Note: Descriptions are shown in the official language in which they were submitted.
CA 02628442 2008-05-02
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TIC 2005/G009 Ticona GmbH
Process for Manufacturing Ultra High Molecular Weight Polymers Using Novel
Bridged Metallocene Catalysts
The invention relates to a process of manufacturing ultra high molecular
weight
polymers via the polymerization and co-polymerization of olefins using
catalysts and
their catalyst systems.
Ultra high molecular weight ethylene polymers refer to a viscosimetrically
determined
molecular weight of greater than 1 x 106 mol/g. Because of their extraordinary
properties, such as higher abrasion resistance and low sliding friction, such
polymers
have a multitude of uses. Consequently, they are used in materials handling,
bulk
materials handling, as well as in medical applications such as joint sockets
in
prosthetic joints.
Because of these novel properties, the processing of ultra high molecular
weight
polyethylene is highly complex. Ram-extrusion and compression molding of
powdered raw materials are processes used to produce molded parts, whereby the
molded parts manufactured often still exhibit the characteristics of the raw
powder.
Films and fibers are produced using solution or gel processes, which require a
large
amount of solvents. An objective is therefore to develop new ultra high
molecular
weight polyethylenes, which have improved processability.
According to the present state of technology, ultra high molecular weight
polyethylene is manufactured according to the low pressure process using
heterogeneous Ziegler catalysts. Such catalysts are, for example, described in
the
following patent documents: EP186995, DE3833445, EP575840 and
US20020045537.
Other known catalysts for olefin polymerization are single site catalysts.
According
to the present state of technology, ultra high molecular weight polymers are
manufactured using these catalysts only in exceptional cases and under
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economically unprofitable conditions. Consequently, heterogeneous constrained-
geometry catalysts form ultra high molecular weight polyethylene only with
moderate
activity and increased long chain branching, which can lead to reduced
hardness
and worse abrasion properties. With so-called phenoxy-imine catalysts, UHMWPE
is obtained only at low activity at economically unprofitable temperature
levels.
Examples of these as well as other metallocenes are described in W09719959,
W00155231, Adv. Synth. Catal 2002, 344, 477-493, EP0798306 as well as in
EP0643078.
Surprisingly, bridged single site catalysts with a suitable ligand structure
were found,
which in connection with aluminoxanes as co-catalysts, not only permitted the
manufacture of ultra high molecular weight polyethylenes with a
viscosimetrically
determined molecular weight of greater than 1 x 106 mol/g, but also produced
products with improved processability. The reason for the improved
processability,
without being bound to a theory, has to do with the narrower molecular weight
distribution Mw/Mn of 2 to 6 compared to polymers that were manufactured using
Ziegler catalysts and have a molecular weight distribution Mw/Mn of 3 to 30.
The process according to the invention also contradicts the prejudice that
economically manufacturing ultra high molecular weight polymers is impossible
using
aluminoxanes as co-catalysts. Through its novel ligand structure, the catalyst
is
sterically shielded enough against the primary mechanism for low molecular
weight
products to result, namely the chain transfer to aluminoxane, without however
losing
its economically necessary activity to the monomers.
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The object of the present invention is a process to manufacture ultra high
molecular
weight polymers using the compounds of Formula I
R5
R4
R6
R7 OLC R3
Ri
-R2
R8
R15
R10 _________________________________
R13
Ri
R12
Formula I
whereby:
M1 is a transition metal of the 3rd to 6th group of the periodic table,
whose
oxidation level does not equal zero, and is preferably Ti, Zr, Hf, V, Mo, Sc,
Y,
Cr and Nb; and
R1 is hydrogen or a C1-C20-carbonaceous group or a halogen atom; and
R2 is hydrogen or a C1-C20 carbonaceous group or a halogen atom; and
R3, R1 are each identical or different and are each a C1-C20 carbonaceous
group,
provided that at least one radical R3 orRi is a C2-C20 carbonaceous group;
and
R4, R5, Rs, R7, R5, R10, R11, R12, R13, R14, .-.15
I-K
are each identical or different and are
each hydrogen or a halogen atom or a C1-C20 carbonaceous group, whereby
two or several consecutively can form a cyclic system; and
R9 forms a bridge between the ligands, which can be shown by the following
formulae:
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/ 17
R16._m2 R17
R16-m2--R17
R16¨fe_R17
R16 ¨C¨R17
whereby:
M2 is either silicon, germanium or tin; and
17
R are each identical or different and equal to hydrogen or a C1-C20
carbonaceous group or a halogen atom.
In the present invention, a C1-C20 carbonaceous group is understood to be
preferably the radicals
Ci-C20 ¨alkyl, in particular methyl, ethyl, n-propyl, i-propyl, n-butyl, i-
butyl, s-butyl, t-
butyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl, or
cyclooctyl,
Ci-C20 alkenyl, in particular ethenyl, propenyl, butenyl, pentenyl,
cyclopentenyl,
hexenyl, cyclohexenyl, octenyl or cyclooctenyl,
Ci-C20 alkinyl, in particular ethinyl, propinyl, butinyl, pentinyl, hexinyl or
octinyl, C6-
C20 aryl, in particular benzylidene, o-methoxybenzylidene, 2,6-
dimethylbenzylidene,
phenyl, biphenyl, naphthyl, anthracenyl, triphenylenyl, [1,1',3',11-terpheny1-
2'-yl,
binaphthyl, or phenanthrenyl,
C1-C20 fluoralkyl, in particular, trifluoromethyl, pentafluoroethyl or 2,2,2-
trifluoroethyl,
C6-C20 fluoroaryl, in particular pentafluorophenyl, 3,5-
bistrifluoromethylphenyl,
pentafluorobenzylidene, 3,5-bistrifluoromethylbenzylidene, tetrafluorophenyl,
or
heptafluoronaphthyl,
C1-C20 alkoxy, in particular methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy,
i-
butoxy, s-butoxy, or t-butoxy,
C6-C20 aryloxy, in particular phenoxy, naphthoxy, biphenyloxy, anthracenyloxy,
phenanthrenyloxy,
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C7-C20 arylalkyl, in particular o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylphenyl,
2,6-
diethylphenyl, 2,6-di-i-propylphenyl, 2,6-di-t-butylphenyl, o-t-butylphenyl, m-
t-
butylphenyl, p-t-butylphenyl,
07-C20 alkylaryl, in particular benzyl, ethylphenyl, propylphenyl,
diphenylmethyl,
5 triphenylmethyl, or naphthalinylmethyl,
C7-C20 aryloxyalkyl, in particular o-methoxyphenyl, m-phenoxymethyl, p-
phenoxymethyl,
C12-C20 aryloxyaryl, in particular p-phenoxyphenyl, C5-C20 heteroaryl, in
particular 2-
pyridyl, 3-pyridyl, 4-pyridyl, chinolinyl, isochinolinyl, acridinyl,
benzochinolinyl, or
benzoisochinolinyl,
04-020 heterocycloalkyl, in particular furyl, benzofuryl, 2-pyrolidinyl, 2-
indolyl, 3-
indolyl, 2,3-dihydroindolyl,
08-020 arylalkenyl, in particular o-vinylphenyl, m-vinylphenyl, p-vinylphenyl,
C8-C20 arylalkinyl, in particular o-ethynylphenyl, m-ethynylphenyl, or p-
ethynylphenyl,
02-020 heteroatomic group, in particular carbonyl, benzoyl, oxybenzoyl,
benzoyloxy,
acetyl, acetoxy, or nitrile, whereby one or more 01-020 carbonaceous groups
can
form a cyclic system.
