Note: Descriptions are shown in the official language in which they were submitted.
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SUPPORTED CATALYST COMPONENT, SUPPORTED CATALYST, PREPARATION PROCESS,
POLYMERIZATION PROCESS, COMPLEX COMPOUNDS, AND THEIR PREPARATION
This invention relates to a supported catalyst component comprising a support
material, an organometal compound, and an activator compound, to a supported
catalyst
comprising said supported catalyst component and a transition metal compound,
to a process
for preparing such a supported catalyst component and catalyst, to a
polymerization process
using such a supported catalyst, to complex compounds for use as activator
compounds, and to
a process for making such complex compounds.
Background of the invention
Homogeneous or non-supported ionic transition metal catalysts are known for
their high catalytic activity in olefin polymerizations. Under polymerization
conditions where
polymer is formed as solid particles, these homogeneous (soluble) catalysts
form polymer
deposits on reactor walls and stirrers which deposits should be removed
frequently as they
prevent an efficient heat-exchange necessary for cooling the reactor contents
and cause
excessive wear of the moving parts in the reactor. The polymers produced by
these soluble
catalysts further have a low bulk density which limits the commercial utility
of both the
polymer and the process. In order to solve these problems, several supported
ionic catalysts
have been proposed for use in particle forming polymerization processes.
WO-91 /09882 describes a supported ionic metallocene catalyst prepared by
combining i) a bis(cyclopentadienyl) metal compound containing at least one
ligand capable of
reacting with a proton, ii) an activator component comprising a cation capable
of donating a
proton and a bulky, labile anion capable of stabilizing the metal cation
formed as a result of
reaction between the metal compound and the activator component, and iii) a
catalyst support
material. The support material may be subjected to a thermal or chemical
dehydrati'arr°'
treatment. In some of the examples triethylaluminum was added for this
purpose. The
maximum bulk density reported in the examples of W091 /09882 is 0.17 g/cm3 and
the catalyst
efficiency is not satisfactory.
WO-94/03506 describes a supported ionic catalyst prepared by combining i) a
monocyclopentadienyl metal compound, ii) an activator component comprising a
cation which
will irreversibly react with at least one ligand contained in said metal
compound and an anion,
said anion being a chemically stable non-nucleophilic anionic complex, and
iii) a catalyst
support material, optionally followed by prepolymerizing said supported
catalyst system with
an olefinic monomer. The support material may be treated with a hydrolyzable
organoadditive, preferably a Group 13 alkyl compound such as triethylaluminum.
The catalyst
efficiencies obtained in WO-94/03506, however, are very low. WO-94/03509
suggests the use
of supported ionic catalysts such as described in WO-94/03506 for use in a gas
phase
polymerization process.
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WO-93/21238 discloses tris(pentafluorophenyl)borane complexes of water,
alcohols, mercaptans, silanols, oximes, and mixtures thereof. These neutral
complexes may be
converted to acidic salts of their conjugate bases by reaction with amines.
These complexes and
acidic salts thereof together with Group 4 transition metal compounds,
especially
metallocenes, were disclosed as being useful as homogeneous olefin
polymerization catalysts.
WO-93/11172 relates to polyionictransition metal catalyst compositions. It is
suggested that polyanionic activators are used to prepare a catalyst system of
enhanced
performance by immobilizing the catalyst on a support material. It is
believed, however, that
the teachings in WO-93/11172 do not suffice for preparing a supported catalyst
based on
surface-hydroxyl groups containing support materials. Figure 1, Formula 3 and
page 26, line 25
suggest so-called alcohol-functionalized synthons to be used in making the
polyanionic
activators. Several methods are suggested to make catalyst supports based on
polyanionic
activators made from alcohol-functionalized synthons, as discussed below. In a
first method
(page 26, line 32-36 and Fig. 1 Formula 6) the alcohol functionalized synthon
is converted into
silYlhalide analogs by treatment with R'~SiCl4_~ (j = 0 to 3). As indicated
therein, HCI is liberated
which should be adsorbed by a tertiary amine. This, however, will give the by-
product R3NH.CI.
The ammonium chloride thus formed is not a suitable activator compound for a
transition
metal catalyst because the chloride anion is not a non-coordinating anion
which is typically
required for such type of catalyst, and the catalyst thus made will not have
substantial catalyst
activity. The compound of Formula 6 may be reacted with a hydroxylated
substrate such as
silica gel, alumina or metal oxides (page 34, lines 25-28 and Figure 1 route
C). When using the
compound of Formula 6 equivalents of HCI may be liberated, which compound and
the possibly
suggested by-product ammonium chloride will provide catalyst systems having
only
insignificant catalytic activities.
On page 32, lines 11-18 further methods are suggested for making catalyst
supports from the alcohol-functionalized synthons: acid catalyzed dehydration
of
hydroxylated surfaces (such as amorphous silica), and esterification or
transesterification of
discrete or polymeric materials containing more than one carboxylic acid or
ester per molecule,
polymer chain or particle. All such reactions liberate water, which is a
poison for transition
metal catalysts.
