (39%).
lithium 4-(3',5'-dimethylphenyl),2-isopropylindenide
[0746] 4-(3',5'-dimethylphenyl)-2-isopropylindene (5.5 g, 21 mmol)
was dissolved in 80 mL of pentane. To this solution was added 8.3
mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir
4 hours at room temperature. A white solid precipitated from
solution and was collected by frit filtration and washed with
additional pentane. Yield was 3.3 g (60%).
Dimethylsiladiylbis[4-(3',5'-dimethylphenyl),2-isopropylindene
[0747] SiMe.sub.2Cl.sub.2 (0.69 g, 5.4 mmol) was dissolved in 80 mL
of TUF. While stirring, lithium
4-(3',5'-dimethylphenyl)-2-isopropylindenide (2.9 g, 11 mmol) was
added as a dry powder and the contents allowed to stir overnight at
room temperature. The solvent was removed in vacuo and the residue
was taken up in pentane and filtered to removed LiCt salts. The
pentane was removed in vacuo to yield a flaky white solid (2.1 g,
67%)
Dimethylsiladiylbis[4-(3',5'-dimethylphenyl)-2-isopropylindene]ZrCl.sub.2
[0748]
Dimethylsiladiylbis[4-(3',5'-dimethylphenyl)-2-isopropylindene]
(2.1 g, 3.6 mmol) was dissolved in 60 mL of Et.sub.2O. While
stirring, 2.9 mL of n-BuLi (2.5M in hexane) was added and allowed
to stir at room temperature for two hours. After this time, the
solution was cooled to -35.degree. C. and ZrCl.sub.4 (0.83 g, 3.6
mmol) was added and allowed to stir at room temperature for 3
hours. The solvent was then removed in vacuo and the residue taken
up in toluene and filtered to remove LiCl salts. The filtrate was
then concentrated and chilled to -35.degree. C. to induce
crystallization. 0.24 g (6.0%) of pure racemic compound was
obtained.
Supported Metallocene Catalyst System 9
dimethylsiladiylbis[4-(3',5'-dimethylphenyl).sub.2-isopropylindene]zirconi-
um dichloride/MAO
[0749] In a 100 mL round bottom flask
dimethylsiladiylbis[4-(3',5'-dimethy-
lphenyl)-2-isopropylindene)zirconium dichloride (0.066 g) was added
to the MAO solution (6.74 g, 7.2 mL) and stirred twenty minutes.
This was filtered through a medium glass frit funnel and washed
with toluene (14 mL). To the combined filtrates was added
dehydrated silica (4.0 g, Davison 948 Regular, 600.degree. C.
dehydration). This slurry was stirred for twenty minutes, then
dried at 40.degree. C. for two minutes under vacuum on a rotary
evaporator until the liquid evaporated, and then the solid was
further dried a total of about two hours and thirty minutes. The
supported catalyst was recovered as a purple, free flowing solid
(5.11 g).
Example 10
[9-silafluorenebis(4-(3',5'-dimethylphenyl)-2-isopropylindene]zirconium
dichloride
[0750] 2,2'-Dibromobiphenyl
[0751] To a stirred solution of o-dibromobenzene (47.3 g, 0.2 mol)
in 450 mL of anhydrous THF was added 76.4 mL of n-BuLi (1.OM in
Et.sub.2O). The o -dibromobenzene solution was cooled in a dry
ice/acetone bath. The yellow-green reaction mixture was allowed to
warm to 5.degree. C. and was then hydrolyzed with 100 mL of 5%
hydrochloric acid. The resulting layers were separated and the
aqueous layer extracted 4 times with 4.times.20 mL portions of
diethyl ether. The ether washings were combined with the original
organic layer, the whole was dried over sodium sulfate, filtered,
and concentrated by distillation until the distillation temperature
reached 70.degree. C. The residue was treated with 50 mL of
absolute ethanol and cooled to give 2,2'-dibromobiphenyl. Yield was
2.32 g (7.4%)
9,9-Dichloro-9-silafluorene
[0752] Lithium wire (3.33 g, 0.08 mol) was washed with pentane,
carefully cut into small pieces, and suspended in 150 mL of
Et.sub.2O. While stirring, 2,2-dibromobiphenyl (25 g, 0.08 mol) 100
mL of diethyl ether was added dropwise over 1 hour and the contents
were allowed to stir for 10 hours. The mixture was filtered through
a frit to remove any unreacted Li and LiBr. The filtrated was
loaded into an addition funnel and slowly dropped into a solution
containing SiC.sub.14 (50 g, 0.08 mol) in 200 mL of Et.sub.2O.
After addition, the contents were stirred at room temperature for 5
hours. The solvent was removed in vacuo and 300 mL of pentane was
added. The solution was filtered to remove LiCl and the solvents
were again removed in vacuo. The solids were then loaded into a
sublimator and allowed to sublime at 150.degree. C. under fall
vacuum. Yield was 10.0 g (51%).
