U.S. patent application number 16/963709 was filed with the patent office on 2021-03-18 for 1,2-phenylene bridged 1-indenyl-2-indenyl metallocene complexes for olefin polymerisation.
The applicant listed for this patent is SABIC GLOBAL TECHNOLOGIES B.V.. Invention is credited to Vincenzo BUSICO, Roberta CIPULLO, Nicolaas Hendrika FRIEDERICHS, Bogdan A. GUZEEV, Coen HENDRIKSEN, Dmitry Y. MLADENTSEV, Dmitry V. UBORSKY, Antonio VITTORIA, Alexander Z. VOSKOBOYNIKOV.
Application Number | 20210079032 16/963709 |
Document ID | / |
Family ID | 1000005262750 |
Filed Date | 2021-03-18 |
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United States Patent
Application |
20210079032 |
Kind Code |
A1 |
HENDRIKSEN; Coen ; et
al. |
March 18, 2021 |
1,2-PHENYLENE BRIDGED 1-INDENYL-2-INDENYL METALLOCENE COMPLEXES FOR
OLEFIN POLYMERISATION
Abstract
The invention relates to a metallocene complexes according to
formula (I), (I) wherein R.sub.1 and R.sub.2 are independently
selected from H, an alkyl or an aryl group, wherein R.sub.3 is a
C1-C10 alkyl group, wherein R' is selected from H, an alkyl group,
an aryl group and wherein different R' substituents can be
connected to form a ring structure and wherein B is a 1,2 phenylene
bridging moiety, which can be optionally substituted, wherein Mt is
selected from Ti, Zr and Hf, X is an anionic ligand, z is the
number of X groups and equals the valence of Mt minus 2. The
invention also relates to a catalyst comprising the reaction
product of the metallocene complex and a cocatalyst. Further the
invention relates to a (co)polymerisation process of olefinic
monomers. ##STR00001##
Inventors: |
HENDRIKSEN; Coen; (Geleen,
NL) ; FRIEDERICHS; Nicolaas Hendrika; (Geleen,
NL) ; VOSKOBOYNIKOV; Alexander Z.; (Moscow, RU)
; VITTORIA; Antonio; (Avella, IT) ; BUSICO;
Vincenzo; (Napoli, IT) ; CIPULLO; Roberta;
(Napoli, IT) ; MLADENTSEV; Dmitry Y.; (Moscow,
RU) ; GUZEEV; Bogdan A.; (Moscow, RU) ;
UBORSKY; Dmitry V.; (Moscow, RU) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SABIC GLOBAL TECHNOLOGIES B.V. |
BERGEN OP ZOOM |
|
NL |
|
|
Family ID: |
1000005262750 |
Appl. No.: |
16/963709 |
Filed: |
January 23, 2019 |
PCT Filed: |
January 23, 2019 |
PCT NO: |
PCT/EP2019/051654 |
371 Date: |
July 21, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 10/02 20130101;
C08F 4/76 20130101; C07F 17/00 20130101 |
International
Class: |
C07F 17/00 20060101
C07F017/00; C08F 10/02 20060101 C08F010/02; C08F 4/76 20060101
C08F004/76 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 24, 2018 |
EP |
18153200.3 |
Claims
1. Metallocene complex according to formula I, ##STR00041## wherein
R.sub.1 and R.sub.2 are independently selected from H, an alkyl or
an aryl group, wherein R.sub.3 is a C1-C10 alkyl group, wherein R'
is selected from H, an alkyl group, an aryl group and wherein
different R' substituents are optionally connected to form a ring
structure, and wherein B is a 1,2 phenylene bridging moiety, which
is optionally substituted, wherein Mt is selected from Ti, Zr and
Hf, X is an anionic ligand, z is the number of X groups and equals
the valence of Mt minus 2.
2. The metallocene complex according to claim 1, wherein Mt is
zirconium or hafnium.
3. The metallocene complex according to claim 1, wherein X is a
methyl group, Cl, Br or I.
4. The metallocene complex according to claim 1, wherein R.sub.1
and R.sub.2 are chosen from H, methyl or phenyl groups.
5. The metallocene complex according to claim 1, wherein R.sub.3 is
chosen from a methyl or isopropyl group.
6. The metallocene complex according to claim 5, wherein bridge B
is a 1,2 phenylene bridge.
7. A catalyst comprising the metallocene complex according to claim
1 and a cocatalyst.
8. The catalyst according to claim 7, wherein the cocatalyst
includes aluminium- or boron-containing cocatalysts.
9. Process for the preparation of olefin polymers by polymerising
one or more olefins in the presence of a cocatalyst and the
metallocene complex according to anyone of claims 1-6, wherein the
metallocene complex optionally is immobilized on a support.
10. Polyolefin produced using the catalyst of claim 7.
11. Polyolefin according to claim 10, wherein the polyolefin is a
copolymer of ethylene and one of more of 1-butene, 1-hexene,
1-octene, vinyl-cyclohexane or 4-methyl-1-pentene.
12. Polyolefin according to claim 11 wherein the polyolefin is a
linear low-density polyethylene (LLDPE) having melt mass flow rate
as determined using ASTM D1238-10 at 190.degree. C./2.16 kg in the
range of from 0.5 to 125 g/10 min and a density in the range of
from 900 kg/m.sup.3 to less than 940 kg/m.sup.3 as determined using
ASTM D1505-10.
13. Articles comprising the polyolefins obtainable by the process
according to claim 9.
14. The metallocene complex according to claim 1, wherein Mt is
zirconium.
15. The metallocene complex according to claim 1, wherein X is a
methyl group or Cl.
16. The catalyst according to claim 7, wherein the cocatalyst
includes aluminoxanes.
Description
[0001] The invention relates to substituted 1,2-phenylene bridged
1-indenyl 2-indenyl metallocene complexes, a catalyst comprising
the substituted metallocene complex, a process for the preparation
of olefin polymers in the presence of substituted metallocene
complexes, the use of the olefin polymers for making articles and
articles comprising an olefin polymer.
[0002] Metallocene complexes together with a cocatalyst form
catalysts that are widely used for olefin polymerisation. In
general, the metallocene complexes are known to have only one
active polymerisation center and are often referred to as single
site catalysts or discrete catalysts to distinguish them from
non-single site catalysts like for instance Ziegler-type catalysts.
The presence of one active center is believed to result in polymers
having a narrow molecular weight distribution (MWD) and narrow
compositional distribution for copolymers of different olefins. An
advantage of metallocene catalysts is their high activity and well
defined structures compared to traditional Ziegler-Natta catalysts.
A further advantage of metallocene catalysts over conventional
Ziegler-type catalysts is that the former can display a higher
reactivity towards alpha-olefins, which is especially beneficial in
copolymerisations of ethylene with such alpha-olefins. Catalysts
with a high reactivity towards alpha-olefins require less
alpha-olefin during the polymerisation in order to reach a desired
alpha-olefin content in the final polymer, which is an advantage in
the commercial preparation of copolymers of ethylene with
alpha-olefins.
[0003] It is well known in the art that the reactivity of
alpha-olefins compared to ethylene decreases upon increasing the
size of the alpha-olefin. For instance, the reactivity decreases
from propylene>1-butene>1-hexene>1-octene, as has been
published for example by Krentsel et al in Polymers and Copolymers
of Higher alpha-Olefins, Carl Hanser Verlag, Munchen 1997 and by
McDaniel et al in Macromolecules 2010 (43) page 8836-8852.
Therefore, especially when copolymerising ethylene with higher
alpha-olefins like 1-hexene, catalysts are needed that display a
high reactivity towards such alpha-olefins.
[0004] An additional complication arises in the preparation of
copolymers of ethylene and alpha-olefins, which is related to the
general observation that the average molecular weight of the
obtained copolymers tends to decrease upon increasing alpha-olefin
content, which for example has been published by Friederichs, Wang,
Budzelaar and Coussens in Journal of Molecular Catalysis A:
Chemical 242 (2005) page 91-104. The combination of high comonomer
reactivity as well as high molecular weight is a challenging target
for developing commercially applicable metallocene catalysts.
[0005] Numerous patent applications are known describing
metallocene catalysts. For example, WO2014/099307 describes
metallocene catalysts for the polymerisation of ethylene to
branched polyethylene using a catalyst containing the metallocene
system
dimethylsilylene(2,3,4,5-tetramethyl-1-cyclopentadienyl)(3-phenyl-1-inden-
yl)zirconium dichloride. EP0372414 discloses a metallocene catalyst
with an ethylene bridged 1-indenyl 2-indenyl zirconium complex.
WO94/11406 discloses 2-indenyl complexes for olefin polymerisation.
WO2015/065681 describes a 1-indenyl bridged catalyst system.
Macromolecules 2004, 37, 2342-2347 (Reybuck and Waymouth) describes
an investigation of bridge and 2-phenyl substituent effects on
ethylene-alfa olefin copolymerisation behavior with dimethylsilyl
bridged bis 1-indenyl/2-indenyl zirconium complexes.
[0006] Metallocenes bearing 2-indenyl ligands are known in the art.
For example, U.S. Pat. No. 6,342,622 (SABIC/DSM) describes
2-indenyl containing bridged metallocenes, in which the bridge
contains an sp2 hybridized carbon. Organometallics, Vol. 20, No.
16, 2001 (Schaverien et al) describes 1,2 ethylene bridged
bis-2-indenyl zirconocenes. These metallocene catalysts result in
polymers having a low molecular weight. Journal of Organometallic
Chemistry, 2004, vol 689, pg 1965-1977 (Alt et al) describes
1,2-naphthylidene bridged metallocenes. In this publication it is
stated that 1,2-naphthylidene bridged metallocenes containing a
fluorenyl and a 2-indenyl ligand result in lower molecular weight
polyethylene compared to its fluorenyl/1-indenyl or
fluorenyl/cyclopentadienyl containing analogues. WO0029415
(Montell) describes methylene bridged bis-2-indenyl zirconocenes,
which also give polymers having a low molecular weight.
[0007] Despite all efforts, there is a need for a highly active
catalyst, which is able to produce polyolefins in a high yield,
having a high reactivity for alpha olefin incorporation (like for
example copolymerisation of ethylene with 1-hexene) and which is
still giving high molecular weight polymers.
[0008] A new family of metallocene complexes has now been
discovered which advantageously can be used for olefin
polymerisation, preferably for ethylene copolymerisation, and which
gives at least one advantage of a higher catalyst activity, a
higher 1-hexene incorporation and/or a high molecular weight
polymer.