In the present invention, a C2-C20 carbonaceous group is understood to be
preferably the radicals
C2-C20 alkyl, in particular ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-
butyl, t-butyl, n-
pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl, or cyclooctyl,
02-020 alkenyl, in particular ethenyl, propenyl, butenyl, pentenyl,
cyclopentenyl,
hexenyl, cyclohexenyl, octenyl or cyclooctenyl,
02-020 alkinyl, in particular ethinyl, propinyl, butinyl, pentinyl, hexinyl or
octinyl,
C6-C20 aryl, in particular benzylidene, o-methoxybenzylidene, 2,6-
dimethylbenzylidene, phenyl, biphenyl, naphthyl, anthracenyl, triphenylenyl,
[1,1',3',11-terpheny1-2'-yl, binaphthyl, or phenanthrenyl,
C2-C20 fluoroalkyl, in particular, 3-trifluoropropyl, 2,2'-trifluoroisopropyl,
06-020
fluoroaryl, in particular pentafluorophenyl, 3,5-bistrifluoromethylphenyl,
pentafluorobenzylidine, 3,5-bistrifluoromethylbenzylidine, tetrafluorophenyl
or
heptafluoronaphthyl,
C2-C20 alkoxy, in particular n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-
butoxy, or t-
butoxy,
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C6-C20 aryloxy, in particular phenoxy, naphthoxy, biphenyloxy, anthracenyloxy,
phenanthrenyloxy,
C7-C20 arylalkyl, in particular o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylphenyl,
2,6-
diethylphenyl, 2,6-di-i-propylphenyl, 2,6-di-t-butylphenyl, o-t-butylphenyl, m-
t-
butylphenyl, p-t-butylphenyl,
C7-C20 alkylaryl, in particular benzyl, ethylphenyl, propylphenyl,
diphenylmethyl,
triphenylmethyl, or naphthalinylmethyl,
C7-C20 aryloxyalkyl, in particular o-methyoxyphenyl, m-phenoxymethyl, p-
phenoxymethyl,
C12-C20 aryloxyaryl, in particular p-phenoxyphenyl,
C5-020 heteroaryl, in particular 2-pyridyl, 3-pyridyl, 4-pyridyl, chinolinyl,
isochinolinyl,
acridinyl, benzochinolinyl, or benzoisochinolinyl,
C4-C20 heterocycloalkyl, in particular furyl, benzofuryl, 2-pyrolidinyl, 2-
indolyl, 3-
indolyl, 2,3-dihydroindolyl,
C8-C20 arylalkenyl, in particular o-vinylphenyl, m-vinylphenyl, p-vinylphenyl,
C8-C20 arylalkinyl, in particular o-ethynylphenyl, m-ethynylphenyl, or p-
ethynylphenyl,
C2-C20 heteroatomic group, in particular benzoyl, oxybenzoyl, benzoyloxy,
whereby
one or more C2-C20 carbon containing groups can form a cyclic system.
In a preferred embodiment of the invention, for Formula 1:
M1 shall be a transition metal of the 4th group of the periodic table,
whose
oxidation level does not equal zero, and is preferably Ti, Zr or Hf; and
R1 shall be hydrogen or a C1-C20-carbonaceous group or a halogen atom;
and
R2 shall be hydrogen or a Ci-C20 carbonaceous group or a halogen atom; and
R3 shall be a C2-C20 carbonaceous group, preferably one cyclized in an
a- or (3-
position or one in an a- or (3- position branched carbonaceous group; and
Rlo shall be a C1-C10 carbonaceous group; and
R4, R6, R7, R8, R10, R11, R13, R14, ,-,15
K shall each be equal to hydrogen; and
R5, R12 shall each be identical or different and shall be a C1-C20
carbonaceous
group, of which two or several consecutively can form a cyclic system; and
R9 shall form a bridge between the ligands, which can be shown by the
following
formulae:
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.,/
R17
R16¨C¨R17
/ 17
R16-C.-R17
Whereby:
M2 is silicon; and
K-16,
R17 are each identical or different and are each hydrogen or a Ci-C20
carbonaceous group or a halogen atom.
In another embodiment of the invention, for Formula 1:
M1 shall be zirconium; and
R1, R2 shall be equal and stand for chlorine, methyl or phenolate; and
R3 shall be an isopropyl-, isobutyl-, cyclopentyl-, cyclohexyl-, tert-
butyl-, or a
phenyl group; and
R10 shall be a C1-C6 carbonaceous group and an alkyl group; and
R4, Rs, R7, R8, R10, R11, R13, R14, -15
K shall each be hydrogen; and
R5, R12 shall be identical and a phenyl group which supports a C1-C4 alkyl
group in
para-position; and
R9 shall form a bridge between the ligands, which can be shown by the
following
formulae:
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R16¨M2¨R17
R16¨C--R17
R16-m2-R17
R16-C-R17
R16-m2___R17
R1'-C-R17
Whereby:
M2 is silicon; and
R16, R17 are each identical or different and are hydrogen or a Ci-C20
carbonaceous
group or a halogen atom.
Illustrative but non-limiting examples for compounds of Formula I are:
Dimethylsilandiy1-(2-isopropy1-4-(p-isopropyl-phenyl)indenyl)(2-methyl-4-(p-
isopropyl-
phenyl)indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-4-(p-tert.-butyl-phenypindenyl)(2-methyl-4-(P-
tert.-
butyl-phenypindenyl)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-4-(p-tert.-butyl-phenypindenyl)(2,7-dimethyl-4-
(P-tert.-
butyl-phenyl) indenyI)-zirconium dichloride,
Dirnethylsilandiy1-(2-isopropy1-4-(p-tert.-butyl-phenyl)indenyl)(2,5,6,7-
tetramethyl-4-
(p-tert.-butyl-phenyl)indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-6-methy1-4-(p-tert.-butyl-phenyl )indenyl)(2,6-
dimethyl-
4-(p-tert.-butyl-phenyl)indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-4-(p-sec.-butyl-phenypindenyl)(2-methyl-4-(p-
sec.
