Note: Descriptions are shown in the official language in which they were submitted.
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A CATALYST SYSTEM BASED ON FLUORINE-CONTAINING METAL COMPLEXES
The present invention relates to a catalyst system based on fluorine-
containing metal
complexes, particularly a catalyst system consisting of metallocene fluorides
and
aluminium alkyls, and relates to the use of said catalyst system for the
polymerisation
of unsaturated compounds, particularly for the polymerisation and
copolymerisation
of olefmes and/or dimes.
The use of metal cyclopentadienyl complexes for the polymerisation of olefines
and
diolefines, particularly the use of metallocene complexes in admixture with
activating
co-catalysts, has long been known.
US 2 827 446 describes a catalyst which is prepared from titanocene dichloride
and
diethylaluminium chloride for the polymerisation of ethylene. However, this
catalyst
is unsuitable for industrial use, since firstly the activity of the catalyst
is too low and
secondly the polymerisation of 1-olefines is not possible.
Highly effective, specific catalyst systems are known for the
(co)polymerisation of
ethylene and/or 1-olefines. These catalysts consist of metallocene dichlorides
in
admixture with aluminoxanes, e.g. methylaluminoxane (MAO). In order to
increase
the activity and selectivity of the catalyst and in order to control the
microstructure,
molecular weight and molecular weight distribution of the products, a
multiplicity of
new metallocene catalysts or metallocene catalyst systems has been developed
in
recent years for the polymerisation of olefinic compounds (e.g. EP 69 951, 129
368,
347 128, 347 129, 351 392, 485 821, 485 823). Chlorine-containing metallocenes
are
usually employed in combination with MAO.
Methods of polymerising olefines are also known in which
metallocene/aluminoxane
catalysts (e.g. EP 308177) are produced in situ.
In WO 97/07141, fluorine-containing semi-sandwich complexes of titanium are
used
in combination with MAO as catalysts for the production ef polystyrene. ~~'O
~,~ 33 ~ 49
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98/36004 describes fluorine-containing complexes, preferably of titanium, and
preferably in combination with MAO, as catalysts for the production of
polybutadiene.
However, the catalyst systems based on aluminoxanes, e.g. MAO, which were
described above have disadvantages which are described in greater detail
below. MAO
is a mixture of different aluminium compounds, the number and structure of
which are
not known accurately. The polymerisation of olefines with catalyst systems
which
contain MAO is therefore not always reproducible. Moreover, MAO is not stable
on
storage and its composition changes under the effect of thermal stresses. MAO
has the
disadvantage of having to be used in considerable excess in order to achieve
high
catalyst activities, and this results in a high content of aluminium in the
polymer.
MAO is also a cost-determining factor. Considerable excesses of MAO are
uneconomic for industrial use.
1 S In order to circumvent these disadvantages, aluminoxane-free
polymerisation catalysts
have been developed in recent years. For example, Jordan et al. in J. Am.
Chem. Soc.,
Vol. 108 (1986), 7410 describe a cationic zirconocene-methyl complex which
contains
tetraphenylborate as a counterion and which polymerises ethylene in methylene
chloride. EP-A 277 003 and EP-A 277 004 describe ionic metallocenes which are
prepared by the reaction of metallocenes with ionising reagents. EP-A 468 537
describes catalysts which possess an ionic structure and which are prepared by
the
reaction of metallocene dialkyl compounds with
tetrakis(pentafluorophenyl)boron
compounds. Ionic metallocenes are suitable as catalysts for the polymerisation
of
olefines. One disadvantage, however, is the high sensitivity of these
catalysts to
impurities, such as moisture and oxygen for example.
Prior art methods of preparing cationic metallocene complexes also have the
disadvantage that the reagents which result in cation formation, e.g.
tetrakis(pentafluorophenyl)boron compounds, are sometimes costly to
synthesise, and
the use thereof is expensive.
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In addition, methods are known for the polymerisation of olefines in which
metallocene dialkyl compounds (EP 427 697) or metallocene dichlorides (WO
92/01723), each in combination with aluminium alkyls and a third component,
e.g.
tris(pentafluorophenyl)boron compounds, are used as catalyst systems.
Metallocene
dichlorides or metallocene dialkyls in combination with aluminium alkyls alone
are
not active as regards polymerisation.
The object of the present invention was to identify an aluminoxane-free
composition
which avoids the disadvantages of the prior art, and the use of which, despite
this,
enables high polymerisation activities to be achieved. Another object was to
identify a
catalyst system with which copolymers of higher molecular weights are
obtained, even
at elevated polymerisation temperatures (>50°C), by the
copolymerisation of ethylene
with 1-olefines, particularly by the solution method. A further object was to
identify
an aluminoxane-free catalyst system for the production of polyolefme rubbers,
1 S particularly EP(D)M.
Surprisingly, it has now been found that catalyst systems based on fluorine-
containing
metal complexes are particularly suitable for achieving the aforementioned
object.