4-(3',5'-dimethylphenyl)-2-isopropylindene
[0753] 4-chloro-2-isopropylindene (10 g, 54 mmol) and
NiCl.sub.2(PPh.sub.3).sub.2 (1.8 g, 2.8 mmol) were dissolved in 150
mL of Et.sub.2O. 3,5-Dimethylphenylmagnesium bromide (54 mmol) as a
Et.sub.2O solution was added under vigorous stirring and the
reaction was stirred overnight at room temperature. After overnight
stirring, the reaction was slowly quenched with H.sub.2Oto
neutralize unreacted Grignard. The solution was subsequently
treated with 100 mL of 10% HCl(aq) neutralized with saturated
sodium bicarbonate aqueous solution. The organic layer was dried
with magnesium sulfate and the solvent was removed by rotary
evaporation. The remaining residue was loaded onto a silica gel
column and eluted with hexane. Yield was 5.5 g (39%).
lithium 443',5'-dimethylphenyl).sub.2-isopropylindene
[0754] 4-(3',5'-dimethylphenyl)-2-methylindene (5.6 g, 24 mmol) was
dissolved in 80 mL of pentane. To this solution was added 9.6 mL of
n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4
hours at room temperature. A white solid precipitated from solution
and was collected by frit filtration and washed with additional
pentane. Yield was 4.5 g (80%).
9-silafluorenebis(4-(3',5'-dimethylphenyl)-2-isopropylindene
[0755] 9,9-dichloro-9-silafluorene (1.4 g, 11 mmol) was dissolved
in 80 mL of THF. To this solution was slowly added lithium
4-(3',5'-dimethylphenyl- )-2-methylindene (3.0 g, 11 mmol) as a dry
powder and the solution was stirred overnight. After this time, the
solvent was removed in vacuo and the residue was taken up in
diethyl ether. The solution was filtered through frit to remove
LiCl and the solvent was removed in vacuo and used as a crude
product (2.1 g) for the next step.
[9-silafluorenebis(4-(3',5'-dimethylphenyl)-2-isopropylindene]ZrCl.sub.2
[0756] The crude solid from the previous step (2.1 g, 3.2 mmot) was
taken up in 50 mL of diethyl ether. To this solution was slowly
added n-BuLi (2.56 mL, 2.5 M in hexane) and then stirred for 3
hours at room temperature. The solution was cooled to -30.degree.
C. and ZrCl.sub.4 (0.74 g, 3.2 mmol) was added as a dry powder and
stirred at room temperature for two hours. The solvent was removed
in vacuo and toluene was added to the crude residue. The solution
was filtered to remove LiCl. The filtrate was concentrated and
pentane was added under heating. The solution was cooled to induce
crystallization. Yield of pure rac/meso metallocene was 120 mgs
(3.8%).
Supported Metallocene Catalyst System 10
Rac/meso
[9-silafluorenebis(4-(3',5'dimethylphenyl)-2-isopropylindene]zirc-
onium dichloride/MAO
[0757] In a 100 mL round bottom flask rac/meso
[9-silafluorenebis(4-(3',5'-
-dimethylphenyl)-2-isopropylindene]zirconium dichloride (0.076 g)
was added to the MAO solution (6.74 g, 7.2 mL) and stirred twenty
minutes. This was filtered through a medium glass frit funnel and
washed with toluene (14 mL). To the combined filtrates was added
dehydrated silica (4.0 g, Davison 948 Regular, 600.degree. C.
dehydration). This slurry was stirred for twenty minutes, then
dried at 40.degree. C. for two minutes under vacuum on a rotary
evaporator until the liquid evaporated, and then the solid was
further dried a total of about two hours and thirty minutes. The
supported catalyst was recovered as a dull purple, free flowing
solid (5.06 g).
POLYMERIZATIONS
Isotactic Polypropylene Homopolymer
[0758] The polymerization procedure for producing homopolymers with
the supported catalyst systems prepared as described above was as
follows. In a clean, dry two liter autoclave which had been flushed
with propylene vapor, TEAL scavenger (0.3 mL, l.5M) was added.
Hydrogen gas was added at this point if indicated. The quantity of
hydrogen is 1.55 millimoles for each psi added as shown in the
Tables. The reactor was closed and filled with 800 mL liquid
propylene. After heating the reactor to the indicated
polymerization temperature, the catalyst was added by washing in
with propylene (200 mL). After the indicated time, typically one
hour, the reactor was cooled, and the excess propylene vented. The
polymer was removed and dried.
Random Copolymer (RCP)
[0759] The polymerization procedure for producing random copolymers
with the supported catalyst systems prepared as described above was
as follows. In a clean, dry two titer autoclave which had been
flushed with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was
added. Hydrogen gas was added at this point if indicated. The
quantity of hydrogen is 1.55 millimoles for each psi added as shown
in the Tables. The reactor was closed and filled with 800 mL liquid
propylene. After heating the reactor to 60.degree. C., a partial
pressure of ethylene was added as indicated and then the catalyst
was added by washing in with propylene (200 mL). Ethylene gas was
fed to maintain a constant pressure. After the indicated time,
typically one hour, the reactor was cooled, and the excess
propylene and ethylene vented. The polymer was removed and
dried.
Impact Copolymers (ICP)
[0760] The polymerization procedure for producing ICP with the
supported catalyst systems prepared as described above was as
follows. In a clean, dry two liter autoclave which had been flushed
with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added.
Hydrogen gas was added at this point The quantity of hydrogen is
1.55 millimoles for each psi added as shown in the Tables. The
reactor was closed and filled with 800 mL liquid propylene. After
heating the reactor to 70.degree. C., the catalyst was added by
washing in with propylene (200 mL). After the indicated time,
typically one hour, the reactor was vented to about 170 psig
pressure and then an ethylene/propylene gas mixture was passed
through the reactor at the rates indicated while maintaining 200
psig. At the end of the gas phase stage, typically 90 to 150
minutes, the reactor was vented and cooled under N2. The granular
ICP polymer was removed and dried.
[0761] Polymerization run numbers 1-14 were made using Supported
Comparison Metallocene Catalyst System 1. Results are reported in
Tables 1 and 2.