butyl-phenyl)indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-4-(p-cyclohexyl-phenyl)indenyl)(2-methyl-4-(p-
cyclohexyl-phenypindeny1)- zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-4-(p-trimethylsilyl-phenypindenyl)(2-methyl-4-
(p-tri
methylsilyl-phenyl)indeny1)- zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-4-(p-adamantyl-phenyl)indenyl)(2-methyl-4-(p-
adamantyl-phenyl)indeny1)- zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-4-(p-tris(trifluoromethyl)methyl-
phenypindenyl)(2-
methyl-4-(p-tris(trifluoromethyl)methyl-phenyl)indenyl)-zirconium dichloride,
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Dimethylsilandiy1-(2-isopropy1-4-phenyl-indenyl)(2-methyl-4-(p-tert.-butyl-
phenyl)indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropyl-4-(p-tert.-butyl-phenyl )indenyl)(2-methy1-4-
phenyl-
indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropyl-4-(p-tert -butyl-phenypindenyl)(2,7-dimethyl-4-
phenyl-
indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-4-(p-tert.-butyl-phenypindenyl)(2,5,6,7-
tetramethyl-4-
phenyl-indenyI)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-6-methy1-4-(p-tert.-butyl-phenyl)indenyl)(2,6-
dimethyl-
4-phenyl-indenyI)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropyl-4-phenyl-indenyl)(2,7 -dimethy1-4-(p-tert.-
butyl-
phenyl)indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-4-phenyl-indenyl)(2,5,6,7-tetramethyl-4-(p-
tert.-butyl-
phenyl)indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-6-methy1-4-phenyl-indenyl)(2,6-dimethyl-4-(p-
tert.-
butyl-phenyl)indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-4-(p-tert.-butyl-phenypindenyl)(2 -methy1-4-(4-
naphthyl)-indenyl)indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-isopropy1-4-(4-naphthyl)-indenyl)indenyl)(2-methyl-4-(p-
tert.-
butyl-phenyl)indenyI)-zirconium dichloride,
Dimethylsilandiyl-bis(2-isopropyl[4,5]-benzo-indenyl)zirconium dichloride,
Dimethylsilandiyl-bis(2-isopropyl-indenyl)zirconium dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(1-naphthyl)-indenyOzirconium dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(2-naphthyl)-indenyl)zirconium dichloride,
Dimethylsilandiyl-bis(2-isopropyl-4-phenyl-indenyl)zirconium dichloride,
Dimethylsilandiyl-bis(2-isopropyl-4-tert.-butyl-indenyl) zirconium dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-isopropyl-indenyl) zirconium dichloride,
Dimethylsilandiyl-bis(2-isopropyl-4-ethyl-indenyl) zirconium dichloride,
Dimethylsilandiyl-bis(2-isopropyl-4- acenaphth-indenyl) zirconium dichloride,
Dimethylsilandiyl-bis(2,4-diisopropyl-indenyl) zirconium dichloride,
Dimethylsilandiyl-bis(2-isopropyl-4-methyl-indenyOzirconium dichloride
Dimethylsilandiyl-bis(2,4,6-triisopropyl-indenyl) zirconium dichloride,
Dimethylsilandiyl-bis(2,4,5-triisopropyl-indenyl)zirconium dichloride,
Dimethylsilandiyl-bis(2-isopropy1-5-isobutyl-indenyl) zirconium dichloride
CA 02628442 2008-05-02
Dimethylsilandiyl-bis(2-isopropyl-5-t-butyl-indenyl)zirconium dichloride,
Dimethylsilandiyl-bis(2-isopropyl-4-(4'-tert-butyl-phenyl )-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropyl-4-(4'-methyl-phenyl)-indenyl) zirconium
dichloride,
5 Dimethylsilandiyl-bis(2-isopropyl-4-(4'-ethyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-trifluoromethyl-pheny1)-indenyl)
zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-methoxy-pheny1)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-tert-butyl-pheny1)-indenyl)zirconium
dimethyl,
10 Dimethylsilandiyl-bis(2-isopropy1-4-(4'-methyl-pheny1)-indenyl)zirconium
dimethyl,
Dimethylsilandiyl-bis(2-isopropyl-4-(4'-ethyl-phenyl)-indenyl) zirconium
dimethyl,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-trifluoromethyl-phenyl)indenyl)
zirconium
dimethyl,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-methoxy-pheny1)-indenyl) zirconium
dimethyl,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-tert.-butyl-pheny1)-indenyl)hafnium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-444'-tert.-butyl-pheny1)-indenyptitanium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-n-propyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-n-butyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-hexyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropyl-4-(4'-sec-butyl-phenyl )-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-methyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-ethyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-n-propyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-n-butyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-hexyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-pentyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-cyclohexyl-pheny1)-indenyl)zirconium
dichloride, Dimethylsilandiyl-bis(2-isopropy1-4-(4'-sec-butyl-pheny1)-
indenyl)zirconium
dichloride, Dimethylsilandiyl-bis(2-isopropy1-4-(4'-tert.-butyl-pheny1)-
indenyl)
zirconium dichloride, Dimethylsilandiyl-bis(2-n-propy1-4-phenyl-
indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-propy1-4-(4'-methyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-propy1-4-(4'-ethyl-phenyl)-indenyl) zirconium
dichloride,
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11
Dimethylsilandiyl-bis(2-n-propy1-4-(4'-iso-propyl-pheny1)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-propy1-4-(4'-n-butyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-propy1-4-(4'-hexyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-propy1-4-(4'-cyclohexyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-propy1-4-(4'-sec-butyl-pheny1)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-propy1-4-(4'-tert. -butyl-phenyl)-indenyl) zirconium
dichloride, Dimethylsilandiyl-bis(2-n-butyl-4-phenyl-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-butyl-4-(4'-methyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-buty1-4-(4'-ethyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-buty1-4-(4'-n-propyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-buty1-4-(4'-iso-propyl-pheny1)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-butyl-4-(4'-n-butyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-buty1-4-(4'-hexyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-buty1-4-(4'-cyclohexyl-pheny1)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-buty1-4-(4'-sec-butyl-pheny1)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-n-buty1-4-(4'-tert.-butyl-pheny1)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-hexy1-4-phenyl-indenyl) zirconium dichloride,
Dimethylsilandiyl-bis(2-hexy1-4-(4'-methyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-hexy1-4-(4'-ethyl-pheny1)-indenyl)zirconium
dichloride,
Dirnethylsilandiyl-bis(2-hexy1-4-(4'-n-propyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-hexy1-4-(4'-iso-propyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-hexy1-4-(4'-n-butyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-hexy1-4-(4'-n-hexyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-hexy1-4-(4'-cyclohexyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-hexy1-4-(4'-sec-butyl-pheny1)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-hexy1-4-(4'-tert. -butyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-phenyl-4-phenyl-indenyl)zirconium dichloride,