The present invention therefore relates to an aluminoxane-free catalyst system
consisting of
a) a fluorine-containing metal complex of formula (I)
AaMFbL~ (I)
wherein
M is a metal from the group comprising zirconium, hafnium, vanadium,
niobium and tantalum,
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A denotes an anionic ligand which is optionally singly- or multiply-
bridged,
F denotes a fluorine atom,
L is a nonionic ligand,
a is 1 or 2,
b is l, 2 or 3, and
c is 0, l, 2, 3 or 4, particularly 1, 2 or 3,
wherein a + b = 3 or 4 if M is zirconium or hafnium,
a + b = 3, 4 or 5 if M = vanadium, niobium or tantalum,
and
b) a compound of formula (II)
M'Y3 (II)
wherein
M denotes boron or aluminium,
and
Y denotes entities which are the same or different, and represents
hydrogen, a linear or branched C1 to C2o alkyl group which is
optionally substituted by silyl groups, a linear or branched C1 to Clo
fluoroalkyl group, a C6 to Clo fluoroaryl group, a C1 to Clo alkoxy
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group, a C6 to C2O aryl group, a C6 to C2o aryloxy group, a C7 to C4o
arylalkyl group, or a C7 to C4o alkylaryl group,
wherein trimethylaluminium is excluded.
Fluorine-containing metal complexes of formula (I) which are particularly
suitable are
those in which
A denotes entities which are the same or different, and represents
a pyrazolyl borate of formula RIB(NZC3R23)3,
an alcoholate or phenolate of formula ORI,
a thiolate of formula SR1,
an amide of formula NR12,
a siloxane of formula OSiRl3,
an acetylacetonate of formula (RICO)2CR1,
an amidinate of formula R1C(NRl)2,
a cyclooctatetraenyl of formula CgH9R~g~ where q represents 0, l, 2, 3, 4, 5,
6
or 7,
a cyclopentadienyl of formula CSHqRIS_q where q represents 0, 1, 2, 3, 4 or 5,
an indenyl of formula C9H~_rRl~ where r represents 0, 1, 2, 3, 4, 5, 6 or 7,
a fluorenyl of formula C13H9_SRIs where s represents 0, l, 2, 3, 4, 5, 6, 7, 8
or 9,
a C1 to CZO alkyl radical, a C6 to Clo aryl radical, or a C7 to C4o alkylaryl
radical,
wherein
R' denotes entities which are the same or different, and represents
hydrogen, a C1 to C2o alkyl group, a C6 to Coo fluoroaryl group, a C1 to
Clo alkoxy group, a C6 to C2o aryl group, a C6 to CIO aryloxy group, a
C2 to Clo alkenyl group, a C7 to C4o arylalkyl group, a C7 to C4o
alkylaryl group. a C8 to C4O arylalkenyl group, a C2 to Clo alkynyl
group, a silyl group ~,vhich is optionally substituted by CmClO
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hydrocarbon radicals, a boryl group, an amino group or a phosphinyl
group, or denote adjacent RI radicals which form a ring system with
the atoms linking them,
S R2 represents hydrogen or a C1-Coo alkyl group, and
M, F, L and a, b, c have the meanings given above.
Examples of suitable nonionic ligands include ethers, thioethers, cyclic
ethers, cyclic
thioethers, amine or phosphines. Other examples of nonionic ligands include
substituted or unsubstituted aromatic compounds, such as benzene, toluene,
dimethylbenzene, trimethylbenzene, pentafluorobenzene, trifluoromethylbenzene,
to(trifluoromethyl)benzene, naphthalene, anthracene and fluorene.
L preferably represents benzene, toluene, trimethylbenzene, naphthalene or
anthracene.
The fluorine-containing metal complexes of formula (I) which are particularly
preferred are those which comprise a cyclopentadienyl ring, which is
optionally
substituted, as a ligand, and fluorine atoms which are directly bonded to the
metal
atom M, wherein M represents zirconium or hafnium. Catalyst systems which
comprise these catalyst components exhibit a good activity for polymerisation.
M is preferably zirconium or vanadium, most preferably zirconium.
According to the invention, a catalyst component is provided which contains at
least
one R3 bridge between at least two ligands A.
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R3 is preferably
. ,. . .
R, R, 4 R4 R4
- 2
-O_ ~ z O- . . -O-
s s s ~s ~s
R
R~ R4 Ra R.~ R~ Re R4 R4
_ i z_
-Rs Rs ..s
~s s ~s
ljmRR x
R~ R~ R~
s
/BR4 , jAIR~ . -Ge- , -O- , -S-, %S0 ,
jSOz ~ jNR4 , jPR~ or jR(O)R4
wherein R4 and RS are the same or different and represent and a hydrogen atom,
a halogen atom or a group which contains a C1-C4o hydrocarbon, such as a C~-
C2o alkyl, a C1-Clo fluoroalkyl, a C1-Clo alkoxy, a C6-C1 4 aryl, a C6-Cio
5 fluoroaryl, a C6-Clo aryloxy, a C2-Clo alkenyl, a C7-C4o arylalkyl, a C7-C4o
alkylaryl, or a C8-C4o arylalkenyl group, or where R4 and RS each form one or
more rings with the atoms linking them and x is an integer from zero to 18, M2
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is silicon, germanium or tin; R3 can also link two units of formula (I) to
each
other.