SUMMARY OF THE INVENTION
[0009] The invention relates to a metallocene complex according to
formula I,
##STR00002##
wherein R.sub.1 and R.sub.2 are independently selected from H, an
alkyl or an aryl group, wherein R.sub.3 is a C1-C10 alkyl group,
wherein R' is selected from H, an alkyl group, an aryl group and
wherein different R' substituents can be connected to form a ring
structure and wherein B is a 1,2 phenylene bridging moiety, which
can be optionally substituted, wherein Mt is selected from Ti, Zr
and Hf, X is an anionic ligand, z is the number of X groups and
equals the valence of Mt minus 2. For example, X may be a
halogenide, an alkoxide, an alkyl group, an aryl group or an
aralkyl group.
[0010] The metallocene complex according to the invention
surprisingly can copolymerise ethylene with alpha olefins in a high
yield with a very high 1-hexene reactivity and a very high
molecular weight. This copolymerisation can take place in the
presence of a cocatalyst and under suitable polymerisation
conditions.
DETAILED DESCRIPTION
[0011] The metallocene complex according to the present invention
has the general structure according to formula I:
##STR00003##
wherein R.sub.1 and R.sub.2 are independently selected from H, an
alkyl or an aryl group, wherein R.sub.3 is a C1-C10 alkyl group,
wherein R' is selected from H, an alkyl group, an aryl group and
wherein different R' substituents can be connected to form a ring
structure and wherein B is a 1,2 phenylene bridging moiety, which
can be optionally substituted wherein Mt is selected from Ti, Zr
and Hf, X is an anionic ligand, z is the number of X groups and
equals the valence of Mt minus 2.
[0012] R.sub.1 and R.sub.2 are preferably independently selected
from H, a C1-C10 alkyl group or a C6-C10 aryl group. Examples of
suitable alkyl groups are methyl, ethyl, n-propyl, iso-propyl,
butyl, pentyl, hexyl, octyl, decyl and the like. Examples of
suitable aryl groups are substituted or unsubstituted phenyl and
naphthyl groups, preferably phenyl groups, or
3,5-dimethyl-1-phenyl, 3,5-diethyl-1-phenyl,
3,5-diisopropyl-1-phenyl or 3,5-ditertiairbutyl-1-phenybenzyl. More
preferably, R.sub.1 and R.sub.2 are chosen from H, a methyl, ethyl,
n-propyl or iso-propyl group, a butyl group, a hexyl or cyclohexyl
group, or a phenyl group. Most preferably, R.sub.1 and R.sub.2 are
chosen from H, methyl or phenyl groups
[0013] R.sub.3 is preferably a C1-C4 alkyl group, more preferably a
methyl, ethyl, n-propyl or iso-propyl group, most preferably
selected from a methyl or isopropyl group.
[0014] Preferably Mt is zirconium or hafnium, most preferably Mt is
zirconium.
[0015] Preferably X is a monovalent anionic group, selected from
the group consisting of halogen (F, Cl, Br or I), a C1-C20
hydrocarbyl group or a C1-C20 alkoxy group. Preferably X is a
methyl group, Cl, Br or I, most preferably methyl or Cl.
[0016] The metallocene complex according to formula (I) comprises a
2-substituted 1-indenyl group which is bridged through a
1,2-phenylene bridge to a 2-indenyl group, which 2-indenyl group
can be substituted with one or more substituents on the 1 and 3
position. Both 1-indenyl and 2-indenyl ligands can be further
substituted on the 6 membered indenyl ring with alkyl or aryl
substituents.
[0017] The 1,2 phenylene bridge can be substituted on the 3, 4, 5
or 6 position with alkyl or aryl groups. The bridge can also be a
naphtylene group, a phenantrylene or any other aromatic group, as
long as the bridge is being formed by two adjacent carbon atoms in
the aromatic bridge. Preferably the bridge is a 1,2 phenylene
bridge as shown in structure (II). In the context of the present
invention, the 1,2 phenylene bridge may be a bridging moiety
comprising a phenylene group that is bound to a 1-indenyl ligand or
a first of either the 1 or 2 position of the phenylene group, and
to a 2-indenyl ligand at the other of the 1 or 2 position of the
phenylene group, wherein further the phenylene group may be
substituted on the 3,4,5 or 6 position with alkyl or aryl
groups.
##STR00004##
The Support
[0018] The metallocene complex can be immobilized on a support. The
support is preferably an inert support, more preferably a porous
inert support. Examples of porous inert supports materials are
talc, clay and inorganic oxides. Preferably, the support material
is in a finely divided form.
[0019] Suitable inorganic oxide materials include group 2A, 3A, 4A
and 4B metal oxides such as silica, alumina and mixtures thereof.
Other inorganic oxides that may be employed either alone or in
combination with the silica or alumina are magnesia, titania,
zirconia and the like. Other support materials, however, can be
employed, for example finely divided functionalized polyolefins
such as finely divided polyethylene or polystyrene.
[0020] Preferably, the support is a silica having a surface area
between 200 and 900 m.sup.2/g and a pore volume between 0.5 and 4
ml/g.
The Catalyst
[0021] The invention is also directed to a catalyst prepared from
the metallocene complex according to the invention and a
cocatalyst. The cocatalyst should be capable to generate a cationic
specie from the metallocene compound and form a so-called non- or
weakly coordinating anion. Suitable cocatalysts include aluminium-
or boron-containing cocatalysts. Suitable aluminium-containing
cocatalysts comprise aluminoxanes, alkyl aluminium compounds and
aluminium-alkyl-chlorides. The aluminoxanes usable according to the
present invention are well known and preferably comprise oligomeric
linear and/or cyclic or cage-like alkyl aluminoxanes represented by
the formula: R.sup.3--(AlRS.sup.3--O).sub.n--AlR.sup.3.sub.2for
oligomeric, linear aluminoxanes and (--AlR.sup.3--O--).sub.m for
oligomeric, cyclic aluminoxanes; wherein n is 1-40, preferably n is
10-30; m is 3-40, preferably m is 3-30 and R.sup.3 is a Ci to 08
alkyl group and preferably a methyl group. Further other
organoaluminium compounds can be used such as trimethylaluminium,
triethylaluminium, triisopropylaluminium, tri-n-propylaluminium,
triisobutylaluminium, tri-n-butylaluminium,
tri-tert-butylaluminium, triamylaluminium; dimethylaluminium
ethoxide, diethylaluminium ethoxide, diisopropylaluminium ethoxide,
di-n-propylaluminium ethoxide, diisobutylaluminium ethoxide and
di-n-butylaluminium ethoxide; dimethylaluminium hydride,
diethylaluminium hydride, diisopropylaluminium hydride,
di-n-propylaluminium hydride, diisobutylaluminium hydride and
di-n-butylaluminium hydride.
[0022] Suitable boron-containing cocatalysts include
trialkylboranes, for example trimethylborane or triethylborane
and/or perfluoroarylborane and/or
perfluoroarylborate-compounds.
[0023] In the process to produce olefin polymers by polymerising
one or more olefins in the presence of a metallocene complex
preferably an organoaluminium cocatalyst is present.
[0024] More preferably, methylaluminoxane, trialkylboranes,
perfluoroarylboranes or perfluoroarylborates are used as the
cocatalyst.
Olefin Polymerisation
[0025] In another aspect, the invention relates to a process for
the preparation of olefin polymers by polymerising one or more
olefins in the presence of a cocatalyst and the metallocene complex
of the invention, wherein the metallocene complex optionally is
immobilized on a support.
[0026] The process to produce the olefin polymers may start with
the reaction of the metallocene complex according to the invention
with the cocatalyst. This reaction can be performed in the same
vessel as the reaction vessel wherein the olefin polymers are
produced or in a separate vessel, whereafter the mixture of the
metallocene complex and the cocatalyst is fed to the reaction
vessel. During the reaction described above an inert solvent can be
used.
[0027] The polymerisation, can be adequately carried out in a
slurry process, a solution process or a gas-phase process.
[0028] In the mixture of the metallocene complex and an
organoaluminium cocatalyst, the cocatalyst is used in an amount of
10 to 100,000 mol, preferably from 10 to 10,000 mol per mol of the
transition metal compound.
[0029] In the mixture of the metallocene complex and an
organoborane or organoborate cocatalyst, the cocatalyst is used in
an amount of 0,1 to 100 mol, preferably from 0,5 to 100 mol per mol
of the transition metal compound.
[0030] The solvent used in a slurry process to produce olefin
polymers may be any organic solvent usually used for the
polymerisation. Examples of solvents are benzene, toluene, xylene,
propane, butane, pentane, hexane, heptane, cyclohexane and
methylene chloride. Also the olefin to be polymerised can be used
as the solvent.
[0031] In the polymerisation process, an additional compound can be
used as a scavenger compound to scrub undesirable impurities from
the polymerisation medium that can adversely affect the catalyst
productivity. Examples of such undesired impurities are oxygen,
water, alcohols and the like. Suitable scavenging agents are metal
alkyl compounds, such as aluminium alkyl, magnesium alkyl, or zinc
alkyl compounds. The aluminium alkyl compound for the purpose of
scavenging the impurities can also be an aluminoxane compound. Also
partially pacified aluminium alkyl compounds can be used. For
instance, the reaction product of an aluminium alkyl with a
sterically hindered phenol can be used.
[0032] In the process to produce olefin polymers the polymerisation
conditions, like for example temperature, time, pressure, monomer
concentration can be chosen within wide limits. The polymerisation
temperature is in the range from -100 to 300.degree. C., preferably
0 to 240.degree. C., more preferably 50 to 200.degree. C. The
polymerisation time is in the range of from 10 seconds to 20 hours,
preferably from 1 minute to 10 hours, more preferably from 5
minutes to 5 hours. The ethylene pressure during polymerisation is
in the range from 1 to 3500 bar, preferably from 1 to 2500 bar,
more preferably from 1 to 1000 bar, even more preferably from 1 to
500 bar, most preferably from 1 to 100 bar. The molecular weight of
the polymer can be controlled by use of hydrogen in the
polymerisation. The polymerisation may be conducted by a batch
process, a semi-continuous process or a continuous process and may
also be conducted in two or more steps of different polymerisation
conditions. The polyolefin produced is separated from the
polymerisation solvent and dried by methods known to a person
skilled in the art.
[0033] In the process to produce olefin polymers the olefin which
is polymerised can be one type of olefin or can be mixtures of
different olefins. The polymerisation thus includes
homopolymerisation and copolymerisation. Examples of olefins are
.alpha.-olefins such as ethylene, propylene, 1-butene, 1-pentene,
3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene,
1-hexene, 1-octene, 1-nonene, 1-decene; conjugated and
non-conjugated dienes such as butadiene, 1,4-hexadiene,
5-ethylidene-2-norbornene, dicyclopentadiene,
4-methyl-1,4-hexadiene and 7-methyl-1,6-octadiene; cyclic olefins
such as cyclobutene and other olefinic compounds such as isobutene,
vinyl-cyclohexane and styrene but is not limited thereto.