Dimethylsilandiyl-bis(2-pheny1-4-(4'-methyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-pheny1-4-(4'-ethyl-pheny1)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-pheny1-4-(4'-n-propyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-pheny1-4-(4'-iso-propyl-pheny1)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-phenyl-4-(4'-n-butyl-phenyl)-indenyl) zirconium
dichloride,
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12
Dimethylsilandiyl-bis(2-phenyl-4-(4'-n-hexyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-pheny1-4-(4'-cyclohexyl-pheny1)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-phenyl-4-(4'-sec-butyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-pheny1-4-(4'-tert.-butyl-phenyl)-indenyl) zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-tert.-butyl-pheny1)-
indenyl)zirconiumbis(dimethylamine),
Dimethylsilandiyl-bis(2-isopropyl-4-(4'-tert. -butyl-phenyl)-indenyl)zirconium
dibenzyl,
Dimethylsilandiyl-bis(2-ethyl-4-(4'-tert. -butyl-phenyl)-indenyl)zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropy1-4-(4'-tert.-butyl-pheny1)-indenyl) zirconium
dimethyl,
Dimethylsilandiy1-(2-methy1-4-azapentalene)(2-isopropy1-4-(4'-methyl-pheny1)-
indenyl) zirconium dichloride,
Dimethylsilandiy1-(2-methy1-5-azapentalene)(2-isopropy1-4-(4'-methyl-phenyl)-
indenyl) zirconium dichloride,
Dimethylsilandiy1-(2-methy1-6-azapentalene)(2-isopropy1-4-(4'-methyl-pheny1)-
indenyl) zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-azapentalene)(2-isopropy1-4-(4'-ethyl-
phenyl)indenyl)zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-thiapentalene)(2-isopropy1-4-(4'-n-propyl-
pheny1)-
indenyl)zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-azapentalene)(2-isopropy1-4-(4'-isopropyl-
pheny1)-
indenyl)zirconium dichloride,
Dimethylsilandiy1-(2-methy1-6-azapentalene)(2-isopropy1-4-(4'-isopropyl-
pheny1)-
indenyl)zirconium dichloride,
Dimethylsilandiy1-(2,5-dimethy1-6-thiapentalene)(2-isopropy1-4-(4'-isopropyl-
pheny1)-
indenyI)-zirconium dichloride,
Dimethylsilandiy1-(2-methy1-6-oxapentalene)(2-isopropy1-4-(4'-isopropyl-
pheny1)-
indenyl) zirconium dichloride,
Dimethylsilandiy1-(2-methy1-6-azapentalene)(2-isopropy1-4-(4'-n-butyl-pheny1)-
indeny1)-
zirconium dichloride,
Dimethylsilandiy1-(2-methy1-5-thiapentalene)(2-isopropy1-4-(4'-n-butyl-pheny1)-
indenyl) zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-oxapentalene)(2-isopropy1-4-(4'-n-butyl-pheny1)-
indenyl) zirconium dichloride,
CA 02628442 2008-05-02
13
Dimethylsilandiy1-(2-methy1-4-thiapentalene)(2-isopropy1-4-(4'-s-butyl-pheny1)-
indenyl) zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-oxapentalene)(2-isopropy1-4-(4'-s-butyl-pheny1)-
indenyl) zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-azapentalene)(2-isopropy1-4-(4'-tert. -butyl-
phenyI)-
indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-methy1-6-azapentalene)(2-isopropy1-4-(4'-tert.-butyl-
pheny1)-
indeny1)- zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-azapentalene)(2-isopropy1-4-(4'-n-pentyl-pheny1)-
indenyI)- zirconium dichloride,
Dimethylsilandiy1-(2-methyl-N-pheny1-6-azapentalene)(2-isopropy1-4-(4'-n-
pentyl-
pheny1)-indeny1)- zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-oxapentalene)(2-isopropy1-4-(4'-n-pentyl-pheny1)-
indenyl) zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-azapentalene)(2-isopropy1-4-(4'-n-hexyl-pheny1)-
indenyl) zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-thiapentalene)(2-isopropy1-4-(4'-n-hexyl-pheny1)-
indenyl) zirconium dichloride,
Dimethylsilandiy1-(2-methy1-6-thiapentalene)(2-isopropy1-4-(4'-n-hexyl-pheny1)-
indenyl) zirconium dichloride,
Dimethylsilandiy1-(2, 5-Dimethy1-4-thiapentalene)(2-isopropy1-4-(4'-n-hexyl-
pheny1)-
indeny1)- zirconium dichloride,
Dimethylsilandiy1-(2, 5-Dimethy1-6-thiapentalene)(2-isopropy1-4-(4'-n-hexyl-
pheny1)-
indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2,5-dimethy1-6-thiapentalene)(2-isopropy1-4-(4'-cyclohexyl-
pheny1)-
indeny1)- zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-azapentalene)(2-isopropy1-4-(4'-trimethylsilyl-
pheny1)-
indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-thiapentalene)(2-isopropy1-4-(4'-tri methylsilyl-
phenyI)-
indenyI)- zirconium dichloride,
Dimethylsilandiy1-(2-methy1-5-thiapentalene)(2-isopropy1-4-(4'-trimethylsilyl-
pheny1)-
indeny1)- zirconium dichloride,
Dimethylsilandiy1-(2-methy1-6-thiapentalene)(2-isopropy1-4-(4'-trimethylsilyl-
pheny1)-
indenyI)-zirconium dichloride,
CA 02628442 2008-05-02
14
Dimethylsilandiy142,5-Dimethy1-4-azapentalene)(2-isopropyl-4-(4'-adamantyl-
phenyl)-indenyl)- zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-thiapentalene)(2-isopropy1-4-(4'-adamantyl-
pheny1)-
indenyI)-zirconium dichloride,
Dimethylsilandiy1-(2-methy1-6-thiapentalene)(2-isopropy1-4-(4'-adamantyl-
pheny1)-
indeny1)- zirconium dichloride,
Dimethylsilandiy1-(2, 5-dimethy1-4-thiapentalene)(2-isopropy1-4-(4'-adamantyl-
pheny1)-indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-azapentalene)(2-isopropy1-4-(4'-
tris(trifluoromethyl)-
methyl-phenyl)-indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2,5-Dimethy1-4-azapentalene)(2-isopropy1-4-(4'-
tris(trifluoromethyl)methyl-pheny1)-indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-thiapentalene)(2-isopropy1-4-(4'-
tris(trifluoromethyl)methyl-pheny1)-indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-methy1-6-thiapentalene)(2-isopropy1-4-(4'-
tris(trifluoromethyl)-
methyl-pheny1)-indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-methyl-N-pheny1-6-azapentalene)(2-isopropy1-4-(4'-tert-
butyl-
pheny1)-indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-methyl-4-azapentalene)(2-isopropylindenyl) zirconium
dichloride,
Dimethylsilandiy1-(2-methyl-N-pheny1-4-azapentalene)(2-isopropylindeny1)-
zirconium
dichloride,
Dimethylsilandiy1-(2-methy1-4-thiapentalene)(2-isopropylindenyl)zirconium
dichloride,
Dimethylsilandiy1-(2-methy1-5-thiapentalene)(2-isopropylindenyl)zirconium
dichloride,
Dimethylsilandiy1-(2-methy1-6-thiapentalene)(2-isopropylindenyl) zirconium
dichloride,
Dimethylsilandiy1-(2-methy1-4-azapentalene)(2-isopropy1-4-phenyl-indeny1)-
zirconium
dichloride,
Dimethylsilandiy1-(2-methy1-5-azapentalene)(2-isopropy1-4-phenyl-indeny1)-
zirconium
dichloride,
Dimethylsilandiy1-(2-methy1-6-azapentalene)(2-isopropy1-4-phenyl-indeny1)-
zirconium dichloride,
Dimethylsilandiy1-(2-methyl-N-pheny1-4-azapentalene)(2-isopropy1-4-phenyl-
indeny1)-
zirconium dichloride,
CA 02628442 2008-05-02
Dimethylsilandiy1-(2-methyl-N-pheny1-5-azapentalene)(2-isopropy1-4-phenyl-
indeny1)-
zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-thiapentalene)(2-isopropy1-4-phenyl-indeny1)-
zirconium dichloride,
5 Dimethylsilandiy1-(2-methy1-5-thiapentalene)(2-isopropy1-4-phenyl-
indeny1)-zirconium