[0762] Polymerization run numbers 15-25 made using Supported
Comparison Metallocene Catalyst System 2 Results are reported in
Tables 3 and 4.
[0763] Polymerization run numbers 26-39 were made using Supported
Metallocene Catalyst System 3A. Results are reported in Tables 5
and 6.
[0764] Polymerization run numbers 40-45 were made using Supported
Metallocene Catalyst System 3B. Results are reported in Tables 7
and 8.
[0765] Polymerization run numbers 46-64 were made using Supported
Metallocene Catalyst System 3C. Results are reported in Tables 9
and 10.
[0766] Polymerization run numbers 65-71 were made using Supported
Metallocene Catalyst System 4. Results are reported in Tables 11
and 12.
[0767] Polymerization run numbers 72-88 were made using Supported
Metallocene Catalyst System 5. Results are reported in Tables 13
and 14.
[0768] Polymerization run numbers 89-98 were made using Supported
Metallocene Catalyst System 6. Results are reported in Tables 15
and 16.
[0769] Polymerization run numbers 99-1ll were made using Supported
Metallocene Catalyst System 7. Results are reported in Tables 17
and 18.
[0770] Polymerization run numbers 112-116 were made using Supported
Metallocene Catalyst System 8. Results are reported in Tables 19
and 20.
[0771] Polymerization run numbers 117-132 were made using Supported
Metallocene Catalyst System 9. Results are reported in Tables 21
and 22.
[0772] Polymerization run numbers 133 and 134 were made using
Supported Metallocene Catalyst System 10. Results are reported in
Tables 23 and 24.
POLYMER ANALYSIS
[0773] Molecular weight determinations were made by gel permeation
chromatography (GPC) according to the following technique.
Molecular weights and molecular weight distributions were measured
using a Waters 150C gel permeation chromatography equipped with
Shodex (Showa Denko) AT-806MS columns and a differential refractive
index (DRI) detector operating at 145.degree. C. with
1,2,4-trichlorobenzene as the mobile phase at a 1.0 mL/min. flow
rate. The sample injection volume was 300 microliters. The columns
were calibrated using narrow polystyrene standards to generate a
universal calibration curve. The polypropylene calibration curve
was established using k=8.33.times.10.sup.-5 and a=0.800 as the
Mark-Houwink coefficients. The numerical analyses were performed
using Waters "Expert-Ease" software running on a VAX 6410
computer.
[0774] Ethylene amounts in the random copolymers were determined by
FT-FR using a calibration obtained from samples whose composition
was determined by NMR.
[0775] DSC melting points were determined on commercial DSC
instruments and are reported as the second melting point. The
polymer granules weighing less than 10 milligrams were heated to
230.0.degree. C. for ten minutes and then cooled from 2300C to
50.degree. C. at 10.degree. C./minute. The sample is held at 50C
for five minutes. The second melt is then recorded as the sample is
heated from 50.degree. C. to 200.degree. C. at a rate of 10.degree.
C./minute. The peak temperature is recorded as the second melting
point.
1TABLE 1 racemic dimethylsiladiyl(2-methyl-4-phenyl- indenyl).sub.2
zirconium dichloride/MAO - comparison Metallocene Catalyst Cat Time
C.sub.2.sup.=/C.sub.3.sup.= System TEMP. Amount Yield Efficiency
C2= H2 split flow rates RUN # (Comparison) (.degree. C.) (mg) (g)
(Kg/g cat) (delta psi) (delta psi) (min.) (l/min.) 1 1 60 67 274.7
4.10 0 0 60 -- 2 1 60 45 71.7 1.59 0 0 60 -- 3 1 60 40 134.1 3.35
10 0 60 -- 4 1 60 42 221.5 5.27 20 0 60 -- 5 1 60 30 121.3 4.04 55
0 60 -- 6 1 60 30 130.2 4.34 70 0 60 -- 7 1 60 30 101.8 3.39 20 0
60 -- 8 1 70 45 293.5 6.52 -- 50 60 -- 9 1 70 31 198.9 6.42 -- 50
60 -- 10 1 70 30 291.9 9.73 -- 50 60/150 4.0/1.0 11 1 70 30 231.3
7.71 -- 50 60/90 4.0/1.0 12 1 70 30 224.8 7.49 -- 50 60/90 4.1/0.9
13 1 70 30 209.9 7.00 -- 50 60/90 3.6/1.4 14 1 70 30 208.2 6.94 --
50 60/90 4.0/1.0
[0776]
2TABLE 2 racemic dimethylsiladiyl(2-methyl-4-phenyl- indenyl).sub.2
zirconium dichloride/MAO - comparison Metallocene Ethylene Catalyst
Total in Total Melting IV System Ethylene Rubber Rubber Final MFR
Point Of RUN # (Comparison) (wt %) (wt %) (wt %) (g/10 min.)
(.degree. C.) MW MWD Copolymer 1 1 -- -- -- 0.16 149.2 600.0 2.00
-- 2 1 -- -- -- 0.54 148.2 664.9 1.92 -- 3 1 0.67 -- -- 0.84 142.0
349.0 2.09 -- 4 1 1.28 -- -- 2.57 138.4 280.0 1.95 -- 5 1 3.77 --
-- 6.48 121.4 255.0 2.04 -- 6 1 4.43 -- -- 5.95 116.0 301.0 2.30 --
7 1 1.44 -- -- 2.05 137.5 330.4 2.23 -- 8 1 -- -- -- 99.6 150.3
120.6 3.01 -- 9 1 -- -- -- 58.95 150.9 135.7 3.15 -- 10 1 13.23
49.20 26.89 178.5 151.2 81.2 3.37 0.7520 11 1 7.58 47.37 16.00
134.05 150.6 98.4 3.25 0.687 12 1 7.82 50.04 15.63 127.16 150.0
100.4 3.11 0.708 13 1 5.3 38.96 13.60 201.9 150.43 91.2 3.28 0.779
14 1 0.47 64.32 0.73 97.1 150.8 116.8 3.42 not submit.