[0034] Preferably, at least one of the olefins that is polymerised
is ethylene. More preferably, a mixture of ethylene and at least
one other .alpha.-olefin of 3 or more carbon atoms is
polymerised.
[0035] Preferably, the other olefin of 3 or more carbon atoms is
chosen from 1-butene, 1-hexene, 1-octene, vinyl-cyclohexane or
4-methyl-1-pentene.
[0036] Preferably, the olefin comonomer is present in an amount of
about 5 to about 50 percent by weight in the ethylene-olefin
copolymer, more preferably an amount of from about 7 to about 40
percent by weight in the ethylene .alpha.-olefin copolymer.
[0037] For example, a linear low density polyethylene (LLDPE)
having a melt mass flow rate (also known as melt flow index) as
determined using ASTM D1238-10 (190.degree. C./2.16 kg) which
ranges from 0.5 to 125 g/10 min and a density in the range from 900
kg/m.sup.3 to less than 940 kg/m.sup.3 as determined using ASTM
D1505-10 may be obtained. For example, the density of the LLDPE
ranges from about 915 kg/m.sup.3 to less than 940 kg/m.sup.3, for
example between 915 and 925 kg/m.sup.3. For example, the melt flow
index of the LLDPE ranges from 0.3 to 3 g/10min, for example from
0.5 to 1.5 g/10 min.
[0038] The polymerisation may be performed via a gas-phase process,
via a slurry process or via a solution process. The production
processes of polyethylene are summarised in "Handbook of
Polyethylene" by Andrew Peacock (2000; Dekker; ISBN 0824795466) at
pages 43-66.
[0039] The various processes may be divided into solution
polymerisation processes employing homogeneous (soluble) catalysts
and processes employing supported (heterogeneous) catalysts. The
latter processes include both slurry and gas phase processes.
[0040] When carrying out a slurry or gas phase process, a so-called
continuity agent or anti-static agent or anti-fouling agent may be
added to reactor.
[0041] The invention is also directed to a polyolefin, for example
polyethylene, preferably high density polyethylene (HDPE)
obtainable or obtained by the process of the invention, for example
by copolymerising ethylene and at least one other olefin in the
presence of a metallocene complex according to the invention or a
composition, wherein the metallocene complex according to the
invention is immobilized on a support.
[0042] As defined herein, in linear low density polyethylene, the
term "linear" means that the polymer is substantially linear, but
may contain some long chain branching.
[0043] "Long chain branching" (LCB) means a chain length longer
than the short chain branch that results from the incorporation of
the .alpha.-olefin(s) into the polymer backbone. Each long chain
branch will have the same comonomer distribution as the polymer
backbones and can be as long as the polymer backbone to which it is
attached.
[0044] As a practical matter, current .sup.13C nuclear magnetic
resonance spectroscopy cannot distinguish the length of a long
chain branch in excess of six carbon atoms. However, there are
other known techniques useful for determining the presence of long
chain branches in ethylene polymers. Two such methods are gel
permeation chromatography coupled with a low angle laser light
scattering detector (GPC-LALLS) and gel permeation chromatography
coupled with a differential viscometer detector (GPC-DV). In
addition, melt-rheology, for example determining the behavior of
the polymer melt under different shear rates, is frequently used to
indicate the presence of long chain branching. The use of these
techniques for long chain branch detection and the underlying
theories have been well documented in the literature.
[0045] See, for example, Zimm, G. H. and Stockmayer, W. H., J.
Chem. Phys., 17,1301 (1949) and Rudin, A., Modern Methods of
Polymer Characterization, John Wiley & Sons, New York (1991 pp.
103-112).
[0046] It has been found that with the metallocene complex of the
invention or with the composition of the invention wherein the
metallocene complex of the invention is present on a support, it is
possible to produce polyethylene from ethylene and at least one
other olefin, for example an olefin having up to 8 carbon atoms,
with a high incorporation of the at least one other olefin.
[0047] The amount of incorporation of the at least one other
olefin, for example an a-olefin in the polyethylene is expressed by
the amount of branches per 1000 carbon atoms.
[0048] The presence of short chain branching of up to 6 carbon
atoms in length can be determined in ethylene polymers by using
.sup.13C nuclear magnetic resonance (NMR) spectroscopy and is
quantified using the method described by Randall (Rev. Macromol.
Chem. Phys., C.29, V. 2 & 3, p. 285-297).
[0049] Therefore, the invention also relates to a polyolefin,
preferably polyethylene, for example linear low density
polyethylene (LLDPE). The low density polyethylene, for example
LLDPE, preferably has an amount of branches per 1000 carbon atoms
as determined using .sup.13C NMR of at least 18, for example of at
least 19, for example at least 20 and/or for example at most 50,
for example at most 40, for example at most 30, for example at most
25.
[0050] The number average molecular weight (Mn) of the polyolefin,
for example polyethylene, for example LLDPE of the invention may
vary between wide ranges and may for example be in the range from
1000 to 200000 Da.
[0051] For example, the Mn of the polyolefin of the invention may
be at least 1500, for example at least 2000, for example at least
20,000, for example at least 50,000 and/or for example at most
150,000, for example at most 110,000, for example at most 100,000,
for example at most 70,000 Da.
[0052] The weight average molecular weight (Mw) of the polyolefin,
for example polyethylene, for example LLDPE of the invention may
also vary between wide ranges and may for example be in the range
from 1500 to 500000. For example, the Mw of the polyolefin of the
invention may be at least 2500, for example at least 10,000, for
example at least 50,000, for example at least 100,000 and/or for
example at most 400,000, for example at least 350,000, for example
at most 300,000, for example at most 250,000.
[0053] For purpose of the invention, the Mw and Mn are determined
using SEC (Size Exclusion Chromatography) using
1,2,4-trichlorobenzene or o-dichlorobenzene as an eluent, and
calibrated using linear polyethylene or polystyrene standards.
[0054] The molecular weight distribution (that is Mw/Mn) of the
polyolefin of the invention may for example vary from 2 to 5, from
2.1 to 4 or from 2.5 to 3.5.
[0055] The polyolefin obtained or obtainable by the process of the
invention may be mixed with suitable additives.
[0056] Examples of suitable additives for polyethylene include but
are not limited to the additives usually used for polyethylene, for
example antioxidants, nucleating agents, acid scavengers,
processing aids, lubricants, surfactants, blowing agents,
ultraviolet light absorbers, quenchers, antistatic agents, slip
agents, anti-blocking agents, antifogging agents, pigments, dyes
and fillers, and cure agents such as peroxides. The additives may
be present in the typically effective amounts well known in the
art, such as 0.001 weight % to 10 weight % based on the total
composition.
[0057] The polyolefins of the invention and compositions comprising
said polyolefins may suitably be used for the manufacture of
articles. For example, the polyolefins and compositions of the
invention may be manufactured into film, for example by
compounding, extrusion, film blowing or casting or other methods of
film formation to achieve, for example uniaxial or biaxial
orientation. Examples of films include blown or cast films formed
by coextrusion (to form multilayer films) or by lamination and may
be useful as films for packaging, for example as shrink film, cling
film, stretch film, sealing films, oriented films, snack packaging,
heavy duty bags, grocery sacks, baked and frozen food packaging,
medical packaging, industrial liners, membranes, etc. in
food-contact and non-food contact applications, agricultural films
and sheets.
[0058] Therefore, in another aspect, the invention also relates to
articles comprising the polyolefins obtainable by the process of
the invention.
[0059] In yet another aspect, the invention also relates to use of
the polyolefins obtainable by the process of the invention for the
preparation of articles, for example for the preparation of
films.
[0060] In yet another aspect, the invention relates to a process
for the preparation of articles using the polyolefin according to
the invention.
[0061] It is further noted that the term `comprising` does not
exclude the presence of other elements. However, it is also to be
understood that a description on a product comprising certain
components also discloses a product consisting of these components.
Similarly, it is also to be understood that a description on a
process comprising certain steps also discloses a process
consisting of these steps.
[0062] The invention will hereafter be elucidated by way of the
following examples, without being limited thereto.
EXAMPLES
General Considerations
[0063] All manipulations were carried out under an atmosphere of
dry, O.sub.2-free N.sub.2 employing an Innovative Technology glove
box and a Schlenk vacuum-line. Tetrahydrofuran (THF), toluene,
methylene chloride, hexane and pentane were purified with a
Grubbs-type column system manufactured by Innovative Technology and
dispensed into thick-walled Schlenk glass flasks equipped with
Teflon-valve stopcocks. Pyridine was dried over the appropriate
agents and distilled into the same kind of storage flasks.
Anhydrous benzene (Alfa, 99.8%, packaged under argon) was purchased
and used as received. Deuterated solvents were dried over the
appropriate agents, vacuum-transferred into storage flasks with
Teflon stopcocks and degassed accordingly (CDCl.sub.3,
C.sub.6D.sub.6 and CD.sub.2Cl.sub.2). .sup.1H, .sup.11B, .sup.13C
and .sup.31 P NMR spectra were recorded at 25.degree. C. Bruker 400
MHz spectrometers. Chemical shifts are given relative to SiMe.sub.4
and referenced to the residue solvent signal (.sup.1H, .sup.13C).
.sup.11B and .sup.31P resonances were referenced externally to
(BF.sub.3Et.sub.2O) and 85% H.sub.3PO.sub.4, respectively. Chemical
shifts are reported in ppm and coupling constants as scalar values
in Hz. ZrCl.sub.4(Me.sub.2S).sub.2.sup.,
1TiCl.sub.4(THF).sub.2.sup.2 and TiCl.sub.4(Me.sub.2S).sub.2.sup.3
were prepared as reported in, respectively, Sassmannshausen, J.
Organometallics 2000, 19, 482-489; Seenivasan, K.; Sommazzi, A.;
Bonino, F.; Bordiga, S.; Groppo, E. Chemistry-a European Journal
2011, 17, 8648-8656 and Suren Lewkebandara, T.; McKarns, P. J.;
Haggerty, B. S.; Yap, G. P. A.; Rheingold, A. L.; Winter, C. H.
Polyhedron 1998, 17, 1-9. ZrCl.sub.4(THF).sub.2 (Strem) was
purchased and used as received.
Synthesis of ligands and catalyst precursors.