dichloride,
Dimethylsilandiy1-(2-methy1-6-thiapentalene)(2-isopropy1-4-phenyl-indeny1)-
zirconium
dichloride,
Dimethylsilandiy1-(2-methy1-4-oxapentalene)(2-isopropy1-4-phenyl-indeny1)-
zirconium
10 dichloride,
Dimethylsilandiy1-(2-methy1-4-azapentalene)(2-isopropy1-4, 5-benzo-indenyI)-
zirconium dichloride,
Dimethylsilandiy1-(2-methyl-N-pheny1-4-azapentalene)(2-isopropy1-4,5-benzo-
indenyI)-zirconium dichloride,
15 Dimethylsilandiy1-(2-methyl-N-pheny1-5-azapentalene)(2-isopropy1-4,5-benzo-
indeny1)- zirconium dichloride,
Dimethylsilandiy1-(2-methyl-N-pheny1-6-azapentalene)(2-isopropy1-4,5-benzo-
indeny1)-zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-thiapentalene)(2-isopropy1-4,5-benzo-indeny1)-
zirconium dichloride,
Dimethylsilandiy1-(2-methy1-5-thiapentalene)(2-isopropy1-4,5-benzo-indeny1)-
zirconium dichloride,
Dimethylsilandiy1-(2-methy1-6-thiapentalene)(2-isopropy1-4,5-benzo-indeny1)-
zirconium dichloride,
Dimethylsilandiy1-(2-methy1-4-oxapentalene)(2-isopropy1-4,5-benzo-indeny1)-
zirconium dichloride,
Dimethylsilandiy1-(2-methy1-5-oxapentalene)(2-isopropy1-4,5-benzo-indeny1)-
zirconium dichloride,
Dimethylsilandiy1-(2-methy1-6-oxapenta(ene)(2-isopropyl-4,5-benzo-indeny1)-
zirconium dichloride,
Dimethylsilandiyl-bis(2-isopropyl-4-azapentalene)zirconium dichloride,
Dimethylsilandiyl-bis(2-isopropyl-N-pheny1-4-azapentalene)zirconium
dichloride,
Dimethylsilandiyl-bis(2-isopropyl-4-thiapentalene)zirconium dichloride,
CA 02628442 2008-05-02
16
as well as the corresponding titanium and hafnium compounds and also various
bridges of dimethylsilandiyl according to Formula I such as
dimethylmethandiyl,
diphenylmethandiyl, ethandiyl, 1,2-dimethylethandiyl, dipropylsilandiyl,
dibutylsilandiyl, dipentylsilandiyl, dihexylsilandiyl, diheptylsilandiyl,
dioctylsilandiyl,
dinonylsilandiyl, didecylsilanediyl, diundecylsilandiyl, didodecylsilandiyl.
The synthesis of the compounds of Formula I according to the invention can be
conducted according to processes known to one skilled in the art. An example
therefor is set forth in the following.
Cl Ph
Cl 0 Ph-B(OH)2
CN
Ph
Ph
411rC;
2
I. _______________________________ BuLi, M2R2C17
.
2. BuLi, MIC14 M2R2c:M1
400 C12
410P
Ph
The compounds of Formula I according to the invention are particularly suited
to be
components of catalyst systems to manufacture polyolefins through the
polymerization of at least one olefin in the presence of a catalyst that
contains at
least one co-catalyst and at least one compound of Formula I according to the
invention.
Ethylene is preferred as the olefin. In a preferred embodiment of the
invention,
ethylene is polymerized using the catalysts according to the invention,
whereby
polymerization is understood to be both the homo-polymerization of ethylenes
as
well as the co-polymerization of ethylene with other olefins. The ethylene
used in the
process can, if desired, contain still other olefins that are selected from
the group
that is formed by
CA 02628442 2008-05-02
17
1-olefin with 2-20, preferably 2 to 10 C atoms, such as propene, 1-butene, 1-
pentene, 1-hexene, 1-decene, 4-methyl-1-pentene or 1-octene, styrene, dienes
such
as 1,3-butadiene, 1,4-hexadiene, vinyl norbornene, norbornadiene, ethyl
norbornadiene and cyclo-olefins such as norbornene, cyclopentadiene,
tetracyclododecene or methyl norbornenes as well as mixtures of same.
Particular preference is given to co-polymerizing the ethylene used with one
or more
1-olefins with 2 to 8 C atoms such as propene, 1-butene, 1-pentene, 1-hexene,
styrene or butadiene.
A co-monomer fraction of 0.1 to 10%, is preferred, preferably 0.5 to 9% and in
particular 2 to 5%.
Particular preference is given to the co-polymerization of ethylene with the
co-
monomer propene.
Further preference is given to the process according to the invention whereby
the
ethylene used is homo-polymerized or co-polymerized with propene.
Particular preference is given to the process according to the invention
whereby the
ethylene used is homo-polymerized.
The ethylene polymers and co-polymers manufactured with the process according
to
the invention are ultra high molecular weight, since they have a
viscosimetrically
determined molecular weight of greater than 1 x 106 mol/g.
Preference is also given to polyethylenes with a molecular weight of greater
than 1 x
106 mol/g that can be obtained using the process according to the invention.
The viscosimetric measurements are made in Decalin at 135 C and a
concentration
of 0.1g (polymer)/1 I (Decalin). The molecular weight can be derived from the
viscosity number.
The polymerization is conducted at a temperature of -20 to 300 C, preferably 0
to
200 C, most especially preferred at 20 to 100 C. The pressure is from 0.5 to
2000
CA 02628442 2008-05-02
18
bar, preferably 1 to 64 bar. The polymerization can be conducted in solution,
in bulk,
in suspension or in emulsion, continuously or in batches, in one or more
stages.
Suitable solvents for the polymerization are, for example, aliphatic
hydrocarbons
such as pentane, hexane and the like or aromatic hydrocarbons such as benzene,
toluene, xylole and the like, or ethers such as diethyl ether, dibutyl ether,
methyl-tert-
butyl ether, tetrahydrofuran, dioxane, anisole, diphenyl ether and ethyl-
phenyl ether,
as well as halogenated solvents such as dichloromethane, trichloromethane,
chloro-
benzene, bromo-benzene and the like. Mixtures of various solvents in various
proportions can also be used according to the invention.
Ultra high molecular weight ethylene polymers and co-polymers are obtained
through the polymerization of at least one olefin in the presence of catalyst
systems
of at least one compound of Formula I and one co-catalyst.
In a preferred embodiment of the invention, the catalyst system used in the
process
according to the invention contains at least one co-catalyst.
The co-catalyst that, together with at least one transition metal compound of
Formula
I, forms the catalyst system, contains at least one aluminoxane compound, or
another Lewis acid, or an ionic compound, which reacts with the transition
metal
compound to convert it into a cationic compound.
Particular preference is given to catalyst systems that contain at least one
Lewis acid
as co-catalyst.
As aluminoxane, preference is given to using a compound of the general Formula
II.
(R A10)q
Formula II
Other suitable aluminoxanes could, for example, be cyclic as in Formula III
___________________________________ A RI 0
q+2
Formula III
CA 02628442 2008-05-02
19
or linear as in Formula IV
/R
Al 0 __________________________________ Al 0 _____ Al
q \
Formula IV
or of a cluster type as in Formula V.
A I
111111711rIll
le/ R
Al immainftiummumo
Formula V
Such aluminoxanes are, for example, described in JACS 117 (1995), 6465-74,
Organometallics 13 (1994), 2957-2969.
The radical R in the Formulae II, Ill, IV and V may be identical or different
and are
each a Ci-C20-hydrocarbon group such as a C1-C6 alkyl group, a C6-C18 aryl
group,
benzyl or hydrogen, and q stands for an integer of 2 to 50, preferably 10 to
35.