[0777]
3TABLE 3 racemic dimethylsiladiyl(2-methyl-4-[1-nap-
hthyl]indenyl).sub.2 zirconium dichloride/MAO - comparison
Metallocene Cat Time C.sub.2.sup.=/C.sub.3.sup.= Catalyst Amount
Yield Efficiency C2= H2 split flow rates RUN # System (mg) (g)
(Kg/g cat) (delta psi) (delta psi) (min.) (l/min.) 15 2 76 332.0
4.37 -- 40 60 -- 16 2 61 260.8 4.28 -- 35 60/120 4.0/1.0 17 2 60
266.2 4.44 -- 35 60/120 4.4/0.6 18 2 60 272.6 4.54 -- 35 60/120
4.2/0.8 19 2 61 196.9 3.23 -- 35 60 -- 20 2 61 121.2 1.99 20 5 60
-- 21 2 61 118.1 1.94 30 5 60 -- 22 2 61 137.7 2.26 40 5 60 -- 23 2
62 141.9 2.29 50 5 60 -- 24 2 60 138.6 2.31 40 10 60 -- 25 2 62
234.8 3.79 -- 50 60/90 4.0/1.0
[0778]
4TABLE 4 racemic dimethylsiladiyl(2-methyl-4-[1-nap-
hthy]indenyl).sub.2zirconium dichloride/MAO - comparison Ethylene
Metallocene Total in Total Melting IV Catalyst Ethylene Rubber
Rubber Final MFR Point Of RUN # System (wt %) (wt %) (wt %) (g/10
min.) (.degree. C.) MW MWD Copolymer 15 2 -- -- -- 4.08 150.5 299.1
2.78 -- 16 2 7.76 47.27 16.42 4.76 151.7 212.1 2.68 1.6567 17 2
16.39 61.45 26.67 1.3 150.8 230.9 3.33 1.7048 18 2 9.74 51.52 18.91
4.98 151.0 210.4 2.96 1.7127 19 2 -- -- -- 3.12 151.0 278.0 2.49 --
20 2 1.27 -- -- 0.19 138.43 603.0 2.59 -- 21 2 1.75 -- -- 0.15
136.10 614.8 2.59 -- 22 2 2.25 -- -- 0.196 131.90 604.5 2.31 -- 23
2 2.82 -- -- 0.213 127.83 579.0 2.36 -- 24 2 2.39 -- -- 0.225
131.63 542.8 2.41 -- 25 2 3.803 48.39 7.86 4.95 151.43 176.8 2.94
1.425
[0779]
5TABLE 5 racemic dimethylsiladiyl-bis-(4-(3',5'-di--
tertbutylphenyl)-2- methylindenyl) zirconium dichloride/MAO
Metallocene Cat Time C.sub.2.sup.=/C.sub.3.sup.= Catalyst Amount
TEMP. Yield Efficiency C2= H2 split flow rates RUN # System (mg)
(.degree. C.) (g) (Kg/g cat) (delta psi) (delta psi) (min.)
(l/min.) 26 3A 46 60 37.8 0.82 -- 0 60 -- 27 3A 47 60 83.4 1.8 5 0
60 -- 28 3A 45 60 125.8 2.8 10 0 60 -- 29 3A 46 60 135.0 2.9 20 0
60 -- 30 3A 45 60 268.7 6.0 35 0 58 -- 31 3A 20 70 111.2 5.6 -- 35
60 -- 32 3A 32 70 192.8 6.0 -- 35 60 -- 33 3A 32 70 186.9 5.8 -- 25
60/60 4.0/1.0 34 3A 33 70 227.0 6.9 -- 35 60/90 4.0/1.0 35 3A 33 70
245.5 7.4 -- 35 60/120 4.0/1.0 36 3A 32 70 204.9 6.4 -- 35 60/60
3.6/1.4 37 3A 30 70 194.7 6.5 -- 35 45/120 4.0/1.0 38 3A 30 70
238.0 7.9 -- 35 60/120 4.4/0.6 39 3A 33 70 266.9 8.1 -- 35 60/120
4.2/0.8
[0780]
6TABLE 6 racemic dimethylsiladiyl-bis-(4-(3',5'-di--
tertbutylphenyl)-2-methylindenyl) zirconium dichloride/MAO Ethylene
Metallocene Total in Total Melting IV Catalyst Ethylene Rubber
Rubber Final MFR Point Of RUN # System (wt %) (wt %) (wt %) (g/10
min.) (.degree. C.) MW MWD Copolymer 26 3A -- -- -- 0.12 156.63
681.3 2.44 -- 27 3A 0.095 -- -- 0.6 153.77 569.1 2.43 -- 28 3A 0.34
-- -- 1.63 150.23 428.2 2.49 -- 29 3A 1.3 -- -- 2.65 144.43 316.8
1.91 -- 30 3A 1.8 -- -- 4.78 140.97 271.4 1.86 -- 31 3A -- -- --
15.03 156.77 192.9 2.37 -- 32 3A -- -- -- 6.88 157.37, 220.4 2.50
-- 143.3 minor 33 3A 4.58 41.88 10.9 7.37 156.57 267.8 3.65 1.003
34 3A 3.87 41.02 9.43 15.37 156.57 185.2 3.21 0.957 35 3A 6.18
41.17 15.0 15.88 156.97 172.2 3.44 0.841 36 3A 3.84 27.28 14.1
12.76 157.17 227.4 3.32 0.824 37 3A 7.45 39.17 19.0 18.61 156.50
163.8 3.23 0.844 38 3A 11.19 54.72 20.4 6.76 157.37 233.5 3.62
1.039 39 3A 7.88 46.66 16.9 12.75 156.43 194.6 3.17 0.876
[0781]
7TABLE 7 racemic dimethylsiladiyl-bis-(4-(3',5'-di--
tertbutylphenyl)- 2-methylindenyl) zirconium dimethyl/NCA
Metallocene Cat Time C.sub.2.sup.=/C.sub.3.sup.= RUN Catalyst