The following examples, which are not claimed to be complete, illustrate the
organometallic fluorides which are particularly preferred in general formula
(I):
ethylenebis(indenyl)zirconium difluoride
ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium difluoride
ethylenebis(2-methylindenyl)zirconium difluoride
ethylenebis(2,4-dimethylindenyl)zirconium difluoride
dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)zirconium difluoride
dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)zirconium difluoride
dimethylsilandiylbis(2-methyl-4-phenylindenyl)zirconium difluoride
dimethylsilandiylbis(2-ethyl-4-phenylindenyl)zirconium difluoride
dimethylsilandiylbis(2-methyl-4-(1-naphthyl)indenyl)zirconium difluoride
dimethylsilandiylbis(indenyl)zirconium difluoride
dimethylsilandiylbis(2-methyl-4-ethylindenyl)zirconium difluoride
dimethylsilandiylbis(2-methyl-4-isopropylindenyl)zirconium difluoride
dimethylsilandiylbis(2-methyl-4-methylindenyl)zirconium difluoride
dimethylsilandiylbis(2-ethyl-4-methylindenyl)zirconium difluoride
dimethylsilandiylbis(2-methyl-a-acenaphth-1-indenyl)zirconium difluoride
phenylmethylsilandiylbis(2-methyl-4-phenylindenyl)zirconium difluoride
phenylmethylsilandiylbis(2-methyl-indenyl)zirconium difluoride
ethylenebis(2-methyl-4,5 -benzoindenyl)zirconium difluoride
ethylenebis(2-methyl-4,6-diisopropylindenyl)zirconium difluoride
ethylenebis(2-methyl-4-phenylindenyl)zirconium difluoride
ethylenebis(2-ethyl-4phenylindenyl)zirconium difluoride
ethylenebis(2-methyl-4-(1-naphthyl)indenyl)zirconium difluoride
ethylenebis(indenyl)zirconium difluoride
ethylenebis(2-methyl-4-ethylindenyl)zirconium difluoride
ethylenebis(2-methyl-4-isopropylindenyl)zirconium difluoride
ethylenebis(2-methyl-4-methylindenyl)zirconiui~n dit~uoride
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ethylenebis(2-ethyl-4-methylindenyl)zirconium difluoride
ethylenebis(2-methyl-a-acenaphth-1-indenyl)zirconium difluoride
bis(2-methyl-4,5-benzoindenyl)zirconium difluoride
bis(2-methyl-4,6-diisopropylindenyl)zirconium difluoride
S bis(2-methyl-4-phenylindenyl)zirconium difluoride
bis(2-ethyl-4-phenylindenyl)zirconium difluoride
bis(2-methyl-4-(1-naphthyl)indenyl)zirconium difluoride
bis(indenyl)zirconium difluoride
bis(2-methyl-4-ethylindenyl)zirconium difluoride
bis(2-methyl-4-isopropylindenyl)zirconium difluoride
bis(2-methyl-4-methylindenyl)zirconium difluoride
bis(2-ethyl-4-methylindenyl)zirconium difluoride
bis(2-methyl-a-acenaphth-1-indenyl)zirconium difluoride
bis(n-butyl-cyclopentadienyl)zirconium difluoride
bis(cyclopentadienyl)zireonium difluoride
bis(pentamethylcyclopentadienyl)zirconium difluoride
cyclopentadienylzirconium trifluoride
pentamethylcyclopentadienylzirconium trifluoride
(2-methyl-4,5-benzoindenyl)zirconium trifluoride
(2-methyl-4,6-diisopropylindenyl)zirconium trifluoride
(2-methyl-4-phenylindenyl)zirconium trifluoride
(2-ethyl-4-phenylindenyl)zireonium trifluoride
(2-methyl-4-(1-naphthyl)indenyl)zireonium trifluoride
indenylzirconium trifluoride
(2-methyl-4-ethylindenyl)zirconium trifluoride
(2-methyl-4-isopropylindenyl)zirconium trifluoride
(2-methyl-4-methylindenyl)zireonium trifluoride
(2-ethyl-4-methylindenyl)zirconium trifluoride
(2-methyl-a-aeenaphth-1-indenyl)zirconium trifluoride
(n-butyl-cyelopentadienyl)zirconium trifluoride
isopropylidene(9-fluorenyl)cyclopentadienylzirconium trifluoride
diphenylmethylene(9-fluorenyhcyvlopentadienylzirconiurn difl~:orjde
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phenylmethylmethylene(9-fluorenyl)cyclopentadienylzirconium difluoride
dimethylsilandiyl(9-fluorenyl)cyclopentadienylzirconium difluoride
isopropylidene(9-fluorenyl)(3-methyl-cyclopentadienyl)zirconium trifluoride
diphenylmethylene(9-fluorenyl)(3-methyl-cyclopentadienyl)zirconium difluoride
S phenylmethylmethylene(9-fluorenyl)(3-methyl-cyclopentadienyl)zirconium
difluoride