Preferably, the radicals R are identical and are each methyl, isobutyl, n-
butyl, phenyl
or benzyl, in particular methyl.
If the radicals Rare different, they are preferably methyl and hydrogen,
methyl and
isobutyl, or methyl and n-butyl, containing hydrogen or isobutyl or n-butyl
preferably
up to 0.01-40% (number of radicals R).
CA 02628442 2008-05-02
The aluminoxane can be manufactured in various ways according to known
processes. One of the methods is, for example, reacting an aluminum
hydrocarbon
compound and/or a hydridoaluminum hydrocarbon compound with water (gaseous,
5 solid, liquid or bound¨for example as water of crystallization) in an
inert solvent
(such as toluene).
To prepare an aluminoxane having different alkyl groups R, two different
aluminum
trialkyls (AIR3 + AIR'3), corresponding to the desired composition and
reactivity, are
10 reacted with water (see S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-
A-
0,302,424).
Regardless of the type of preparation, a variable content of unreacted
aluminum
feed compound, present in free form or as an adduct, is common to all
aluminoxane
15 solutions.
As Lewis acid, preference is given to using at least one boron or
organoaluminum
compound containing C1-C20 carbonaceous groups, such as branched or
unbranched alkyl or haloalkyl groups, such as methyl, propyl, isopropyl,
isobutyl,
20 trifluoromethyl, unsaturated groups such as aryls, or haloaryls, such as
phenyl, tolyl,
benzene groups, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl,
pentafluorophenyl, 3,4,5 trifluorophenyl and 3,5 di(trifluoromethyl)phenyl.
Examples of Lewis acids are trimethylalunninum, triethylaluminum,
triisobutylaluminum, tributylaluminum, trifluoroborane, triphenylborane,
tris(4-
fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-
fluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(tolyl)borane,
tris(3,5-
dimethylphenyl)borane, tris(3,5-difluorophenyl)borane, and/or tris(3,4,5-
trifluorophenyl)borane. Particular preference is given to
tris(pentafluorophenyl)borane.
As ionic cocatalysts, preference is given to using compounds that contain a
noncoordinating anion, such as tetrakis(pentafluorophenyl)borate,
tetraphenylborate,
SbF6-, CF3S03- or CI04-.
CA 02628442 2008-05-02
21
As cationic counterions, use is made of protonated Lewis bases such as, for
example, methyl amine, aniline, N,N-dimethylbenzylamine, as well as their
derivatives, N,N-dimethylcyclohexylamine and its derivatives, dimethylamine,
diethylamine, N-methylaniline, diphenylamine, N,N-dimethylaniline,
trimethylamine,
triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N,N-
dimethylaniline, p-nitro-N,N-dimethylaniline, triethylphosphine,
triphenylphosphine,
diphenylphosphine, tetrahydrothiophene, or triphenylcarbenium.
Examples of such ionic compounds are
Triethylammoniumtetra(phenyl)borate,
Tributylammoniumtetra(phenyl)borate,
Trimethylammoniumtetra(tolyl)borate,
Tributylammoniumtetra(tolyl)borate,
Tributylammoniumtetra(pentafluorophenyOborate,
Tributylammoniumtetra(pentafluorophenyl)aluminate,
Tripropylammoniumtetra(dimethylphenyl)borate,
Tributylammoniumtetra(trifluoromethylphenyl)borate,
Tributylammoniumtetra(4-fluorophenyl)borate,
N,N-Dinnethylaniliniumtetra(phenyOborate,
N,N-Diethylaniliniumtetra(phenyl)borate,
N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)borate,
N,N-Dimethylaniliniumtetrakis(pentafluorophenypaluminate,
Di(propyl)ammoniumtetrakis(pentafluorophenyl)borate,
Di(cyclohexyl)ammoniumtetrakis(pentafluorophenyl)borate,
Triphenylphosphoniumtetrakis(phenyl)borate,
Triethylphosphoniumtetrakis(phenyl)borate,
N,N-Dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate
N,N-Dimethylbenzylammoniumtetrakis(pentafluorophenyOborate
Diphenylphosphoniumtetrakis(phenyl)borate,
Tri(methylphenyl)phosphoniumtetrakis(phenyl)borate,
Tri(dimethylphenyl)phosphoniumtetrakis(phenyl)borate,
Triphenylcarbeniumtetrakis(pentafluorophenyl)borate,
Triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate,
CA 02628442 2008-05-02
22
Triphenylcarbeniumtetrakis(phenyl)aluminate,
Ferroceniumtetrakis(pentafluorophenyl)borate and/or
Ferroceniumtetrakis(pentafluorophenyl)aluminate.
Preference is given to triphenylcarbeniumtetrakis(pentafluorophenyl)borate
and/or
N,N-dimethylaniliniumtetrakis(pentafluorophenyOborate.
Mixtures of at least one Lewis acid and at least one ionic compound can also
be
used.
Further suitable cocatalyst components are borane or carborane compounds such
as
7,8-dicarbaundecaborane(13),
Undecahydride-7,8-dimethy1-7,8-dicarbaundecaborane,
Dodecahydride-1-pheny1-1,3-di-carbanonaborane,
Tri(butypammoniumundecahydride-8-ethyl-7,9-dicarbaundecaborate,
4-carbanonaborane(14)bis(tri(butyl)ammonium)nonaborate,
Bis(tri(butyl)annmonium)undecaborate,
Bis(tri(butyl)annmonium)dodecaborate,
Bis(tri(butyl)ammonium)decachlorodecaborate,
Tri(butyl)ammonium-1-carbadecaborate,
Tri(butyl)ammonium-1-carbadodecaborate,
Tri(butyl)ammonium-1-trimethylsily1-1-carbadecaborate
Tri(butypammoniumbis(nonahydride-1,3-di-carbonnonaborate)cobaltate(111),
Tri(butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)ferrate(111).
Further useful co-catalyst systems are combinations of at least one of the
aforementioned amines and if desired, a support with organoelement compounds,
as
they are described in patent WO 99/40129.
The supports with organoelennent compounds named in WO 99/40129 are also
components of this invention.
CA 02628442 2008-05-02
23
Preferred components of these co-catalyst systems are the compounds of
Formulae
A and B,
R18
R18
/R18
B-0¨A1-0¨B
R18 R18 Formula A
R18
R18
/R18
18
Ris R
Formula B
whereby
R18 r=si,
I a hydrogen atom, a halogen atom, a C1-C20 carbonaceous group, in
particular C1-C20 alkyl, C1-C20 haloalkyl, C1-C10 alkoxy, C6-C2oaryl, C6-C20
haloaryl, C6-C20 aryloxy, C7-C20 arylalkyl, C7-C40 haloarylalkyl, C7-C20
alkylaryl
or C7-C20 haloalkylaryl. R18 can also be an OS1R3 group, whereby R is
identical or different and has the same meaning as R18.
Further preferred co-catalysts are general compounds that are formed by the
reaction of at least one compound of Formula C and/or D and/or E with at least
one
compound of formula F.
Rf19B-(LR18)g
Formula C
R218B-X1-EiR218
Formula D
R18
0
Formula E
I ' Translator's Note: The verb is missing in the original.