Amount Temp. Yield Efficiency H2 split flow rates NUMBER System
(mg) (.degree. C.) (g) (Kg/g cat) (delta psi) (min.) (l/min.) 40 3B
47 60 2.9 0.06 0 60 -- 41 3B 202 60 17.2 0.85 0 60 -- 42 3B 33 70
162.9 4.94 35 60 -- 43 3B 34 70 203.1 5.97 35 60/120 4.2/0.8 44 3B
31 70 187.5 6.05 35 60/120 4.4/0.6 45 3B 31 70 169.7 5.47 35 60/60
4.2/0.8
[0782]
8TABLE 8 racemic dimethylsiladiyl(4-(3',5'-di-tertb-
utylphenyl)-2-methylindenyl) zirconium dimethyl/NCA Ethylene
Metallocene Total in Total Melting IV RUN Catalyst Ethylene Rubber
Rubber Final MFR Point Of NUMBER System (wt %) (wt %) (wt %) (g/10
min.) (.degree. C.) MW MWD Copolymer 40 3B -- -- -- DNA 156.63
821.6 1.98 -- 41 3B -- -- -- 0.075 158.43 898.8 -- 42 3B -- -- --
14.7 159.1 202.3 2.30 -- 43 3B 7.284 49.49 14.7 28.01 158.23 161.2
2.40 0.908 44 3B 11.13 55.59 20.0 12.3 157.83 180.8 2.29 1.073 45
3B 3.96 48.66 8.14 23.7 158.1 158.8 2.25 1.055
[0783]
9TABLE 9 racemic dimethylsiladiyl-bis-(4-(3',5'-di-
tertbutylphenyl)-2-methylindenyl) zirconium dimethyl/MAO
Metallocene Cat Catalyst Amount TEMP. Yield Efficiency C2= H2 Time
RUN # System (mg) (.degree. C.) (g) (Kg/g cat) (delta psi) (delta
psi) (min.) 46 3C 50 70 166.5 3.3 -- 50 60 47 3C 50 70 60.9 1.2 --
25 60 48 3C 50 70 153.4 3.1 -- 60 60 49 3C 34 60 17.8 0.52 20 0 60
50 3C 35 60 89.1 2.5 20 20 60 51 3C 36 60 96.4 2.7 30 20 60 52 3C
36 60 84.9 2.4 50 20 60 53 3C 60 60 130.3 2.2 30 35 40 54 3C 51 70
138.6 2.7 -- 60 60 55 3C 50 70 65.6 1.3 -- 40 60 56 3C 50 70 117.6
2.4 -- 55 60 57 3C 50 70 65.9 1.3 -- 40 60 58 3C 150 70 252.4 1.68
-- 40 55 59 3C 101 70 191.0 1.9 -- 50 60 60 3C 50 70 133.0 2.7 --
55 60 61 3C 51 70 90.7 1.8 -- 55 60 62 3C 62 60 92.7 1.5 30 10 60
63 3C 51 70 122.3 2.4 -- 55 60 64 3C 102 70 229.6 2.3 -- 55 60
[0784]
10TABLE 10 racemic dimethylsiladiyl-bis-(4-(3',5'-d- i-
tertbutylphenyl)-2-methylindenyl) zirconium dimethyl/NCA
Metallocene Total Melting RUN Catalyst Ethylene Final MFR Point #
System (wt %) (g/10 min.) (.degree. C.) MW MWD 46 3C -- 12.53
157.03 187.7 2.33 47 3C -- 0.803 156.9 445.3 2.10 48 3C -- 109.65
157.5 109.1 2.46 49 3C 1.3 6.92 145.43 357.9 1.83 50 3C 1.4 17.01
145.1 203.7 2.04 51 3C 2.1 19.33 139.30 188.7 1.97 52 3C 3.0 27.96
133.63 162.9 1.76 53 3C 1.7 50.22 142.7 152.3 2.52 54 3C -- 486
158.23 79.9 2.84 55 3C -- 6.2 158.17 338.2 2.77 56 3C -- 66.37
157.77 133.7 2.60 57 3C -- 2.42 158.03 381.7 2.62 58 3C -- 5.38
158.3 344.6 2.60 59 3C -- 15.59 157.97 289.3 2.75 60 3C -- 76.4
158.23 125.0 2.14 61 3C -- 5.95 158.63 245.1 2.58 62 3C 1.0 5.93
140.57 277.0 1.83 63 3C -- 6.75 157.7 234.4 3.00 64 3C -- 6.3
157.43 240.2 2.52
[0785]
11TABLE 11 racemic[9-silafluorenebis(4-(3',5'-di-t--
butylphenyl)-2-methylindenyl] zirconium dichloride/MAO Metallocene
Cat Time C.sub.2.sup.=/C.sub.3.sup.= Catalyst Amount TEMP. Yield
Efficiency H2 split flow rates RUN # System (mg) (.degree. C.) (g)
(Kg/g cat) (delta psi) (min.) (l/min.) 65 4 299 60 13.2 0.04 0 6 --
66 4 61 60 35.0 0.57 0 60 -- 67 4 60 70 81.3 1.4 35 60 -- 68 4 32
70 96.2 3.0 35 60/90 4.0/1.0 69 4 30 70 93.3 3.1 35 60/120 4.0/1.0
70 4 31 70 83.9 2.7 35 60/90 3.6/1.4 71 4 30 70 77.8 2.6 35 60/120
4.2/0.8
[0786]
12TABLE 12 racemic[9-silafluorenebis(4-(3',5'-di-t--
butylphenyl)-2-methylindenyl]zirconium dichloride/MAO Metallocene
Total Ethylene in Total Final Melting IV Catalyst Ethylene Rubber
rubber MFR Point of RUN # System (wt %) (wt %) (wt %) (g/10 min.)