dimethylsilandiyl(9-fluorenyl)(3-methyl-cyclopentadienyl)zirconium difluoride
isopropylidene(9-fluorenyl)(3-isopropyl-cyclopentadienyl)zirconium difluoride
diphenylmethylene(9-fluorenyl)(3-isopropyl-cyclopentadienyl)zirconium
difluoride
phenylmethylmethylene(9-fluorenyl)(3-isopropyl-cyclopentadienyl)zirconium
difluoride
dimethylsilandiyl(9-fluorenyl)(3-isopropyl-cyclopentadienyl)zirconium
difluoride
isopropylidene(2,7-di-tert.-butyl-9-fluorenyl)cyclopentadienylzirconium
difluoride
diphenylmethylene(2,7-di-tert.-butyl-9-fluorenyl)cyclopentadienylzirconium
difluoride
phenylmethylmethylene(2,7-di-tert.-butyl-9-fluorenyl)cyclopentadienylzirconium
difluoride
dimethylsilandiyl(2,7-di-tert.-butyl-9-fluorenyl)cyclopentadienylzirconium
difluoride
ethylenebis(indenyl)hafnium difluoride
ethylenebis(4,5,6,7-tetrahydroindenyl)hafnium difluoride
ethylenebis(2-methylindenyl)hafnium difluoride
dimethylsilandiylbis(indenyl)hafnium difluoride
bis(indenyl)hafnium difluoride
bis(cyclopentadienyl)hafnium difluoride
bis(pentamethylcyclopentadienyl)hafnium difluoride
cyclopentadienylhafnium trifluoride
pentamethylcyclopentadienylhafnium trifluoride
indenylhafnium trifluoride
(n-butyl -cyclopentadienyl)hafnium trifluoride
isopropylidene(9-fluorenyl)cyclopentadienylhafnium difluoride.
Fluorides of the metallocenes described in WO 98/01487 are also suitable as
compounds of formula {I).
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Metallocene fluorides can be prepared as described in J. Chem. Soc. (A), 1969,
2106-
2116, for example. In particular, the preparation of the compound ethylene-
bistetrahydroindenyl)zirconium difluoride is described in Organometallics
1998, 17,
page 2097.
Compounds of formula (IIa) are particularly suitable as compounds of formula
(II):
wherein
M' denotes aluminium,
R6, R7, R8, R9 and Rl° are identical or different and represent
hydrogen, a linear or
branched C~ to CS alkyl group which is optionally substituted by silyl groups,
,
a linear or branched C1 to CS fluoroalkyl group, a C1 to CS alkoxy group, a C6
to C2° aryl group, or a C6 to C2° aryloxy group,
Z represents an alkylene, alkenylene or alkynylene radical which is optionally
singly- or multiply-substituted,
m is 0,1 or 2,
n is 1, 2 or 3 and Y has the meaning given above.
Compounds of formula (IIb) are preferred
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(11b)
n
wherein
Rl l is hydrogen or a group which contains a C1-C4o carbon chain, such as a
C1-C2O alkyl, a C1-Coo fluoroalkyl, a C~-CIO alkoxy, a C6-C~4 aryl, a C6-Clo
fluoroaryl, a CS-CIO aryloxy, a C~-Clo alkenyl, a C7-C4o arylalkyl, a C7-C4o
alkylaryl, or a Cg-C4o arylalkenyl group,
and
R6, R7, Rg, R9, Rl°, Y and M have the meanings given above.
Examples of compounds of formula (II) which are particularly suitable include
triethylaluminium, diethylaluminium hydride, triisobutylaluminium, diisobutyl-
aluminium hydride, triisohexylaluminium, tris-(2,3,3-trimethyl-
butyl)aluminium, tris-
(2,3-dimethylhexyl)aluminium, tris-(2,3-dimethyl-butyl)aluminium, tris-(2,3-
dimethylpentyl)aluminium, tris-(2,3-dimethyl-heptyl)aluminium, tris-(2-methyl-
3-
ethylpentyl)aluminium, tris-(2-methyl-3-ethyl-hexyl)aluminium, tris-(2-methyl-
3-
ethylheptyl)aluminium, tris-(2-methyl-3-propyl-hexyl)aluminium, tris-(2-ethyl-
3-
methylbutyl)aluminium, tris-(2-ethyl-3-methyl-pentyl)aluminium, tris-(2,3-
diethyl-
pentyl)aluminium, tris-(2-propyl-3-methyl-butyl)aluminium, tris-(2-iso-propyl-
3-
methyl-butyl)aluminium, tris-(2-isobutyl-3-methyl-pentyl)aluminium, tris-
(2,3,3-
trimethyl-pentyl)aluminium, tris-(2,3,3-trimethyl-hexyl)aluminium, tris(2-
ethyl-3,3-
dimethyl-butyl)aluminium, tris-(2-ethyl-3,3-dimethyl-pentyl)aluminium, tris-(2-
isopropyl-3,3-dimethyl-butyl)aluminium, tris-(2-
trimethylsilylpropyl)aluminium, tris-
(2-methyl-3-phenyl-butyl)aluminium, tris-{2-ethyl-3-phenyl-butyl)aluminium.