CA 02628442 2008-05-02
24
Ris
Al
18,"R
Formula F
whereby:
R18 has the same meaning as mentioned above; and
R19 can be a hydrogen atom or a boron free C1-C20 carbonaceous group
such as
C1-C20 alkyl, C6-C2oaryl, C7-C20 arylalkyl, C7-C20 alkylaryl; and
X1 is an element of the 16th group of the periodic table or an NR group,
whereby
R is a hydrogen atom or a C1-C20 hydrocarbon radical such as C1-C20-Alkyl or
C1-C20 Aryl; and
is an element of the 16th group of the periodic table or an NR group, whereby
R is a hydrogen atom or a C1-C20 hydrocarbon radical such as C1-C20-alkyl or
Cl-C20 aryl;
is an integer from 0 to 3;
is an integer from 0 to 3, whereby z + y cannot equal 0;
is an integer from Ito 10.
If desired, the organoelement compounds are combined with an organometallic
compound of Formulae II to V and/or VI,
[M3R2001c Formula VI
whereby M3 is an element of the 1, 2, and 13th group of the periodic table, R2
is
identical or different and is a hydrogen atom, a halogen atom, a C1-C40
carbonaceous group, in particular a C1-C20 alkyl, a C6-C2oaryl, a C7-C20 aryl-
alkyl, or
a C7-C20 alkyl-aryl group, r is an integer from 1 to 3 and k is an integer of
1 to 4.
Examples for the co-catalytically effective compounds of Formulae A and B are:
CA 02628442 2008-05-02
F 0 F
H3C-11/41-0-8-0-tikl-CH3
CH3 CH,
F 0 F
F F
A1-0-8-0-Al
F F
H3C¨\ F F
Hae
F F F
F * F
*F
= F
B¨O¨A1-0-6 F
F
igabi õAllot F
F 111, F F 11111 F
F F F tot F
CH 3
F I
B-0-A1-0-B F
F riahF F.F
F F F
5
CA 02628442 2008-05-02
26
F * F
( CH3 F
f
F B¨O¨Al¨O¨B
F idat F F * F
F F F
The organometallic compounds of Formula F are preferably uncharged Lewis
acids,
whereby M2 stands for lithium, magnesium and/or aluminum, in particular
aluminum.
Examples of preferred organometallic compounds of Formula F are
trimethylaluminum, triethylaluminum, triisopropylaluminum, trihexylaluminum,
trioctylaluminum, tri-n-butylaluminum, tri-n-propylaluminum,
triisoprenealuminum,
dimethylaluminum monochloride, diethylaluminum monochloride,
diisobutylaluminum
monochloride, methylaluminum sesquichloride, ethylaluminunn sesquichloride,
dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum
hydride,
dimethylaluminum(trimethylsiloxide), dimethylaluminum(triethylsiloxide),
phenylalane, pentafluorophenylalane, and o-tolylalane.
Further co-catalysts, which may be in unsupported or supported form, are the
compounds mentioned in EP-A-924223, DE-A-19622207, EP-A-601830, EP-A-
824112, EP-A-824113, EP-A-811627, W09711775 and DE-A-19606167.
Moreover, the catalysts according to the invention can be homogeneously as
well as
well as heterogeneously supported.
In a preferred embodiment, it is claimed that the compound of Formula I used
in the
process according to the invention is used in the form of a catalyst system in
supported form.
The support component of the catalyst system can be any organic or inorganic,
inert
solid, in particular a porous support such as talc, inorganic oxides and
finely divided
polymer powder (e.g., polyolefin).
CA 02628442 2008-05-02
27
Suitable inorganic oxides may be found in the groups 2, 3, 4, 5, 13, 14, 15,
and 16 of
the periodic table. Examples for the oxides preferred as supports include
silicon
dioxide, aluminum oxide, and also mixed oxides of the elements calcium,
aluminum,
silicon, magnesium, titanium and corresponding oxide mixtures as well as
hydrotalcite. Other inorganic oxides that can be used either alone or in
combination
with the aforementioned preferred oxidic supports, are e.g. MgO, Zr02, TiO2 or
B203,
to name a few.
The support materials used have a specific surface area in the range from 10
to
1000 m2/g, a pore volume in the range from 0.1 to 5 ml/g and a mean particle
size of
1 to 500 pm. Prefererence is given to supports with a specific surface area in
the
range of 50 to 500 pm, a pore volume in the range from 0.5 to 3.5 ml/g and a
mean
particle size in the range of 5 to 350 pm. Particular preference is given to
supports
having a specific surface area in the range from 200 to 400 m2/g, a pore
volume in
the range from 0.8 to 3.0 ml/g, and a mean particle size of 10 to 200 pm.
If the support material used naturally exhibits a low moisture content or
residual
solvent content, the dehydration or drying before use can be omitted. If this
is not
the case, as when using silica gel as support material, dehydration or drying
is
advisable. Thermal dehydration or drying of the support material can be
carried out
under a vacuum and a simultaneous blanketing with inert gas (e.g., nitrogen).
The
drying temperature is in the range from 100 to 1000 C, preferably from 200 to
800 C. The pressure is not critical in this instance. The drying process can
last from
1 to 24 hours. Shorter or longer drying times are possible, provided that
establishment of equilibrium with the hydroxyl groups on the support surface
can
take place under the conditions chosen, which normally takes from 4 to 8
hours.
Dehydration or drying of the support material can also be carried out by
chemical
means, by reacting the adsorbed water and the hydroxyl groups on the surface
with
suitable passivating agents. Reaction with the passivating reagent can convert
all or
part of the hydroxyl groups into a form which does not lead to any adverse
interaction with the catalytically active centers. Suitable passivating agents
are, for
example, silicon halides and silanes, e.g. silicon tetrachloride,
chlortrimethylsilane,
dimethylamino trichlorosilane, or organometallic compounds of aluminum, boron
and
CA 02628442 2008-05-02
28
magnesium, for example trinnethylaluminum, triethylaluminum,
triisobutylaluminum,
triethylborane, dibutylmagnesium. Chemical dehydration or passivation of the
support material is carried out, for example, by reacting a suspension of the
support
material in a suitable solvent with the passivating reagent either in pure
form or as a
solution in a suitable solvent in the absence of air and moisture. Suitable
solvents
are, for example, aliphatic or aromatic hydrocarbons such as pentane, hexane,
heptane, toluene or xylene. Passivation is carried out at from 25 C to 120 C,
preferably from 50 to 70 C. Higher and lower temperatures are possible. The
reaction time is from 30 minutes to 20 hours, preferably from 1 to 5 hours.
After the
chemical dehydration is complete, the support material is isolated by
filtration under
inert conditions, washed one or more times with suitable inert solvents as
described
above and subsequently dried in a stream of inert gas or under reduced
pressure.
Organic support materials such as finely divided polyolefin powders (e.g.,
polyethylene, polypropylene or polystyrene) can also be used and should
likewise be
freed of adhering moisture, solvent radicals or other impurities by
appropriate
purification and drying operations prior to use.
To prepare the supported catalyst system, at least one of the above-described
compounds of Formula I is brought in contact with at least one co-catalyst
component in a suitable solvent, preferably giving a soluble reaction product,
an
adduct or a mixture.
The preparation so obtained is then mixed with the dehydrated or passivated
support
material, the solvent removed and the resulting supported catalyst system
dried, to
ensure that all or most of the solvent is removed from the pores of the
support
materials. The supported catalyst is obtained as a free flowing powder.