(.degree. C.) MW MWD Copolymer 65 4 -- -- -- 0.65 156.17 412 149.3
-- 66 4 -- -- -- 0.075 156.23 710.8 2.71 -- 67 4 -- -- -- 3.59
156.5 270.7 2.82 -- 68 4 4.814 54.74 8.8 69.59 155.43 119.4 3.22 69
4 6.624 49.55 13.4 9.84 156.5 200.0 3.56 70 4 3.095 42.72 7.2 14.54
155.97 194.5 3.52 71 4 7.691 54.36 14.1 10.61 157.17 207.1 3.50
[0787]
13TABLE 13 racemic[9-silafluorenebis(4-(3',5'-di-t--
butylphenyl)-2-isopropylindenyl] zirconium dichloride/MAO
Metallocene Cat Time C.sub.2.sup.=/C.sub.3.sup.= Catalyst Amount
TEMP. Yield Efficiency C2= H2 split flow rates RUN # System (mg)
(.degree. C.) (g) (Kg/g cat) (delta psi) (delta psi) (min.)
(l/min.) 72 5 300 60 11.8 0.04 -- 0 10 -- 73 5 120 70 116.8 0.97 --
10 60 -- 74 5 121 70 127.6 1.1 -- 10 60/90 4.0/1.0 75 5 62 70 126.4
2.0 -- 20 60 -- 76 5 63 70 139.5 2.2 -- 35 60 -- 77 5 60 70 151.4
0.40 -- 20 60/90 4.2/0.8 78 5 62 70 246.2 4.0 -- 35 60/90 4.2/0.8
79 5 60 70 218.9 3.6 -- 35 60/120 4.2/0.8 80 5 62 70 249.8 4.0 --
50 60 -- 81 5 61 70 233.1 3.8 -- 35 60/120 4.4/0.6 82 5 61 60 184.2
3.0 10 20 60 -- 83 5 60 60 202.6 3.4 20 20 60 -- 84 5 60 60 209.6
3.5 30 20 60 -- 85 5 60 70 157.9 2.6 -- 35 30/120 4.4/0.6 86 5 63
70 200.5 3.2 -- 35 60 -- 87 5 60 70 223.9 3.7 -- 35 60/120 4.2/0.8
88 5 60 70 196.1 3.3 -- 35 60/180 4.2/0.8
[0788]
14TABLE 14 racemic[9-silafluorenebis(4-(3',5'-di-t--
butylphenyl)-2-isopropylindenyl]zirconium dichloride/MAO
Metallocene Total Ethylene in Total Final Melting IV Catalyst
Ethylene Rubber rubber MFR Point of RUN # System (wt %) (wt %) (wt
%) (g/10 min.) (.degree. C.) MW MWD Copolymer 72 5 -- -- -- 0.82
160.78 381.6 2.01 -- 73 5 -- -- -- 2.85 159.17 267.3 1.80 -- 74 5
4.297 32.93 13.0 3.56 161.1 255.7 2.03 2.92 75 5 -- -- -- 11.53
158.83 191.5 2.25 -- 76 5 -- -- -- 24.03 159.43 166.6 1.98 -- 77 5
2.449 32.63 7.5 12.0 159.7 194.7 2.11 2.06 78 5 2.012 42.53 4.7
110.44 159.1 116.8 2.48 2.21 79 5 3.389 40.38 8.4 32.37 158.5 173.2
2.71 2.55 80 5 -- -- -- 499.99 157.9 85.7 2.25 -- 81 5 4.093 47.35
8.6 41.24 158.57 147.0 2.32 2.87 82 5 0.87 -- -- 9.54 151.17 204.2
2.39 -- 83 5 1.4 -- -- 18.53 146.17 182.3 2.14 -- 84 5 2.4 -- --
24.5 138.5 172.2 1.93 -- 85 5 4.732 46.4 10.2 118.7 158.23 119.7
2.39 86 5 -- -- -- 28.17 158.37 -- 87 5 3.081 44.21 7.0 61.24
158.83 88 5 -- -- -- 15.7 158.77 --
[0789]
15TABLE 15 dimethylsiladiyl-bis-(2-methyl-4-(3',5'--
di-methylphenyl)indenyl)zirconium dichloride/MAO Metallocene Cat
Time C.sub.2.sup.=/C.sub.3.sup.= Catalyst TEMP. Amount Yield
Efficiency C2= H2 split flow rates RUN # System (.degree. C.) (mg)
(g) (Kg/g cat) (delta psi) (delta psi) (min.) (l/min.) 89 6 60 45
72.7 1.6 0 0 60 -- 90 6 60 45 111.9 2.5 5 0 60 -- 91 6 60 47 155.6
3.3 10 0 60 -- 92 6 60 46 204.9 4.5 20 0 60 -- 93 6 60 45 244.5 5.4
35 0 60 -- 94 6 70 30 251.2 8.4 -- 35 60/90 4.0/1.0 95 6 70 30
236.8 7.9 -- 35 60/90 3.6/1.4 96 6 70 32 259.5 8.7 -- 35 60/90
4.2/0.8 97 6 70 33 249.4 7.6 -- 35 60/90 4.4/0.6 98 6 70 33 186.8
5.7 -- 35 60
[0790]
16TABLE 16 dimethylsiladiyl-bis-(2-methyl-4-(3',5'--
di-methylphenyl)indenyl)zirconium dichloride/MAO Metallocene Total
Ethylene in Total Final Melting IV Catalyst Ethylene Rubber Rubber
MFR Point of RUN # System (wt %) (wt %) (wt %) (g/10 min.)