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(2,3-dimethyl-3-phenyl-butyl)aluminium, tri-(2-phenylpropyl)aluminium,
tribenzyl-
aluminium, triphenylaluminium, tri(neopentyl)aluminium, and tri(trimethyl-
silylmethyl)aluminium. Triisobutylaluminium and tri-(2,4,4-trimethylpentyl)-
aluminium are particularly preferred. The compounds of formula (II) may also
be
present as mixtures.
Trialkylaluminium compounds and dialkylaluminium hydrides can be prepared by
the
method described in Liebigs Annalen der Chemie, Volume 629, pages 14-19.
The present invention further relates to the use of the new catalyst systems
for the
polymerisation of unsaturated compounds, particularly of olefines and dimes.
In this
respect, polymerisation should be understood to include both homo- and
copolymerisation of said unsaturated compounds. Substances which are used in
particular for polymerisation include C2-Clo alkenes such as ethylene,
propylene,
butene-l, pentene-1, hexene-l, octene-1 and isobutylene, and arylalkenes such
as
styrene. The following substances are used in particular as dimes: conjugated
dimes
such as 1,3-butadiene, isoprene or 1,3-pentadiene, and unconjugated dimes such
as
1,4-hexadiene, 1,5-heptadiene, 5,7-dimethyl-1,6-octadiene, 7-methyl-1,6-
octadiene,
4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene and
dicyclo-
pentadiene.
The catalysts according to the invention are suitable for the production of
rubbers
based on copolymers of ethylene with one or more of the aforementioned a-
olefmes
and the aforementioned dimes. The catalysts according to the invention are
particularly suitable for the production of EP(D)M. The catalyst system
according to
the invention is also suitable for the polymerisation of cyclo-olefines such
as norbor-
nene, cyclopentene, cyclohexene or cyclooctane, and for the copolymerisation
of
cycloolefines with ethylene or a-olefines.
Polymerisation can be conducted in a liquid phase, in the presence or absence
of an
inert solvent, or in the gas phase. Suitable solvents include aromatic
hydrocarbons
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such as benzene and/or toluene, or aliphatic hydrocarbons such as propane,
hexane,
heptane, octane, isobutane, cyclohexane or mixtures of different hydrocarbons.
It is possible to use the catalyst system according to the invention on a
support.
Examples of suitable support materials include: inorganic or organic polymeric
supports such as silica gel, zeolites, carbon black, activated carbon,
alumina,
polystyrene and polypropylene.
The support materials are preferably thermally and/or chemically pretreated in
order to
adjust the water content or concentration of OH groups to defined values or to
keep
them as low as possible. Chemical pretreatment may consist of the reaction of
the
support. with an aluminium alkyl, for example. Inorganic supports are usually
heated
at 100°C to 1000°C for 1 to 100 hours before use. The surface of
inorganic supports
such as these, particularly of silica (Si02), ranges between 10 and 100 m2/g,
preferably
between 100 and 800 m2/g. The particle diameter ranges between 0.1 and 500
micrometer (p), preferably between 10 and 200 ~..
Polymerisation is generally conducted at pressures of 1 to 1000, preferably 1
to 100
bar. Polymerisation can be conducted in customary reactors, continuously or
batch-
wise.
For economic reasons, the pressures employed do not often exceed the value of
30
bar, preferably 20 bar. According to the invention, polymerisation is
conducted in one
or more reactors or reaction zones, e.g. in a reactor cascade. If a plurality
of reactors is
used, different polymerisation conditions can be employed.
Polymerisation is generally effected at temperatures within the range from
0°C to
200°C, preferably from 20°C to 150°C, more preferably
from 40°C to 120°C, most
preferably from 60°C to 120°C.
The molar ratio of polymerisable monomer to the compound of formula (I) falls
within the range from 1 x 10'° : 1 to 100 : l, preferably from 1 x lOs
: 1 to 1000 : 1.
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The molar ratio of the compound of formula (II) to the compound of formula (I)
falls
within the range from 10,000 : 1 to 0.1 : 1, preferably from 1000 : 1 to 1: 1.