Another object of the present invention is a process to depict a free flowing
and, if
desired, pre-polymerized supported catalyst system comprising the following
steps:
a) preparation of a mixture of at least one compound of Formula I and at least
one co-catalyst in a suitable solvent or suspension medium;
b) application of the mixture obtained from Step a) to a porous, preferably
inorganic, dehydrated support;
CA 02628442 2008-05-02
29
c) removal of most of the solvent from the resulting mixture;
d) isolation of the supported catalyst system;
e) if desired, a pre-polymerization of the supported catalyst system obtained
using one or several olefinic monomer(s), to obtain a pre-polymerized
supported catalyst system.
Preferred solvents in step a) are hydrocarbons and hydrocarbon mixtures that
are
liquid at the reaction temperature chosen and in which the individual
components are
preferably dissolved. The solubility of the individual components is, however,
not a
prerequisite, as long as the reaction product from the compound of Formula I
and the
co-catalyst is soluble in the solvent chosen. Examples for the suitable
solvents
include alkanes such as pentane, isopentane, hexane, heptane, octane, and
nonane; cycloalkanes such as cyclopentane and cyclohexane; and aromatics such
as benzene, toluene, ethylbenzene and diethylbenzene. Very particular
preference
is given to toluene.
The amounts of aluminoxane and compound of Formula I used in the preparation
of
the supported catalyst system can be varied over a wide range. Preference is
given
to a molar ratio of aluminum to transition metal in the compound of Formula I
of 10 :
1 to 1000: 1, very particularly preferably from 50: 1 to 500: 1.
In the case of methylaluminoxane preference is given to using 30% strength
toluene
solutions; the use of 10% strength solutions is, however, also possible. To
carry out
the preactivation, the compound of Formula I in the form of a solid is
dissolved in a
solution of the aluminoxane in a suitable solvent, It is also possible to
dissolve the
compound of Formula I separately in a suitable solvent and then to combine
this
solution with the aluminoxane solution. Preference is given to using toluene.
The preactivation time is from 1 minute to 200 hours.
The preactivation can take place at room temperature (25 C). The use of higher
temperatures can, in certain cases, shorten the time required for the
preactivation
and produce an additional increase in activity. In this case, a higher
temperature
means a range from 50 to 100 C.
CA 02628442 2008-05-02
The pre-activated solution or the mixture is then combined with an inert
support
material, usually silica gel, which is in the form of a dry powder or as a
suspension in
one of the aforementioned solvents.
5 Preference is given to using the support material as powder. The order of
addition is
immaterial. The preactivated metallocene co-catalyst solution or the
metallocene co-
catalyst mixture can be added to the support material or else the support
material
can be introduced to the solution.
10 The volume of the preactivated solution or the metallocene co-catalyst
mixture can
exceed 100% of the total pore volume of the support material used or else can
be up
to 100% of the total pore volume.
The temperature at which the preactivated solution or the metallocene co-
catalyst
15 mixture is brought in contact with the support material can vary in the
range from 0 to
100 C. Lower or higher temperatures are, however, also possible.
All or the major part of the solvent is subsequently removed from the
supported
catalyst system, whereby the mixture can be stirred and, if necessary, also
heated.
20 Preference is given to removing both the visible portion of the solvent
as well as the
portion in the pores of the support material. The removal of the solvent can
be
carried out in a conventional fashion with application of vacuum and/or
flushing with
inert gas. In the drying process, the mixture can be heated until the free
solvent has
been removed, which usually takes from 1 to 3 hours at a preferred temperature
of
25 from 30 to 60 C. The free solvent is the visible portion of solvent in
the mixture. In
this context, residual solvent is the portion which is enclosed in the pores.
As an
alternative to complete removal of the solvent, it is also possible for the
supported
catalyst system to be dried only to a particular residual solvent content,
with the free
solvent having been completely removed. The supported catalyst system can
30 subsequently be washed with a low-boiling hydrocarbon such as pentane or
hexane
and dried again.
The supported catalyst system can either be used directly for the
polymerization of
olefins or can be prepolymerized using one or more olefinic monomers prior to
use in
CA 02628442 2012-12-18
31
a polymerization process. An example of the prepolymerization of supported
catalyst systems is described in WO 94/28034.
A small amount of an olefin, preferably an a-olefin (for example vinyl
cyclohexane,
styrene or phenyldimethylvinylsilane) as modifying component or an anti-static
can
be added as additive during or after the preparation of the supported catalyst
system. The molar ratio of additive to Metallocene components (compound
according to Formula I) is preferably from 1:1000 to 1000:1, very particularly
preferably from 1:20 to 20:1.
Another object of the invention is the use of the catalyst systems according
to the
invention, containing at least one compound according to Formula I and at
least one
co-catalyst to manufacture ultra high molecular weight ethylene homo- or co-
polymers.
Particular preference is given to the catalyst system being present in
supported form.
CA 02628442 2008-05-02
32
The invention is depicted through the following examples that, however do not
limit
the invention.
General information: preparation and handling of organometallic compounds were
carried out in the absence of air and moisture under argon (Schlenk technique
or
glove box). All solvents required were purged with argon and dried over
molecular
sieves before use.
The following catalysts are used in the examples:
4PPC: 4.
Me2S1 ZrCl2
41, 44P C-_-
ZrCl2
Me2Sic____
1
40'
4P IC: _________________________
Me2Si ZrCl2
41Wv 3
2
CA 02628442 2008-05-02
33
VP 44.
44IPC 411PCI
Me2Si ZrCl2 Me2Si ZrCl2
4.' 4410P
# #
4
Example 1:
5 Depiction of the supported catalysts
1. Activation:
In an annealed flask under inert gas 0.128 mmol catalyst is dissolved in 20 ml
toluene and mixed with 6 ml (28.8 mmol, 1.672 g) MAO (30% in toluene). The
mixture is stirred for one hour at room temperature.
2. Supporting:
In an annealed flask under inert gas 6 g S102 (Grace XPO 2107, dried) is
placed and
suspended with 30 ml abs. toluene. A suspension that can be slightly stirred
results,
to which the activated catalyst (from 1.) is then added. It is stirred for 10
min and
then the solvent is removed in a vacuum to up to no more than 5% residual
moisture.
Examples 2-6:
Homopolymerization of ethylene
In a 2 I steel autoclave 1.5 I Exxsol is placed and mixed with 15 mmol of an
aluminum alkyl (e.g., tri-isobutylaluminum). The reactor is then brought to
the
desired temperature and an ethylene pressure of 7-15 bar is built up. At the
start of
CA 02628442 2008-05-02
34
the polymerization 9 pmol of the relevant catalyst (see table 1) suspended in
Exxsol
is added. It is polymerized for one hour and the reaction is stopped when the
ethylene pressure degrades. The polymer is filtered and dried in a vacuum at
80 C.
Finally, the yield and the molecular weight are determined.
Example Catalyst Pressure C2 Temperature Yield Mv
2 (comparison) 1 10 bar 70 C 70 g
0.7 x 106 g/mol
3 2 10 bar 70 C 61 g
2.2 x 106 g/mol
4 3 10 bar 70 C 64g
1.1 x 106 g/mol
5 4 10 bar 70 C 98 g
1.8 x 106 g/mol
6 5 10 bar 70 C 114g 2.7 x 106
g/mol
It therefore shows that ultra high molecular weight products are formed only
when
the bridged metallocene catalysts are used.