Preparation of Catalyst ID 135:
[0064] (2E)-3-(2-bromophenyl)-1-phenylprop-2-en-1-one
##STR00005##
[0065] A mixture of 36.05 g (300 mmol) of 1-phenylethanone and
55.51 g (300 mmol) of 2-bromobenzaldehyde was added dropwise to a
solution of 15 g of NaOH in a mixture of 90 ml of 95% EtOH and 140
ml of water. The resulting mixture was stirred for 12 h at r.t.,
then, diluted with 1500 ml of water and extracted with 3.times.250
ml of dichloromethane. The combined extract was dried over
K.sub.2CO.sub.3, passed through a short pad of silica gel 60 (40-63
um) and evaporated to dryness. The residue was distilled in vacuum
(b.p. 195-205.degree. C./6 mm Hg) to afford 65.38 g (76%) of
(2E)-3-(2-bromophenyl)-1-phenylprop-2-en-1-one.
[0066] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 8.15 (d, J=15.7
Hz, 1H), 8.07-7.99 (m, 2H), 7.73 (dd, J=7.7 Hz, J=1.6 Hz, 1H),
7.64-7.55 (m, 2H), 7.55-7.47 (m, 2H), 7.44 (d, J=15.7 Hz, 1H), 7.35
(tm, J=7.6 Hz, 1H), 7.23 (td, J=7.7 Hz, J=1.6 Hz, 1H).
3-(2-Bromophenyl)indan-1-one
##STR00006##
[0068] To polyphosphoric acid (prepared from 660 g of
P.sub.4O.sub.10 and 540 g of 85% H.sub.3PO.sub.4) 65.38 g (227.7
mmol) of (2E)-3-(2-bromophenyl)-1-phenylprop-2-en-1-one were added
at 140.degree. C. and the resulting mixture was stirred at this
temperature for 0.5 h. Then, it was poured onto 2 kg of ice. The
product was extracted with 4.times.300 ml of dichloromethane. The
combined extract was washed with aqueous solution of
K.sub.2CO.sub.3, dried over K.sub.2CO.sub.3, passed through a short
pad of silica gel 60 (40-63 um) and evaporated to dryness. The
residue was purified by column chromatography on silica gel 60
(40-63 um; eluent: hexanes/dichloromethane=5:1, vol., then
dichloromethane/EtOAc=3:1, vol.). This procedure gave 28.01 g (43%)
of 3-(2-bromophenyl)indan-1-one as a white solid.
[0069] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.84 (d, J=7.7
Hz, 1H), 7.68-7.59 (m, 2H), 7.47 (t, J=7.7 Hz, 1H), 7.38 (d, J=7.7
Hz, 1H), 7.19 (t, J=7.3 Hz, 1H), 7.12 (t, J=7.3 Hz, 1H), 6.79 (d,
J=7.3 Hz, 1H), 5.14 (dd, J=8.3 Hz, J=3.3 Hz, 1H), 3.35 (dd, J=19.4
Hz, J=8.3 Hz, 1H), 2.53 (dd, J=19.4 Hz, J=3.3 Hz, 1H).
1-(2-Bromophenyl)-3-methoxyindane
##STR00007##
[0070] To a mixture of 47.2 g (164.37 mmol) of
3-(2-bromophenyl)indan-1-one and 7.0 g (185.0 mmol) of NaBH.sub.4
in 160 ml of THF 80 ml of methanol were added dropwise for 5 h at
5.degree. C. This mixture was stirred overnight at r.t. and then
evaporated to dryness. The residue was partitioned between 500 ml
of dichloromethane and 500 ml of 1 M HCl. The organic layer was
separated, and the aqueous layer was additionally extracted with
250 ml of dichloromethane. The combined organic extract was dried
over Na.sub.2SO.sub.4 and evaporated to dryness to give a white
mass. To a solution of thus obtained 3-(2-bromophenyl)indan-1-ol in
450 ml of DMSO 55 g (0.98 mol) of KOH and 53 g (0.373 mol) of Mel
were added. This mixture was stirred for 5 h at ambient
temperature. The formed solution was decanted from an excess of
KOH, the latter was additionally washed with 3.times.150 ml of
dichloromethane. The combined organic solution was washed with 2000
ml of water. The organic layer was separated, and the aqueous layer
was extracted with 2.times.100 ml of dichloromethane. The combined
organic extract was washed with 7.times.1000 ml of water, dried
over Na.sub.2SO.sub.4, and then evaporated to dryness. The residue
was purified by column chromatography on silica gel 60 (40-63 um;
eluent: hexanes/dichloromethane=2:1, vol., then 1:3, vol.). This
procedure gave 48.97 g (98%) of 1-(2-bromophenyl)-3-methoxyindane
as a white solid.
[0071] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.58 (d, J=7.9
Hz, 1H), 7.48 (d, J=7.1 Hz, 1H), 7.34-7.22 (m, 2H), 7.19 (t, J=7.4
Hz, 1H), 7.12-7.00 (m, 3H), 4.92 (t, J=6.5 Hz, 1H), 4.77 (t, J=8.0
Hz, 1H), 3.47 (s, 3H), 3.10-2.98 (m, 1H), 1.95-1.84 (m, 1H).
2-[2-(3-Methoxy-2,3-dihydro-1H-inden-1-yl)phenyl]-4,4,5,5-tetramethyl-1,3-
,2-dioxaborolane
##STR00008##
[0072] To a solution of 36.54 g (120.52 mmol) of
1-(2-bromophenyl)-3-methoxyindane in 350 ml of THF 48.2 ml (120.5
mmol) of 2.5 M n-butyllithium in hexanes were added dropwise at
-50.degree. C. over 0.5 h. This mixture was stirred for 0.5 h at
-50.degree. C., then the resulting solution was cooled to
-78.degree. C., and 19.0 g (182.9 mmol) of trimethyl borate was
added in one portion. The reaction mixture was stirred overnight at
r.t., then it was quenched by addition of 200 ml of 2N hydrochloric
acid. The resulting mixture was stirred for 0.5 h, then extracted
with 2.times.500 ml of ether. The combined extract was evaporated
and dried in vacuum to give yellowish oil. To the solution of this
oil in 150 ml of THF 14.0 g (118.5 mmol) of pinacol were added and
this mixture was stirred at r.t. overnight, then, additionally for
3 h at reflux. After evaporation, the crude product was purified by
column chromatography on silica gel 60 (40-63 um; eluent:
hexanes/dichloromethane=1:1, vol., then 1:5, vol.). This procedure
gave 22.46 g (53%) of
2-[2-(3-methoxy-2,3-dihydro-1H-inden-1-yl)phenyl]-4,4,5,5-etramethyl-1,3,-
2-dioxaborolane as a white solid.
[0073] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.82 (dd, J=7.5
Hz, J=1.2 Hz, 1 H), 7.46 (d, J=7.1 Hz, 1H), 7.33 (td, J=7.5 Hz,
J=1.4 Hz, 1H), 7.29-7.17 (m, 3H), 7.11 (d, J=7.7 Hz, 1H), 6.99 (d,
J=7.1 Hz, 1H), 5.09 (t, J=8.2 Hz, 1H), 4.94 (t, J=6.8 Hz, 1H), 3.48
(s, 3H), 3.00 (ddd, J=12.8 Hz, J=8.2 Hz, J=7.1 Hz, 1H), 1.93 (ddd,
J=12.8 Hz, J=8.3 Hz, J=6.8 Hz, 1H), 1.35 (s, 6H), 1.34 (s, 6H).
2-(1H-Inden-2-yl)-2'-(3-methoxy-2,3-dihydro-1H-inden-1-yl)biphenyl
##STR00009##
[0074] A mixture of 9.14 g (26.1 mmol) of
2-[2-(3-methoxy-2,3-dihydro-1H-inden-1-yl)phenyl]-4,4,5,5-tetramethyl-1,3-
,2-dioxaborolane, 7.08 g (26.1 mmol) of 2-(2-bromophenyl)-1
H-indene, 7.5 g (70.8 mmol) of Na.sub.2CO.sub.3, 500 mg (0.98 mmol,
3.75 mol. %) of Pd(P.sup.tBu.sub.3).sub.2, 40 ml of water and 110
ml of 1,2-dimethoxyethane (DME) was refluxed for 6 h. DME was
evaporated on a rotary evaporator, and 200 ml of water and 400 ml
of dichloromethane were then added to the residue. The organic
layer was separated, and the aqueous layer was additionally
extracted with 50 ml of dichloromethane. The combined extract was
dried over K.sub.2CO.sub.3 and then evaporated to dryness to give a
dark-red solid. The crude product was purified by flash
chromatography on silica gel 60 (40-63 um,
hexane/dichloromethane=2:1, vol., then, 1:2, vol.) to give 8.58 g
(79%) of 2-(1H-inden-2-yl)
-2'-(3-methoxy-2,3-dihydro-1H-inden-1-yl)biphenyl as a yellowish
oil which completely solidified at r.t..
[0075] .sup.1H NMR (400 MHz, CDCl.sub.3): 5 7.62 (d, J=7.7 Hz) and
7.56 (dd, J=7.5 Hz, J=1.2 Hz) {sum 1H}, 7.50-6.80 (m, 15H), 6.47
(s) and 6.39 (d, J=7.5 Hz) {sum 1 H}, 4.71 (t, J=7.1 Hz) and 4.67
(t, J=6.9 Hz) {sum 1H}, 4.13 (t, J=8.3 Hz) and 4.01 (t, J=8.5 Hz)
{sum 1 H}, 3.54-3.28 (2 s and m, 5H), 2.73-2.54 (m) and 2.51-2.46
(m) {sum 1 H}, 1.81-1.70 (m, 1H).
2-(1 H-Inden-2-yl)-2'-(1 H-inden-3-yl)biphenyl (L135)
##STR00010##
[0077] To a solution of 8.58 g (20.7 mmol) of
2-(1H-inden-2-yl)-2'-(3-methoxy-2,3-dihydro-1H-inden-1-yl)biphenyl
in 250 ml of toluene 150 mg of TsOH was added, and this mixture was
refluxed with Dean-Stark head for 15 min and then cooled to r.t..
The resulting solution was washed with 10% aqueous
Na.sub.2CO.sub.3. The organic layer was separated and the aqueous
layer was extracted with 2.times.100 ml of dichloromethane. The
combined organic solution was dried over
[0078] K.sub.2CO.sub.3 and then passed through a short pad of
silica gel 60 (40-63 um). The silica gel pad was additionally
washed with 50 ml of dichloromethane. The filtrate was evaporated
almost to dryness and the residue was dissolved in 100 ml of
n-hexane. Yellowish powder precipitated from this solution over 1.5
hours at r.t. was filtered to give 6.22 g (79%) of
2-(1H-inden-2-yl)-2'-(1 H-inden-3-yl)biphenyl as a mixture of
isomers.