S The polymers which are obtainable by the method according to the invention
are
primarily suitable for the production of mouldings of all types.
The invention is explained in greater detail with reference to the following
examples.
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Examples
General information: The preparation and manipulation of organometallic
compounds, as well as the polymerisation experiments, were conducted with the
exclusion of air and moisture using argon as a protective gas (Schlenk
technique). All
necessary solvents were rendered absolute before use by boiling for several
hours over
a suitable drying agent, followed by distillation under argon.
The following compounds were purchased commercially:
from Witco: triisobutylaluminium (TIBA), tri-(2,4,4-trimethylpentyl)-aluminium
(TIOA), ethylenebis(tetrahydroindenyl)zirconium dichloride;
from Akzo Nobel: methylaluminoxane (PMAO; 30% solution in toluene),
diisobutylaluminium chloride (DIBAC);
from Aldrich: trimethylaluminium (TMA, 2.0 molar solution in toluene);
from MCAT: ethylenebis(tetrahydroindenyl)zirconium difluoride
from Messer Griesheim GmbH: ethylene, propylene (purity 3.5);
Tri-(2-phenyl-propyl)aluminium was prepared as described in Annalen der
Chemie,
Volume 629, 1960, page 18.
Polymer characterisation: the intrinsic viscosity was determined in an
Ubbelohde
capillary viscometer at 140°C in o-dichlorobenzene as the solvent
(mufti-point
measurement). DSC measurements were made using an apparatus supplied by Perkin-
Elmer termed a DSC-2 differential scanning calorimeter, using the following
procedure: two heating runs from -90°C to +180°C at a heating
rate of 20K/min, rapid
cooling at 320K/min to -90°C, flushing with nitrogen, weighing 12.3 mg
of sample
into standard capsules. Determination of the polymer composition by IR
spectroscopy
was effected according to ASTM D 3900. The Mooney viscosity ML(1+4)
125°C was
determined according to ASTM 1646 / DIN 53523.
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Example 1
Polymerisation of ethylene
S00 ml toluene (freshly rendered absolute) and 0.5 ml tris-(2,4,4-
trimethylpentyl)aluminium were placed in a 1.4 litre steel autoclave. This
solution was
heated to a controlled temperature of 40°C. Ethylene was then metered
in until the
reactor internal pressure rose to 7 bar. Polymerisation was initiated by
adding a
mixture of 1.25 ~mol ethylenebis(tetrahydroindenyl)zirconium difluoride and
0.5 ml
tris-(2,4,4-trimethylpentyl)aluminium, dissolved in 5 ml toluene. After a
polymerisation time of 10 minutes at 40°C and 7 bar, the autoclave was
depressurised,
and the polymer was washed with methanol and dried for 20 hours under vacuum
at
60°C. 13.2 g polyethylene were obtained.
Example 2 (comparative example A)
Polymerisation of ethylene
The polymerisation experiment of Example 1 was repeated, except that the
fluorine-
free compound ethylenebis(tetrahydroindenyl)zirconium dichloride was used
instead
of ethylenebis(tetrahydroindenyl)zirconium difluoride. No polymerisation
occurred.
Example 3
CopolymerisaHon of ethylene and propylene
500 ml toluene (freshly rendered absolute) and 0.3 ml triisobutylaluminium
(TIBA)
were placed in a 1.4 litre steel autoclave which was fitted with a mechanical
stirrer, a
manometer, a temperature sensor, a temperature controller, a catalyst lock and
with
monomer metering devices for ethylene and propylene. The internal temperature
was
set to 60°C using a thermostat. 10 g ethylene and 22 g propylene were
subsequently
added. polymerisation was initiated by adding as solution of 1.2~ ~.moi
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ethylenebis(tetrahydroindenyl)zirconium difluoride in 1.25 ml toluene.
Ethylene and
propylene were continuously added in a quantitative ratio 30:70 so that the
internal
pressure at 60°C remained constant at 7 bar. After a polymerisation
time of 20
minutes, the reaction was stopped, and the polymer was precipitated in
methanol,
isolated and dried for 20 hours at 60°C under vacuum. 19.0 g of a
copolymer were
obtained which had the following composition: 79.3 % by weight ethylene, 20.7
% by
weight propylene (as determined by IR spectroscopy). Measurement of the
intrinsic
viscosity gave a value of 4.45 dl/g.
Examule 4 (comparative example B)
Copolymerisation of ethylene and propylene
The polymerisation experiment of Example 3 was repeated, except that a 1.0 ml
of a
2.0 molar solution of trimethylaluminium in toluene was used instead of 0.3 ml
TIBA.
No polymerisation occurred.
Example 5 (comparative example C)
Copolymerisation of ethylene and propylene
The polymerisation experiment of Example 3 was repeated, except that 1.0 ml of
a 2.0
molar solution of diisobutylaluminium in toluene was used instead of 0.3 ml
TIBA.