(.degree. C.) MW MWD Copolymer 89 6 -- -- -- 0.0245 150.9 937.7
2.10 -- 90 6 -- -- -- 0.17 148.3 671.3 2.15 -- 91 6 0.18 -- -- 0.59
145.03 463.6 2.01 -- 92 6 1.1 -- -- 2.68 140.9 303.8 1.89 -- 93 6
1.8 -- -- 3.98 135.43 255.7 1.74 -- 94 6 8.11 49.7 16.3 4.54 152.57
281.1 3.51 0.866 95 6 5.34 40.32 13.2 6.25 151.97 284.5 3.57 0.861
96 6 9.98 58.47 17.1 7.07 152.43 220.4 3.00 1.420 97 6 14.42 61.66
23.4 19.43 152.1 179.4 2.57 1.091 98 6 -- -- -- 1.79 151.30 327.9
1.98 --
[0791]
17TABLE 17 dimethylsiladiyl-bis-(4-(3',5'-bistriflu-
oromethylphenyl)- 2-methyl-indenyl) zirconium dichloride/MAO
Metallocene TEAL Cat Time C.sub.2.sup.=/C.sub.3.sup.= Catalyst
Amount Amount Yield Efficiency H2 split flow rates RUN # System
(mls) (mg) (g) (Kg/g cat) (delta psi) (min.) (l/min.) 99 7 0.3 45
5.4 0.12 0 60 -- 100 7 0.3 31 82.0 2.6 35 60 -- 101 7 0.3 21 47.3
2.3 35 60 -- 102 7 0.3 30 102.0 3.4 35 60/90 4.0/1.0 103 7 0.3 32
95.2 3.0 35 60/90 3.6/1.4 104 7 0.3 30 97.9 3.3 35 60/120 4.0/1.0
105 7 0.3 32 98.1 3.1 35 90/120 4.4/0.6 106 7 0.3 30 97.3 3.2 35
60/120 4.2/0.8 107 7 0.3 32 44.7 1.4 35 45/120 4.0/1.0 108 7 0.3 60
88.7 1.5 20 109 7 0.3 61 110.8 1.8 20 60/90 4.0/1.0 110 7 0.3 61
134.0 2.2 20 60/90 3.6/1.4 111 7 0.3 61 134.2 2.2 20 60/90
4.2/0.8
[0792]
18TABLE 18 dimethylsiladiyl-bis-(4-(3',5'-bistriflu-
oromethylphenyl)-2-methyl-indenyl) zirconium dichloride/MAO
Metallocene Total Ethylene in Total Final Melting IV Catalyst
Ethylene Rubber rubber MFR Point of RUN # System (wt %) (wt %) (wt
%) (g/10 min.) (.degree. C.) MW MWD Copolymer 99 7 -- -- -- --
154.5 606.8* 3.32 -- 100 7 -- -- -- 31.06 155.23 159.9 3.99 -- 101
7 -- -- -- 28.75 156.5 172.8 3.74 -- minor 142.98 102 7 5.829 52.53
11.1 341.43 154.3 87.4 3.75 1.45 103 7 3.784 44.54 8.5 185.49
154.83 101.8 3.97 0.74 104 7 9.308 52.05 17.9 102.01, 154.7 110.8
3.17 0.80 93.56 105 7 13.09 61.09 21.4 134.68, 154.5 100.0 3.22
1.03 127.37 106 7 15.59 55.49 28.0 36.04, 155.23 148.8 3.40 0.89
32.5 107 7 9.271 51.57 18.0 356.35, 154.3 78.9 3.60 0.77 348.24 108
7 -- -- 4.08, 155.43 285.0 2.93 5.64 109 7 11.75 50.58 23.2 17.27,
154.57 219.5 4.26 0.79 18.28 110 7 11.75 40.45 29.0 35.6 154.70
202.9 4.69 0.78 111 7 14.84 55.87 26.6 14.8 154.70 204.2 4.24
0.84
[0793]
19TABLE 19 dimethylsiladiyl-bis-(4-(3',5'-bistriflu-
oromethylphenyl)-2-methylindenyl) zirconium dichloride/MAO
Metallocene Cat Time C.sub.2.sup.=/C.sub.3.sup.= Catalyst Amount
TEMP. Yield Efficiency H2 split flow rates RUN # System (mg)
(.degree. C.) (g) (Kg/g cat) (delta psi) (min.) (l/min.) 112 8 60
60 40.8 0.68 0 60 -- 113 8 31 70 107.3 3.5 35 60 -- 114 8 30 70
123.6 4.1 35 60/90 4.0/1.0 115 8 30 70 112.2 3.7 35 60/90 3.6/1.4
116 8 30 70 123.8 4.1 35 60/90 4.4/0.6
[0794]
20TABLE 20 dimethylsiladiylbis(4-(3',5'-bis-trimeth-
ylsilyl-phenyl)-2-methylindenyl) zirconium dichloride/MAO
Metallocene Total Ethylene in Total Final Melting IV Catalyst
Ethylene Rubber rubber MFR Point of RUN # System (wt %) (wt %) (wt
%) (g/10 min.) (.degree. C.) MW MWD Copolymer 112 8 -- -- -- 0.13
155.3 594.2 1.92 -- 113 8 -- -- -- 3.59 155.77 269.8 2.19 -- 114 8