[0079] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.95-7.65 (m,
13.5H), 7.05 and 7.04 (2s, sum 1H), 6.91 (t, J=7.3 Hz, 0.45H), 6.68
(dd, J=5.5 Hz, J=2.2 Hz) and 6.66 (dd, J=5.5 Hz, J=1.7 Hz) {sum
1H}, 6.59 (d, J=7.3 Hz, 0.45H), 6.54 and 6.53 (2s, sum 1H), 6.45
(s, 0.55H), 6.32 (dd, J=5.5 Hz, J=1.8 Hz) and 5.95 (dd, J=5.5 Hz,
J=1.6 Hz) {sum 1 H}, 4.51 and 4.50 (2s, sum 1H), 3.60-3.34 (m,
2H).
Catalyst ID 135
##STR00011##
[0081] To a white suspension of 6.18 g (16.16 mmol) of
2,2'-(1H-inden-2-yl)(1H-inden-3-yl)biphenyl (L135) in 200 ml of
ether 13.0 ml (31.6 mmol) of 2.43 M n-butyllithium in hexanes were
added in one portion at -50.degree. C. This mixture was stirred
overnight at r.t., then the resulting yellow solution with a lot of
yellow precipitate was cooled to -50.degree. C., and 3.77 g (16.18
mmol) of ZrCl.sub.4 was added. The reaction mixture was stirred
overnight at r.t. to give orange solution with orange precipitate.
This mixture was evaporated to dryness. The residue was heated with
200 ml of toluene, and the suspension formed was filtered while hot
through glass frit (G4). 280 mg (3.2%) of the title compound were
separated from the resulting filtrate by fractional
crystallization.
[0082] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.98-7.93 (m,
1H), 7.90 (d, J=8.5 Hz, 1H), 7.87 (d, J=8.5 Hz, 1 H), 7.62-7.45 (m,
7H), 7.33-7.08 (m, 5H), 7.04 (d, J=3.7 Hz, 2H), 6.65 (d, J=3.7 Hz,
1H), 6.34 (d, J=2.4 Hz, 1 H), 5.75 (d, J=3.7 Hz, 1H).
Preparation of Catalyst ID's 140, 157, 158, 179, and 182
[0083] 3-(2-Bromophenyl)-2-methyl-1-phenylprop-2-ene-1-one
##STR00012##
[0084] NaOH (11.6 g, 290 mmol, 1.3 equiv.) was dissolved in a
mixture of 100 ml of EtOH and 200 ml of water. The solution was
cooled to r.t., and propiophenone (30.0 g, 224 mmol, 1 equiv.) was
added in one portion. Then, 2-bromobenzaldehyde (41.4 g, 224 mmol,
1 equiv) was added in one portion, and the resulting mixture was
stirred at r.t. overnight and then for 12 h at 60.degree. C. The
reaction mixture was poured into 1000 ml of water and extracted
with diethyl ether (3.times.150 ml). The combined organic extract
was dried over Na.sub.2SO.sub.4, and the solvents were removed in
vacuum. The residue was distilled in vacuum, and fraction with b.p.
135-155.degree. C./1 mbar was collected. It contained ca. 5 mol %
of propiophenone according to .sup.1H NMR spectrum. This procedure
afforded 45.8 g (66%) of the title compound as greenish oil which
was used without further purification.
[0085] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.88-7.93 (m,
2H), 7.62 (d, 1 H, J=8.0 Hz), 7.46-7.59 (m, 3H), 7.33-7.41 (m, 2H),
7.22 (br.s, 1H), 7.19-7.22 (m, 1H), 2.13 (d, 3H, J=1.3 Hz).
3-(2-Bromophenyl)-2-methyl-2,3-dihydro-1H-inden-1-one
##STR00013##
[0086] 3-(2-Bromophenyl)-2-methyl-1-phenylprop-2-ene-1-one (57.4 g,
190 mmol) was added in one portion to the polyphosphoric acid
(prepared from 500 ml of 85% phosphoric acid and 150 g of
P.sub.4O.sub.10). The mixture was stirred at 140.degree. C. for 1
h, then cooled to ambient temperature, and poured into 3000 ml of
water. The crude product was extracted with diethyl ether
(3.times.300 ml). The combined organic extract was dried over
Na.sub.2SO.sub.4 and then evaporated to dryness. The remaining
propiophenone and all other volatiles were removed in high vacuum
using Kugelrohr apparatus. This procedure afforded 34.0 g (59%) of
the title compound as red oil. The product was a mixture of two
diastereomers, A and B, in molar ratio .about.4:1 according to
.sup.1H NMR spectrum.
[0087] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. (7.83, d, 1H in
B, J=7.8 Hz), 7.80 (d, 1H in A, J=7.6 Hz), 7.05-7.65 (m, 6H in A
and B), 6.72-6.85 (m, 1H in A), 6.54 (dd, 1H in B, J=7.2 Hz, J=1.9
Hz), 6.54 (dd, 1H in B, J=8.0 Hz), 4.70-4.85 (m, 1H in A), 3.18
(quint, 1H in B, J=7.7 Hz), 2.50-2.75 (m, 1H in B), 1.44 (d, 3H in
A, J=7.1 Hz), 0.81 (d, 3H in B, J=7.7 Hz).
1-(2-Bromophenyl)-2-methyl-1H-indene
##STR00014##
[0088] 3-(2-Bromophenyl)-2-methyl-2,3-dihydro-1H-inden-1-one (34.0
g, 113 mmol) was dissolved in a mixture of 400 ml of THF and 100 ml
of methanol. NaBH.sub.4 (6.40 g, 170 mmol, 1.5 equiv.) was added in
small portions to this solution. After completion of addition the
reaction mixture was stirred overnight at r.t. and then poured into
1500 ml of water. The product was extracted with diethyl ether
(3.times.100 ml). The combined organic extract was washed with
water, dried over Na.sub.2SO.sub.4 and then evaporated to dryness.
The residue was dissolved in 500 ml of toluene, and catalytic
amount of TsOH was added. The resulting mixture was refluxed using
Dean-Stark apparatus for 10 min, then cooled to r.t. and passed
through a short pad of silica gel 60 (40-63 um). The solution was
evaporated to dryness, the residue was dissolved in hexane, and the
solution was passed through a short pad of silica gel. The
resulting solution was evaporated to dryness. This procedure
afforded 25.0 g (78%) of the title compound as white solid.
[0089] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.63-7.67 (m,
1H), 7.20-7.29 (m, 3H), 7.01-7.10 (m, 3H), 6.58 (m, 1 H), 6.49-6.54
(m, 1 H), 5.06 (s, 1H), 1.94 (br.s, 3H).
[0090] 2-Methyl-1-(2-(3-phenyl-1H-inden-2-yl)phenyl)-1H-indene
(L140)
##STR00015##
[0091] A mixture of 1-(2-bromophenyl)-2-methyl-1 H-indene (3.00 g,
10.5 mmol, 1 equiv.),
4,4,5,5-tetramethyl-2-(3-phenyl-1H-indene-2-yl)-1,3,2-dioxaborolane
(4.00 g, 12.6 mmol, 1.2 equiv.), Na.sub.2CO.sub.3 (2.80 g, 26.3
mmol, 2.5 equiv), toluene (25 ml), ethanol (12 ml), and water (5
ml) was placed in a heavy wall glass pressure vessel. Argon was
bubbled through the mixture for 5 min, and then Pd(PPh.sub.3).sub.4
(0.61 g, 0.53 mmol, 0.05 equiv.) was added. The resulting mixture
was stirred overnight at 110.degree. C., cooled to r.t., diluted
with water, and the crude product was extracted with toluene
(2.times.30 ml). The combined organic extract was washed with
water, dried over Na.sub.2SO.sub.4, and then evaporated to dryness.
The residue was dissolved in hexane, and the obtained solution was
passed through a short pad of silica gel 60 (40-63 um). The solvent
was evaporated, and the residue was recrystallized from hexane.
This procedure afforded 2.50 g (60%) of the title compound as an
off-white solid.
[0092] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.58 (d, 1H,
J=7.2 Hz), 7.47 (d, 1 H, J=7.4 Hz), 7.43 (d, 1H, J=7.5 Hz),
7.21-7.38 (m, 8H), 7.03-7.16 (m, 3H), 6.81 (t, 1H, J=7.3 Hz), 6.38
(s, 1H), 6.33 (d, 1H, J=7.8 Hz), 6.08 (br.s, 1H), 4.46 (s, 1H),
3.91-4.07 (m, 2H), 1.45 (s, 3H).
3-Methyl-1-phenylbutan-1-one
##STR00016##
[0093] Isovaleroyl chloride (50.0 g, 410 mmol, 1.0 equiv) was added
dropwise to the suspension of AlCl.sub.3 (64.0 g, 480 mmol, 1.15
equiv) in dry benzene (330 ml) at 5.degree. C. The cooling bath was
removed and the reaction mixture was allowed to warm to r.t. and
then stirred for 2 h. Then the reaction mixture was poured onto
crushed ice, the organic layer was separated and the aqueous layer
was extracted with benzene (2.times.100 ml). The combined organic
extracts were dried over Na.sub.2SO.sub.4 and evaporated to
dryness. The residue was distilled and fraction with b.p. 70
.degree. C./2 mbar was collected. This procedure gave 52.1 g (78%)
of the product as colorless oil.
[0094] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.93-7.95 (m,
2H), 7.54 (t, 1 H, J=7.4 Hz), 7.44 (t, 2H, J=7.5 Hz), 2.82 (d, 2H,
J=6.9 Hz), 2.24-2.34 (m, 1 H), 0.99 (d, 6H, J=6.7 Hz).
2-((2-Bromophenyl)(hydroxy)methyl)-3-methyl-1-phenylbutan-1-one
##STR00017##
[0095] n-Butyllithium (48.2 ml, 118 mmol, 1.0 equiv) was added
dropwise to a solution of N,N-diisopropylamine (16.6 ml, 118 mmol,
1.0 equiv) in dry THF (400 ml) at -80.degree. C. The resulting
mixture was stirred for 15 min. A solution of
3-methyl-1-phenylbutan-1-one (19.2 g, 118 mmol, 1.0 equiv) in dry
THF (50 ml) was added dropwise to the mixture at the same
temperature. The resulting mixture was stirred for 15 min and a
solution of 2-bromobenzaldehyde (21.8 g, 118 mmol, 1.0 equiv) in
dry THF (50 ml) was added dropwise. The resulting mixture was
stirred for 30 min and the solution of 12M HCl (10.0 ml, 118 mmol,
1.0 equiv) in 40.0 ml of MeOH was added at -80.degree. C. The
reaction mixture was allowed to warm to r.t., stirred for 1 h, and
then poured into water. The mixture was extracted with ether
(3.times.100 ml), the combined organic extracts were dried over
Na.sub.2SO.sub.4 and evaporated to dryness. All volatiles were
removed from the residue under high vacuum using Kugelrohr
apparatus to afford the title product (19.8 g, 48%).