No polymerisation occurred.
Example 6
Terpolymerisation of ethylene, propylene and 5-ethylidene-2-norbornene (ENB)
500 ml toluene (freshly rendered absolute); 1 ml TIBA and 5 ml ENB were placed
in a
1.4 litre steel autoclave which was fitted with a mechanical stirrer, a
manometer, a
temperature sensor, a ternperature controller, a catalyst lcc~ and with
mercrner
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metering devices for ethylene and propylene. The internal temperature was set
to 60°C
using a thermostat. 11 g ethylene and 25 g propylene were subsequently added.
Polymerisation was initiated by adding a solution of 1.25 ~mol
ethylenebis(tetrahydroindenyl)zirconium difluoride and 0.25 ml TIBA, dissolved
in 5
ml toluene. Ethylene and propylene were continuously added in a quantitative
ratio
30:70 in a semi-batch procedure so that the internal pressure at 60°C
remained
constant at 7 bar. After a polymerisation time of 40 minutes, the reaction was
stopped,
and the polymer was precipitated in methanol, isolated and dried for 20 hours
at 60°C
under vacuum. 37.3 g of a terpolymer were obtained which had the following
composition: 64.2 % by weight ethylene, 28.7 % by weight propylene and 7.8 %
by
weight ENB (as determined by IR spectroscopy). DSC investigation gave a glass
transition temperature Tg = -48°C.
Example 7
Terpolymerisation of ethylene, propylene and 5-ethylidene-2-norbornene (ENB)
The polymerisation experiment of Example 6 was repeated, except that
polymerisation was conducted at a temperature of 40°C. 25.9 g of a
terpolymer were
obtained, which had the following composition: 70.5 % by weight ethylene, 24.1
% by
weight propylene and 5.8 % by weight ENB (as determined by IR spectrometry).
DSC
investigation gave a glass transition Tg = -40°C.
Example 8 (comparative example D)
Terpolymerisation of ethylene, propylene and 5-ethylidene-2-norbornene (ENB)
The polymerisation experiment of Example 7 was repeated, except that the
fluorine-
free compound ethylenebis(tetrahydroindenyl)zirconium dichloride was used
instead
of ethylenebis(tetrahydroindenyl)zirconium difluoride. No polymerisation
occurred.
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10
Example 9
Preparation of catalyst solution
48.9 mg ( 124.2 p.mol) ethylenebis(tetrahydroindenyl)zirconium difluoride were
dissolved in 4.7 ml tri(2-phenyl-propyl)aluminium (TPPA). 1.0 ml (26.4 ~.mol
zirconium) of the solution was removed and diluted with 105 ml hexane (freshly
rendered absolute); concentration of catalyst solution: 0.25 mmol Zr/l.
Copolymerisation of ethylene and propylene
500 ml hexane (freshly rendered absolute) and 1.0 g (2.6 mmol) (TPPA) were
placed
in a 1.4 litre steel autoclave which was fitted with a mechanical stirrer, a
manometer, a
temperature sensor, a temperature controller, a catalyst lock and with monomer
metering devices for ethylene and propylene. The internal temperature was set
to 65°C
using a thermostat. 14 g ethylene and 6 g propylene were subsequently added.
Polymerisation was initiated by adding a solution of 5 ml of the catalyst
solution (1.25
~mol zirconium). Ethylene and propylene were continuously added in a
quantitative
ratio of 70:30 so that the internal pressure at 65°C remained constant
at 7 bar. After a
polymerisation time of 20 minutes, the reaction was stopped, and the polymer
was
precipitated in methanol, isolated and dried for 20 hours at 60°C under
vacuum. 21.2
g of a high molecular weight copolymer were obtained which had the following
composition: 77.8 % by weight ethylene, 22.2 % by weight propylene (as
determined
by IR spectroscopy).
Example 10
Copolymerisation of ethylene and propylene
The polymerisation experiment of Example 9 was repeated, except that 13 g
ethylene
and 13 g propylene were used, and were conti_nuouslv added i_n an
ethylene/propylene
quantitative ratio of 50:50. Polymerisation tune: 3~ min~!tes. 37.9 g of a
hig?~
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molecular weight copolymer were obtained, which had the following composition:
72.1 % by weight ethylene; 27.9 % by weight propylene (as determined by IR
spectroscopy).
Examule 11
Copolymerisation of ethylene and propylene
The polymerisation experiment of Example 9 was repeated, except that 12 g
ethylene
and 18 g propylene were used, and were continuously added in an
ethylene/propylene
quantitative ratio of 40:60. Polymerisation time: 45 minutes. 27.2 g of a high
molecular weight copolymer were obtained, which had the following composition:
69.0 % by weight ethylene, 31.0 % by weight propylene (as determined by IR
spectroscopy).