4.148 44.34 9.4 61.05 156.1 128.1 2.79 115 8 4.069 24.09 16.9 19.73
156.97 171.4 3.00 116 8 6.852 52.48 13.1 12.82 156.5 155.6 3.71
[0795]
21TABLE 21 dimethylsiladiylbis[4-(3',5'-dimethylphe-
nyl)-2-isopropylindenyl]zirconium dichloride/MAO Metallocene Cat
Time Catalyst Amount Temp. Yield Efficiency H2 split
C.sub.2.sup.=/C.sub.3.sup.=flow RUN # System (mg) (.degree. C.) (g)
(Kg/g cat) (delta psi) (min.) rates (l/min.) 117 9 304 60 16.6 0.05
0 60 -- 118 9 300 70 47.5 0.16 5 20 -- 119 9 60 70 25.5 0.43 5 60
-- 120 9 121 70 63.0 0.52 5 60 -- 121 9 120 70 79.4 0.66 5 60/90
4.0/1.0 122 9 122 70 99.1 0.81 5 60/90 4.1/0.9 123 9 123 70 71.2
0.57 5 60/90 3.6/1.4 124 9 120 70 95.2 0.79 5 60/120 4.0/1.0 125 9
121 70 143.7 1.2 10 60/90 4.0/1.0 126 9 124 70 167.6 1.4 10 60/90
4.2/0.8 127 9 120 70 101.5 0.85 10 60 -- 128 9 121 70 121.2 1.0 10
60/90 4.4/0.6 129 9 121 70 167.6 1.4 20 60 -- 130 9 124 70 259.3
2.1 35 60 -- 131 9 30 70 99.3 3.31 35 60/90 4.0/1.0 132 9 33 70
80.3 2.4 35 60 --
[0796]
22TABLE 22 dimethylsiladiylbis[4-(3',5'-dimethylphe-
nyl)-2-isopropylindenyl]zirconium dichloride/MAO Metallocene Total
Ethylene in Total IV Catalyst Notebook Ethylene Rubber rubber Final
MFR Melting Point of RUN # System (21810-) (wt %) (wt %) (wt %)
(g/10 min.) (.degree. C.) MW MWD Copolymer 117 9 077 -- -- -- 25.61
154.5 167.1 39.73 -- 118 9 078 -- -- -- 175.39 151.97 129.2 4.86 --
119 9 079 -- -- -- 87.33 152.03 134.5 3.39 -- 120 9 080 -- -- --
76.55 151.83 138.5 2.20 -- 121 9 081 8.199 39.92 20.5 14.16 153.43
213.6 3.05 2.833 122 9 082 7.068 42.81 16.5 15.43 152.03 196.3 3.01
2.505 123 9 083 8.294 26.52 31.3 4.92 152.77 248.0 3.28 2.662 124 9
084 15.85 39.17 40.5 0.479 153.23 306.7 4.14 3.667 125 9 086 7.521
37.72 19.9 27.72 153.03 204.7 3.61 2.202 126 9 087 10.02 44.73 22.4
5.8 152.63 235.8 3.58 3.508 127 9 089 -- -- -- 75.86 151.03 135.8
2.30 -- 128 9 097 21.21 56.17 37.8 0.53 152.10 280.9 3.84 3.356 129
9 104 -- -- -- 84.22 151.83 136.1 2.31 -- 130 9 105 -- -- -- 511.36
150.17 88.7 2.47 -- 131 9 106 2.133 44.04 4.84 824.95 150.17 83.6
2.95 1.29 132 9 107 -- -- -- 906.0 150.30 82.9 2.65 --
[0797]
23TABLE 23 [9-silafluorenebis(4-(3',5'-dimethylphen-
yl)-2-isopropylindene]zirconium dichloride/MAO Metallocene Cat
Catalyst TEMP. Amount Efficiency RUN # System (.degree. C.) (mg)
Yield (g) (Kg/g cat) H2 (delta psi) Time (min.) 133 10 60 302 6.0
0.02 0 60 134 10 70 121 18.4 0.15 10 60
[0798]
24TABLE 24 [9-silafluorenebis(4-(3',5'-dimethylphen- yl)-2-
isopropylindene]zirconium dichloride/MAO Metallocene Catalyst Final
MFR Melting Point RUN # System (g/10 min.) (.degree. C.) MW MWD 133
10 -- 150.9, 467.6 4.98 minor 156.52 134 10 32.07 156.5 104.8
2.71
[0799] While the present invention has been described and
illustrated by reference to particular embodiments, it will be
appreciated by those of ordinary skill in the art, that the
invention lends itself to many different variations not illustrated
herein. For these reasons, then, reference should be made solely to
the appended claims for purposes of determining the true scope of
the present invention.
* * * * *