[0096] .sup.1H NMR (600 MHz, CDCl.sub.3): .delta. 7.53-7.54 (m,
2H), 7.38-7.41 (m, 2H), 7.25 (t, 2H, J=7.8 Hz), 7.20 (dd, 1H, J=7.8
Hz, J=1.4 Hz), 7.03 (t, 1H, J=7.1 Hz), 6.89 (td, 1H, J=7.6 Hz,
J=1.6 Hz), 5.41 (dd, 1H, J=9.4 Hz, J=2.7 Hz), 4.72 (d, 1H, J=9.4
Hz), 3.85 (dd, 1H, J=10.0 Hz, J=2.8 Hz), 2.45-2.51 (m, 1H), 1.30
(d, 3H, J=6.7 Hz), 0.85 (d, 3H, J=6.7 Hz).
2-Benzoyl-1-(2-bromophenyl)-3-methylbutyl methanesulfonate
##STR00018##
[0097] Triethylamine (27.8 g, 275 mmol, 5.0 equiv) was added to a
solution of 2-((2-bromophenyl)
(hydroxy)methyl)-3-methyl-1-phenylbutan-1-one (19.1 g, 55.0 mmol,
1.0 equiv), in 100 ml of dry THF at 0.degree. C. A solution of
methanesulfonyl chloride (7.00 g, 61.0 mmol, 1.1 equiv) in 50 ml of
dry THF was added dropwise at the same temperature and the reaction
mixture was stirred overnight. The mixture was poured into water
and the crude product was extracted with ether (3.times.100 ml),
the combined organic extracts were dried over Na.sub.2SO.sub.4 and
evaporated to dryness. The resulting solid was washed with methanol
to afford the title product as white powder (18.0 g, 77%).
[0098] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.83 (br.s, 2H),
7.48-7.58 (m, 3H), 7.42 (t, 2H, J=7.4 Hz), 7.29 (t, 1H, J=7.5 Hz),
7.12-7.18 (m, 1H), 6.42 (br.s, 1H), 3.99 (br.s, 1H), 2.87 (s, 3H),
1.94 (br.s, 1H), 0.90 (d, 6H, J=6.5 Hz).
2-(2-Bromobenzylidene)-3-methyl-1-phenylbutan-1-one
##STR00019##
[0099] 2-Benzoyl-1-(2-bromophenyl)-3-methylbutyl methanesulfonate
(17.4 g, 41.0 mmol, 1.0 equiv) and DBU (25.0 g, 164 mmol, 4.0
equiv.) were mixed in 200 ml of dry THF and the resulting mixture
was stirred overnight at 60.degree. C. The mixture was poured into
water and the crude product was extracted with ether (3.times.100
ml), the combined organic extracts were dried over Na.sub.2SO.sub.4
and evaporated to dryness to afford the title product as yellow oil
(13.0 g, 96%).
[0100] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of 2 isomers):
.delta. 8.02-8.04 (m), 7.76-7.79 (m), 7.63 (d), 7.58 (t), 7.49 (t),
7.34-7.36 (m), 7.14-7.28 (m), 6.76 (s), 2.91-2.99 (m), 1.25-1.28
(m).
3-(2-Bromophenyl)-2-isopropyl-2,3-dihydro-1H-inden-1-one
##STR00020##
[0101] 2-(2-Bromobenzylidene)-3-methyl-1-phenylbutan-1-one (12.5 g)
was added in one portion to polyphosphoric acid (prepared from 150
ml of 85% phosphoric acid and 150 g of P.sub.4O.sub.10). The
mixture was stirred at 140.degree. C. for 2 h, then cooled to
ambient temperature, and poured into 300 ml of water. The crude
product was extracted with diethyl ether (3.times.200 ml). The
combined organic extract was dried over Na.sub.2SO.sub.4 and then
evaporated to dryness. All other volatiles were removed in high
vacuum using Kugelrohr apparatus. This procedure afforded 10.4 g
(83%) of the title compound as red oil.
[0102] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.79 (d, 1H,
J=7.7 Hz), 7.63 (d, 1H, J=7.2 Hz), 7.52 (t, 1H, J=6.9 Hz), 7.39 (t,
1 H, J=7.4 Hz), 6.84-7.28 (m, 4H), 5.04 (br.s, 1 H), 2.77 (br.s,
1H), 2.49-2.57 (m, 1H), 0.99 (d, 6H, J=6.9 Hz).
1-(2-Bromophenyl)-2-isopropyl-1H-indene
##STR00021##
[0103] 3-(2-Bromophenyl)-2-isopropyl-2,3-dihydro-1H-inden-1-one
(3.00 g, 9.00 mmol, 1.0 equiv) was dissolved in a mixture of 20 ml
of THF and 7 ml of methanol. NaBH.sub.4 (0.52 g, 14.0 mmol, 1.5
equiv.) was added in small portions to this solution. After that,
the reaction mixture was stirred overnight at r.t. and then poured
into 150 ml of water. The product was extracted with diethyl ether
(3.times.50 ml). The combined organic extract was washed with
water, dried over Na.sub.2SO.sub.4 and then evaporated to dryness.
The residue was dissolved in 50 ml of toluene, and a catalytic
amount of TsOH was added. The resulting mixture was refluxed using
Dean-Stark apparatus for 10 min, then cooled to r.t. and passed
through a short pad of silica gel 60 (40-63 um). The filtrate was
evaporated to dryness, the residue was dissolved in hexane, and the
solution obtained was passed through a short pad of silica gel. The
resulting solution was evaporated to dryness. This procedure
afforded 1.60 g (57%) of the title compound as white solid.
[0104] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.66-7.68 (m,
1H), 7.32-7.34 (m, 1H), 7.24 (t, 2H, J=7.6 Hz), 7.04-7.11 (m, 3H),
6.67 (s, 1H), 6.54-6.56 (m, 1H), 5.25 (s, 1 H), 2.36-2.46 (m, 1H),
1.24 (d, 3H, J=6.9 Hz), 1.15 (d, 3H, J=6.9 Hz).
1-(2-(1H-Inden-2-yl)phenyl)-2-isopropyl-1H-indene (L157)
##STR00022##
[0105] A mixture of 1-(2-bromophenyl)-2-isopropyl-1H-indene (0.90
g, 2.90 mmol, 1.0 equiv),
2-(1H-inden-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.77 g,
3.20 mmol, 1.1 equiv), sodium carbonate (0.77 g, 7.30 mmol, 2.5
equiv), tetrakis(triphenylphosphine)palladium (0.17 g, 0.14 mmol,
0.05 equiv), 12 ml of toluene, 6 ml of ethanol and 3 ml of water
was stirred at 100.degree. C. overnight. After cooling to r.t.,
water (20 ml) was added and the mixture was extracted with ethyl
acetate (3.times.30 ml). The combined extracts were dried over
Na.sub.2SO.sub.4 and evaporated in vacuum. Column chromatography on
silica gel 60 (40-63 um, eluent: hexane/dichloromethane=10:1, vol.)
afforded 0.63 g (63%) of the title product as a yellowish
solid.
[0106] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.53 (d, 1H,
J=7.2 Hz), 7.41-7.44 (m, 2H), 7.30-7.34 (m, 2H), 7.22-7.26 (m, 4H),
7.06-7.13 (m, 3H), 6.60 (s, 1H), 6.55 (d, 1H, J=7.7 Hz), 5.10 (s,
1H), 3.75-4.11 (AB quartet, 2H), 2.26-2.37 (m, 1H), 1.16 (d, 3H,
J=6.7 Hz), 0.93 (d, 3H, J=6.9 Hz).
2-(2-(2-Isopropyl-1H-inden-1-yl)phenyl)-1,3-dimethyl-1H-indene
(L158)
##STR00023##
[0107] A mixture of 1-(2-bromophenyl)-2-isopropyl-1H-indene (2.00
g, 6.40 mmol, 1.0 equiv),
2-(1,3-dimethyl-1H-inden-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
(1.90 g, 7.00 mmol, 1.1 equiv), sodium carbonate (1.70 g, 16.0
mmol, 2.5 equiv), tetrakis(triphenylphosphine)palladium (0.37 g,
0.32 mmol, 0.05 equiv), 25 ml of toluene, 12 ml of ethanol and 6 ml
of water was stirred at 100.degree. C. overnight. After cooling to
r.t., water (20 ml) was added and the mixture was extracted with
ethyl acetate (3.times.50 ml). The combined extracts were dried
over Na.sub.2SO.sub.4 and evaporated in vacuum. Column
chromatography on silica gel 60 (40-63 um, eluent:
hexane/dichloromethane=20:1, vol.) afforded 0.27 g (11%) of the
title product as a yellowish solid.
[0108] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of 2 isomers):
.delta. 7.06-7.47 (m), 6.98 (s), 6.64 (s), 6.58 (d), 6.54 (s), 6.50
(d), 4.67 (s), 4.59 (s), 3.86-4.07 (m), 2.43-2.53 (m), 2.22 (s),
2.08 (s), 1.36 (d), 1.30 (d), 1.11-1.18 (m), 0.91 (d).
2-Isopropyl-1-(2-(3-phenyl-1H-inden-2-yl)phenyl)-1H-indene
(L179)
##STR00024##
[0109] A mixture of 1-(2-bromophenyl)-2-isopropyl-1H-indene (2.10
g, 6.70 mmol, 1.0 equiv),
4,4,5,5-tetramethyl-2-(3-phenyl-1H-inden-2-yl)-1,3,2-dioxaborolane
(2.35 g, 7.40 mmol, 1.1 equiv), sodium carbonate (1.70 g, 17.0
mmol, 2.5 equiv), tetrakis(triphenylphosphine)palladium (0.39 g,
0.34 mmol, 0.05 equiv), 25 ml of toluene, 12 ml of ethanol and 6 ml
of water was stirred at 100.degree. C. overnight. After cooling to
r.t., water (20 ml) was added and the mixture was extracted with
ethyl acetate (3.times.50 ml). The combined extracts were dried
over Na.sub.2SO.sub.4 and evaporated in vacuum. Column
chromatography on silica gel 60 (40-63 um, eluent:
hexane/dichloromethane=10:1, vol,) afforded 1.00 g (36%) of the
title product as a yellowish solid.