Example 12
Copolymerisation of ethylene and propylene
The polymerisation experiment of Example 9 was repeated, except that 9 g
ethylene
and 21 g propylene were used, and were continuously added in an
ethylene/propylene
quantitative ratio of 30:70. Polymerisation time: 45 minutes. 24.7 g of a high
molecular weight copolymer were obtained, which had the following composition:
68.6 % by weight ethylene, 31.4 % by weight propylene (as determined by IR
spectroscopy).
Example 13
Preparation of catalyst solution
82.0 mg (208.3 pmol) ethylenebis(tetrahydroindenyl)zirconium difluoride were
dissolved in 7.9 ml TPPA. 2.0 ml (~2.7 umol zirconium) ef the solution was
remei-ea
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and diluted with 24 ml hexane (freshly rendered absolute). Concentration of
catalyst
solution: 2 mmol Zr/1.
Copolymerisation of ethylene and propylene
500 ml hexane (freshly rendered absolute) and 1.5 g (3.9 mmol) (TPPA) were
placed
in a 1.4 litre steel autoclave which was fitted with a mechanical stirrer, a
manometer, a
temperature sensor, a temperature controller, a catalyst lock and with monomer
metering devices for ethylene and propylene. The internal temperature was set
to 60°C
using a thermostat. 10 g ethylene and 50 g propylene were subsequently added.
Polymerisation was initiated by adding a solution of 2.5 ml of the catalyst
solution (5
pmol zirconium) and the temperature was subsequently raised to 80°C.
Ethylene was
continuously added so that the internal pressure at 80°C remained
constant at 11 bar.
After a polymerisation time of 30 minutes, the reaction was stopped, and the
polymer
was precipitated in methanol, isolated and dried for 20 hours at 60°C
under vacuum.
76.5 g of a high molecular weight copolymer were obtained which had the
following
composition: 74.6 % by weight ethylene, 25.4 % by weight propylene (as
determined
by IR spectroscopy). A glass transition temperature Tg = -45°C was
determined by the
DSC method. Measurement of the Mooney viscosity gave a value of ML
1+4(125°C)
= 51 MU.
Example 14
Copolymerisation of ethylene and propylene
The polymerisation experiment of Example 13 was repeated, except that the
catalyst
solution of Example 13 was used after it had been aged for 30 days (storage at
room
temperature). Polymerisation time: 15 minutes. 41.8 g of a high molecular
weight
copolymer was obtained, which had the following composition: 74.1 % by weight
ethylene and 25.,9 % by weight propylene (as determined by IR spectroscopy). A
glass
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transition temperature Tg = -47°C was determined by the DSC method.
Measurement
of the Mooney viscosity gave a value of ML 1+4(125°C) = 52 MU.
Example 15
Copolymerisation of ethylene and propylene
The polymerisation experiment of Example 13 was repeated, except that 70 g
propylene and 10 g ethylene were placed in the autoclave. The catalyst
solution of
Example 13 was used after it had been aged for 30 days (storage at room
temperature).
Ethylene was continuously added at 12 bar and 80°C. Polymerisation
time: 30
minutes. 55.4 g of a high molecular weight copolymer was obtained, which had
the
following composition: 64.4 % by weight ethylene and 35.6 % by weight
propylene
(as determined by IR spectroscopy). Measurement of the Mooney viscosity gave a
value of ML 1+4(125°C) = 53 MU.
Example 16 (comparative example E)
Copolymerisation of ethylene and propylene
The polymerisation experiment of Example 13 was repeated, except that a 30
solution of methylaluminoxane in toluene (3 mmol Al) together with 500 ml
hexane
was placed in the autoclave instead of 1.5 g TPPA (3.9 mmol Al). 5 ~,mol of
the
fluorine-free compound ethylenebis(tetrahydroindenyl)zirconium dichloride was
used
as the catalyst (pre-activated for 15 minutes with a 30 % solution of
methylaluminoxane in toluene, 2.5 mmol Al, molar ratio A1/Zr = 500 : 1).
Polymerisation time: 15 minutes. 36.4 g of a low molecular weight copolymer
were
obtained, which had the following composition: 71 % by weight ethylene and 29
% by
weight propylene (as determined by IR spectroscopy). Measurement of the Mooney
viscosity gave a value of ML 1+4(125°C) = 4 MU.
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Example 17
Terpolymerisation of ethylene, propylene and 5-ethylidene-2-norbornene (ENB)
The polymerisation experiment of Example 13 was repeated, except that 10 g
ethylene, 50 g propylene and 2.5 ml ENB were placed in the autoclave.
Polymerisation temperature: 80°C, Polymerisation time: 30 minutes. 33.7
g of a high
molecular weight copolymer were obtained, which had the following composition:
71.8 % by weight ethylene, 22.0 % by weight propylene and 6.6 % by weight ENB
(as
determined by IR spectroscopy). Measurement of the Mooney viscosity gave a
value
of ML 1+4(125°C) = 41 MU.
CA 02379019 2002-O1-11
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