[0110] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.58 (d, 1H,
J=7.3 Hz), 7.49 (d, 1 H, J=7.9 Hz), 7.26-7.42 (m, 8H), 7.18-7.23
(m, 2H), 7.11 (t, 1 H, J=7.3 Hz), 7.02 (td, 1 H, J=7.6 Hz, J=1.4
Hz), 6.79 (td, 1H, J=7.5 Hz, J=1.1 Hz), 6.44 (s, 1H), 6.31 (dd, 1H,
J=8.0 Hz, J=1.0 Hz), 5.79 (br.s, 1H), 4.64 (s, 1H), 3.99 (AB
quartet, 2H), 1.98-2.09 (m, 1H), 0.96 (d, 3H, J=6.8 Hz), 0.87 (d,
3H, J=6.9 Hz).
4,4,5,5-Tetramethyl-2-(2-(2-methyl-1H-inden-1-yl)phenyl)-1,3,2-dioxaborol-
ane
##STR00025##
[0111] PdCl.sub.2 (0.22 g, 1.20 mmol, 0.05 equiv.) and PPh.sub.3
(0.65 g, 2.50 mmol, 0.1 equiv.) were added to 160 ml of dry THF,
and the mixture was stirred overnight at 60.degree. C.
1-(2-Bromophenyl)-2-methyl-1H-indene (7.00 g, 24.6 mmol, 1.0
equiv.), bis(pinacolato)diboron (6.86 g, 27.0 mmol, 1.1 equiv.),
and KOAc (7.23 g, 73.8 mmol, 3.0 equiv.) were added therein, and
the resulting mixture was stirred at 60.degree. C. overnight and
then poured into 300 ml of water. The product was extracted with
ether (3.times.100 ml). The combined organic extract was dried over
Na.sub.2SO.sub.4 and evaporated to dryness. Purification of the
residue by flash chromatography on silica gel 60 (40-63 um, eluent:
hexane/dichloromethane=10:1, vol.) afforded 4.50 g (55%) of the
title compound as yellow oil.
[0112] .sup.1H NMR (600 MHz, CDCl.sub.3): .delta. 7.88-7.90 (m,
1H), 7.27 (d, 1H, J=7.4 Hz), 7.18-7.21 (m, 3H), 7.11 (d, 1 H, J=7.2
Hz), 7.03 (td, 1H, J=7.4 Hz, J=1.0 Hz), 6.55 (br.s, 1H), 6.48-6.51
(m, 1 H), 5.44 (s, 1H), 1.91 (s, 3H), 1.38 (s, 6H), 1.37 (s,
6H).
2-(2-(2-Methyl-1H-inden-1-yl)phenyl)-1,3-diphenyl-1H-indene
(L182)
##STR00026##
[0113] A mixture of 4,4,5,5-tetramethyl-2-(2-(2-methyl-1
H-inden-1-yl)phenyl)-1,3,2-dioxaborolane (2.00 g, 6.00 mmol, 1.0
equiv), 2-bromo-1,3-diphenyl-1H-indene [synthesized as described in
EP1264835A1] (2.09 g, 6.00 mmol, 1.0 equiv), cesium carbonate (4.89
g, 15.0 mmol, 2.5 equiv), tetrakis(triphenylphosphine)palladium
(0.35 g, 0.30 mmol, 0.05 equiv) and 30 ml of dry dioxane was
stirred at 100.degree. C. overnight. After cooling to r.t., water
(20 ml) was added and the mixture was extracted with ethyl acetate
(3.times.50 ml). The combined extracts were dried over
Na.sub.2SO.sub.4 and evaporated in vacuum. Column chromatography on
silica gel 60 (40-63 um, eluent: hexane/dichloromethane=4:1, vol.)
afforded 0.80 g (29%) of the title product as a yellowish
solid.
[0114] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of isomers):
.delta. 7.27-7.47 (m), 6.96-7.22 (m), 6.75 (d), 6.71 (d), 6.53 (d),
4.70 (s), 4.66 (s), 3.38-3.50 (m), 1.82 (s), 1.52 (s).
General procedure A. Complexes
[0115] To a solution of a bridged ligand (1.0 equiv) in dry THF (15
ml/mmol), n-butyllithium (2.0 equiv) was added dropwise at
-80.degree. C. and the mixture was stirred at r.t. for 1 h.
Then,
[0116] Zr(NMe.sub.2).sub.2Cl.sub.2(THF).sub.2 (1.0 equiv) was added
at -80.degree. C. and the resulting mixture was allowed to warm
slowly to r.t. and then stirred overnight. The mixture was
evaporated to dryness, the residue was taken up in toluene (5
ml/mmol), and the obtained mixture was evaporated to dryness to
remove traces of THF. The residue was dissolved in toluene (5
ml/mmol), the resulting solution was filtered through a pad of
Celite 503. The filtrate was placed into a glass heavy wall
pressure vessel and Me.sub.2SiCl.sub.2 (5.0 equiv) was added in one
portion. The resulting mixture was stirred at 60.degree. C. for 24
h. After cooling to r.t., the mixture was filtered through a pad of
Celite 503 and the filtrate was evaporated to dryness. The residue
was purified by recrystallization.
Catalyst ID 140
##STR00027##
[0118] According to the General procedure A, 0.63 g (32%) of the
title compound (pure single isomer, syn-orientation of the methyl
and phenyl groups) were obtained from
2-methyl-1-(2-(3-phenyl-1H-inden-2-yl)phenyl)-1H-indene, (L140;
1.40 g, 3.53 mmol, 1.0 equiv), n-butyllithium (2.9 ml, 7.11 mmol,
2.0 equiv), Zr(NMe.sub.2).sub.2Cl.sub.2(THF).sub.2(1.40 g, 3.53
mmol, 1.0 equiv) and Me.sub.2SiCl.sub.2 (2.27 g, 17.6 mmol, 5.0
equiv) after isolation of the crude product by recrystallization as
follows. The crude product was dissolved in 50 ml of toluene, and
20 ml of hexane were added. The mixture was then filtered, and the
filtrate was evaporated in vacuum to dryness. The residue was
redissolved in 20 ml of toluene, and 30 ml of hexane was added. The
precipitate formed was filtered and redissolved in 40 ml of hot
toluene. The obtained solution was left overnight at r.t., then
filtered, and the filtrate was evaporated in vacuum until formation
of precipitate started (.about.30 ml). The mixture was left
overnight at r.t., the precipitate formed was filtered, washed with
toluene and dried in vacuum. Thus, the first crop of the product
was obtained. The filtrate was concentrated in vacuum to .about.10
ml and left overnight. The precipitate formed was filtered, washed
with toluene and dried in vacuum to give the second crop of the
product. The two crops were combined and dried in vacuum for 1 h at
50.degree. C. The product contained 0.5 equiv. of toluene according
to .sup.1H NMR spectrum.
[0119] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.89 (d, 1H,
J=8.6 Hz), 7.78 (m, 2H), 7.59-7.70 (m, 2H), 7.56 (td, 1H, J=7.5 Hz,
J=1.5 Hz), 7.46-7.50 (d, 2H), 7.46-7.42 (m, 2H), 7.07-7.37 (m, 9H
+5H in toluene), 6.64 (s, 1H), 6.11 (s, 1 H), 2.37 (s, 3H in
toluene) 1.58 (s, 3H).
Catalyst ID 157
##STR00028##
[0121] According to the General procedure A, 0.85 g (56%) of the
title compound were obtained from
1-(2-(1H-inden-2-yl)phenyl)-2-isopropyl-1H-indene, (L157; 1.05 g,
3.00 mmol, 1.0 equiv), n-butyllithium (2.46 ml, 6.00 mmol, 2.0
equiv), Zr(NMe.sub.2).sub.2Cl.sub.2(THF).sub.2(1.20 g, 3.00 mmol,
1.0 equiv) and Me.sub.2SiCl.sub.2(1.91 g, 15.0 mmol, 5.0 equiv)
after recrystallization of the crude product from 40 ml of
toluene.
[0122] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.49-7.57 (m,
4H), 7.46 (dd, 1 H, J=8.7 Hz, J=0.8 Hz), 7.36-7.40 (m, 2H),
7.28-7.32 (m, 2H), 7.10-7.21 (m, 3H), 6.74 (s, 1H), 6.19-6.21 (m,
1H), 6.05-6.07 (m, 1H), 2.99-3.09 (m, 1H), 1.38 (d, 3H, J=7.0 Hz),
1.09 (d, 3H, J=6.8 Hz).
Catalyst ID 158
##STR00029##
[0124] According to the General procedure A, 0.05 g (16%) of the
title compound were obtained from
2-(2-(2-isopropyl-1H-inden-1-yl)phenyl)-1,3-dimethyl-1H-indene
(L158; 0.23 g, 0.60 mmol, 1.0 equiv), n-butyllithium (0.50 ml, 1.20
mmol, 2.0 equiv), Zr(NMe.sub.2).sub.2Cl.sub.2(THF).sub.2 (0.24 g,
0.60 mmol, 1.0 equiv) and Me.sub.2SiCl.sub.2 (0.37 g, 3.00 mmol,
5.0 equiv) after recrystallization of the crude product from 10 ml
of toluene.
[0125] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.52-7.63 (m,
4H), 7.39-7.44 (m, 2H), 7.27-7.34 (m, 3H), 7.21-7.25 (m, 1H), 7.18
(dd, 1 H, J=8.7 Hz, J=0.8 Hz), 7.04-7.08 (m, 1 H), 6.70 (s, 1 H),
2.88-2.98 (m, 1 H), 2.34 (s, 3H), 2.01 (s, 3H), 1.41 (d, 3H, J=6.8
Hz), 1.11 (d, 3H, J=6.8 Hz).
Catalyst ID 179
##STR00030##
[0127] According to the General procedure A, 1.50 g (44%) of the
title compound were obtained as 1:1 mixture of two isomers from
2-isopropyl-1-(2-(3-phenyl-1H-inden-2-yl)phenyl)-1H-indene (L179;
2.50 g, 5.90 mmol, 1.0 equiv), n-butyllithium (4.80 ml, 11.7 mmol,
2.0 equiv), Zr(NMe.sub.2).sub.2Cl.sub.2(THF).sub.2(2.32 g, 5.90
mmol, 1.0 equiv) and Me.sub.2SiCl.sub.2 (3.60 g, 29.0 mmol, 5.0
equiv).
[0128] Separation of isomers was conducted as follows: a portion
(270 mg) of 1:1 mixture of isomers was recrystallized from 20 ml
hexane-dichloromethane mixture (5:1, vol.) to afford 50 mg of pure
isomer 1 (syn-orientation of the isopropyl and phenyl groups). The
mother liquor was evaporated to 10 ml and the precipitate was
filtered off (a mixture of isomers according to .sup.1H NMR). The
filtrate was evaporated to dryness and the resulting solid was
recrystallized from 10 ml of hexane to afford 35 mg of pure isomer
2 (anti-orientation of the isopropyl and phenyl groups).
[0129] .sup.1H NMR (400 MHz, CDCl.sub.3, isomer 1): .delta. 7.86
(dd, 1H, J=8.7 Hz, J=0.8 Hz), 7.81-7.84 (m, 2H), 7.70-7.72 (m, 1H),
7.62 (td, 1H, J=7.5 Hz, J=1.3 Hz), 7.56 (td, 1H, J=7.5 Hz, J=1.4
Hz), 7.47-7.52 (m, 1H), 7.44 (d, 1H, J=9.4 Hz), 7.29-7.37 (m, 5H),
7.21-7.26 (m, 2H), 7.02-7.09 (m, 2H), 6.72 (s, 1 H), 5.93 (s, 1 H),
1.64-1.74 (m, 1H), 0.98 (d, 3H, J=6.7 Hz), 0.75 (d, 3H, J=6.9
Hz).
[0130] .sup.1H NMR (400 MHz, CDCl.sub.3, isomer 2): .delta. 7.64
(d, 2H, J=9.2 Hz), 7.50-7.57 (m, 3H), 7.45 (d, 1H, J=8.7 Hz),
7.17-7.36 (m, 9H), 6.67-6.71 (m, 2H), 6.28 (s, 1H), 6.16 (d, 1H,
J=8.5 Hz), 2.86-2.97 (m, 1H), 1.40 (d, 3H, J=6.9 Hz), 1.04 (d, 3H,
J=6.9 Hz).
Catalyst ID 182
##STR00031##
[0132] According to the General procedure A, 0.12 g (11%) of the
title compound were obtained from
2-(2-(2-methyl-1H-inden-1-yl)phenyl)-1,3-diphenyl-1H-indene (L182;
0.80 g, 1.70 mmol, 1.0 equiv), n-butyllithium (1.40 ml, 3.40 mmol,
2.0 equiv), Zr(NMe.sub.2).sub.2Cl.sub.2(THF).sub.2 (0.67 g, 1.70
mmol, 1.0 equiv) and Me.sub.2SiCl.sub.2(1.06 g, 8.50 mmol, 5.0
equiv) after recrystallization of the crude product from 20 ml of
toluene and washing the resulting crystals with diethyl ether.
[0133] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 8.13 (d, 1H,
J=7.9 Hz), 8.04 (d, 2H, J=7.5 Hz), 7.94 (d, 1H, J=8.4 Hz),
7.65-7.71 (m, 2H), 7.48-7.54 (m, 3H), 7.41 (d, 1 H, J=8.5 Hz),
7.17-7.36 (m, 9H), 7.14 (d, 1H, J=7.8 Hz), 6.64 (s, 1H), 6.52-6.56
(m, 1 H), 5.83 (d, 1 H, J=8.5 Hz), 1.47 (s, 3H).
Polymerisations
[0134] The polymerisations were carried out in a PPR48 Parallel
Pressure Reactor (PPR) for olefin polymerisation. This equipment,
containing 48 reactors mounted in a triple glove-box, was sold
commercially by the company Symyx, thereafter by the company
Freeslate. The applied polymerisation protocols were as
follows:
[0135] Prior to the execution of a library, the 48 PPR cells
(reactors) undergo bake-and-purge' cycles overnight (8 h at
90-140.degree. C. with intermittent dry N2 flow), to remove any
contaminants and left-overs from previous experiments. After
cooling to glove-box temperature, the stir tops are taken off, and
the cells are fitted with disposable 10 mL glass inserts and PEEK
stirring paddles (previously hot-dried under vacuum); the stir tops
are then set back in place, the cells are loaded with the proper
amounts of toluene (in the range 2.0-4.0 mL), 1-hexene (in the
range 0.05-2.0 mL) and MAO solution (100 .mu.L of 0.1 mol L-1 in
toluene), thermostated at 80.degree. C., and brought to the
operating pressure of 550 kPa (65 psig) with ethylene. At this
point, the catalyst injection sequence is started; proper volumes
of a toluene `chaser`, a solution of the precatalyst in toluene
(typically in the range 0.005-0.05 mmol L-1), and a toluene
`buffer` are uptaken into the slurry needle, and then injected into
the cell of destination. The reaction is left to proceed under
stirring (800 rpm) at constant temperature and pressure with
continuous feed of ethylene for 5-60 min, and quenched by
over-pressurizing the cell with dry air (preferred to other
possible catalyst poisons because in case of cell or quench line
leaks oxygen is promptly detected by the dedicated glove-box
sensor).
[0136] After quenching, the cells are cooled down and vented, the
stir-tops are removed, and the glass inserts containing the
reaction phase are taken out and transferred to a Genevac EZ2-Plus
centrifugal evaporator, where all volatiles are distilled out and
the polymers are thoroughly dried overnight. Reaction yields are
double-checked against on-line monomer conversion measurements by
robotically weighing the dry polymers in a Bohdan Balance Automator
while still in the reaction vials (subtracting the pre-recorded
tare). Polymer aliquots are then sampled out for the
characterizations.
GPC Analysis
[0137] GPC curves are recorded with a Freeslate Rapid GPC setup,
equipped with a set of 2 mixed-bed Agilent PLgel 10 .mu.m columns
and a Polymer Char IR4 detector. The upper deck of the setup
features a sample dissolution station for up to 48 samples in 10 mL
magnetically stirred glass vials, 4 thermostated bays each
accommodating 48 polymer solutions in 10 mL glass vials, and a dual
arm robot with two heated injection needles. With robotic
operation, pre-weighed polymer amounts (typically 1-4 mg) are
dissolved in proper volumes of orthodichlorobenzene (ODCB)
containing 0.40 mg mL-1 of 4-methyl-2,6-di-tert-butylphenol (BHT)
as a stabilizer, so as to obtain solutions at a concentration of
0.5 to 1.0 mg mL-1. After 2-4 h at 150.degree. C. under gentle
stirring to ensure complete dissolution, the samples are
transferred to a thermostated bay at 145.degree. C., and
sequentially injected into the system at 145.degree. C. and a flow
rate of 1.0 mL min-1. In post-trigger delay operation mode, the
analysis time is 12.5 min per sample.
[0138] Calibration is carried out with the universal method, using
10 monodisperse polystyrene samples (Mn between 1.3 and 3700 KDa).
Before and after each campaign, samples from a known i-PP batch
produced with an ansa-zirconocene catalyst are analyzed for a
consistency check.
NMR Characterizations
[0139] 13C NMR spectra are recorded with a Bruker Avance 400 III
spectrometer equipped with a 5 mm High Temperature Cryoprobe, and a
robotic sample changer with pre-heated carousel (24 positions). The
samples (20-30 mg) are dissolved at 120.degree. C. in
tetrachloroethane-1,2-d2 (0.6 mL), added with 0.40 mg mL-1 of BHT
as a stabilizer, and loaded in the carousel maintained at the same
temperature. The spectra are taken sequentially with automated
tuning, matching and shimming. Typical operating conditions for
routine measurements are: 45.degree. pulse; acquisition time, 2.7
s; relaxation delay, 5.0 s; 400-800 transients (corresponding to an
analysis time of 30-60 min). Broad-band proton decoupling is
achieved with a modified WALTZ16 sequence (BI WALTZ16_32 by
Bruker).
[0140] The catalyst activity is indicated by Rp, the calculated
polymerisation rate, expressed as kilograms of copolymer, produced
per mmol of catalyst per mol of ethylene in the reactor-diluent per
hour [kg/(mmol.sub.cat[C.sub.2H.sub.4]h)].
[0141] The hexene (C6) reactivity (in mol % vol %) is expressed as
mol percent hexene-incorporation in the copolymer (C6 inc., in mol
%) per volume percent 1-hexene in the reaction diluent (C6, in vol
%). This reactivity is the averaged value of the polymerisation
runs. Obviously, a higher hexene-incorporation per volume percent
in the reaction-medium indicates a higher hexene reactivity.
[0142] The weight average molecular weight is expressed in
kiloDaltons (kDa)
[0143] The catalysts that were employed in the PPR polymerisation
experiments are presented in table 1 below.
TABLE-US-00001 TABLE 1 Catalyst ID 4 1 135 Molecular structure
##STR00032## ##STR00033## ##STR00034## Catalyst ID 140 158 157
Molecular structure ##STR00035## ##STR00036## ##STR00037## Cat ID
179 182 Molecular structure ##STR00038## ##STR00039##
##STR00040##
[0144] The experimental results are summarized in Table 2.
TABLE-US-00002 TABLE 2 Rp [kg/ C6 react Experi- C6 (mmol.sub.cat Mw
MWD C6 inc [mol %/ ment Cat [vol %] [C.sub.2H.sub.4] h)] [kDa] [-]
[mol %] vol %] A 4 0 1026 -- -- -- 0.08 10 641 8 2 0.8 50 140 -- --
4.3 B 1 0 724 -- -- -- 0.1 10 478 386 2.9 1 40 160 222 3 4.1 C 135
0 517 -- -- -- 0.3 5 233 267 4 1.4 10 152 183 4.7 3.1 D 140 0 836
-- -- -- 0.7 2 645 346 2.2 1.5 10 307 214 2.8 6.0 E 158 0 2290 --
-- -- 1.2 2 460 144 2.1 2.6 10 830 73 2.1 11.2 F 157 0 930 -- -- --
1.4 2 860 161 2.0 2.7 10 850 78 2.1 14.5 G 179 0 5 -- -- -- 1.3 2
60 159 2.5 2.9 10 5 92 2.5 11.2 H 182 0 2 -- -- -- 1.1 2 20 143 2.3
2.3 10 2 73 2.1 10.9
[0145] Experiment A is comparative and reflects example III.5 of
U.S. Pat. No. 6,342,622; Experiment B also is comparative and
reflects example VIII..4 of U.S. Pat. No. 6,342,622; Experiment C
also is comparative. Experiments D through H are experiments
according to the present invention.
[0146] Table 2 illustrates that when using a 1,2-phenylene bridge
between two 2-indenyl moieties (Catalyst complex 4) as described in
U.S. Pat. No. 6,342,622, the molecular weight and the
hexene-reactivity are very low. When replacing the 1,2-phenylene
bridge by a 2,2'-biphenylene bridge between two 2-indenyl moieties
(Catalyst complex 1), the molecular weight is increased, but the
hexene-reactivity remains low. When replacing one 2-indenyl moiety
by a 1-indenyl moiety as in (Catalyst complex 135), the molecular
weight remains high, but although there is an improvement in the
hexene-reactivity, this reactivity still requires improvement.
Surprisingly, when compounds according to the invention are used,
the hexene-reactivity is drastically increased while maintaining
high molecular weight.
* * * * *