A further method is described on page 34, line 34 to page 35, line 37 and page
37,
line 16 to page 38, line 14, as well as in Figure 8. According to that method,
a support material
is provided with anionicfunctionalities by reacting a silane halide orsilane
alkoxide coupling
agent with a hydroxylated surface of silica. On page 35, lines 33-37 it is
suggested to mask or
protect reactive functionalities such as hydroxyl functions (on the silica).
On page 37, lines 20-
31 this is further explained and it is indicated that part of the hydroxyl
functions can be masked
and the remaining part can be converted into said anionic functionalities.
This would enable
varying or adjusting the concentration of (ultimately) anionic
functionalities. A mixture of
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bromophenyl silane trimethoxy and phenylsilane trimethoxy is mentioned in this
context.
Accordingly, the hydroxyl functionalities which are masked or protected are
not used for
preparing anionic functionalities. Besides, using silane halides or silane
alkoxides to react with
surface hydroxyl groups would give as by-product hydrogen halides and alcohols
which are
catalyst poisons. Accordingly, none of the suggested methods are believed to
give effective
supported catalysts.
It would be desirable to provide a supported catalyst and supported catalyst
component thereof, and a polymerization process that is capable of producing
polymers at
good catalyst efficiencies, thereby avoiding or reducing some of the
disadvantages occurring in
the prior art.
Summary of the invention
In one aspect of the present invention there is provided a supported catalyst
component comprising (a) a support material, an organometal compound wherein
the metal is
selected from Groups 2-13 of the Periodic Table of Elements, germanium, tin,
and lead, and (b)
an activator compound comprising 6.1 ) a cation which is capable of reacting
with a transition
metal compound to form a catalytically active transition metal complex, and
b.2) a compatible
anion having up to 100 nonhydrogen atoms and containing at least one
substituent comprising
an active hydrogen moiety.
In a second aspect there is provided a supported catalyst comprising the
ZO supported catalyst component of the invention and (c) a transition metal
compound
containing a substituent capable of reacting with activator compound (b) to
thereby form a
catalytically active transition metal complex.
In a further aspect the invention provides a process for preparing a supported
catalyst component comprising combining a support material (a), an organometal
compound
z5 wherein the metal is selected from Groups 2-13 of the Periodic Table of the
Elements,
germanium, tin, and lead, and an activator compound (b) comprising b.1) a
cation which is
capable of reacting with a transition metal compound to form a catalytically
active transition
metal complex, and b.2) a compatible anion having up to 100 nonhydrogen atoms
and
containing at least one substituent comprising an active hydrogen moiety.
30 In another aspect of the invention there is provided a process for
preparing a
supported catalyst comprising the process for making the supported catalyst
component of the
present invention and the further step of adding a transition metal compound
(c) containing a
substituent capable of reacting with activator compound (b) to thereby form a
catalytically
active transition metal complex.
35 In yet a further aspect the present invention provides an adduct of an
organometal compound wherein the metal is selected from Groups 2-13 of the
Periodic Table
of the Elements, germanium, tin, and lead, and an activator compound
comprising b~1) a cation
which is capable of reacting with a transition metal compound to form a
catalytically active
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transition metal complex and, b.2) a compatible anion having up to 100
nonhydrogen atoms _
and containing at least one substituent comprising an active hydrogen moiety,
obtained by
combining the organometal compound and the activator compound in a suitable
diluent or
solvent, optionally followed by removing the solvent or diluent.
In yet another aspect the invention provides an addition polymerization
process ,
wherein one or more addition polymerizable monomers are contacted with a
supported
catalyst according to the present invention under addition polymerization
conditions. ,
In yet a further aspect there is provided a complex compound comprising a
charge
balancing cation, and a compatible anion corresponding to Formula (I):
~M~m+Qn(Gq(-~-Pr)~)Z]d. (I)
wherein:
M' is a metal or metalloid selected from Groups 5-15 of the Periodic Table of
the
Elements;
Q independently in each occurrence is selected from the group consisting of
1 S hydride, dihydrocarbylamido, halide, hydrocarbyloxide, hydrocarbyl, and
substituted-
hydrocarbyl radicals, including halo-substituted hydrocarbyl radicals, and
hydrocarbyl- and
halohydrocarbyl-substituted organo-metalloid radicals, the hydrocarbyl portion
having from
1 to 20 carbons with the proviso that in not more than one occurrence is Q
halide;
G is a polyvalent hydrocarbon radical, having r+ 1 valencies, bonded to M' and
T;
z0 T is O, S, NR, or PR, wherein R is a
hydrocarbon radical, a trihydrocarbyl silyl radical, a trihydrocarbyl germyl
radical,
or hydrogen;
Pr is hydrogen H or a protecting group;
m is an integer from 1 to 7;
Z5 n is an integer from 0 to 7;
qis1;
r is an integer from 1 to 3;
z is an integer from 1 to 8;
d is an integer from 1 to 7; and n+z-m = d.
30 According to a further aspect the present invention provides a method for
preparing a complex compound containing an anion corresponding to the Formula
(I).
IM~m+Q~(Ga(T-Pr).)Zld (I)
wherein:
M' is a metal or metalloid selected from Groups 5-15 of the Periodic Table of
the
35 Elements;
Q independently in each occurrence is selected from the group consisting of
hydride, dihydrocarbylamido, halide, hydrocarbyloxide, hydrocarbyl, and
substituted-
hydrocarbyl radicals, including halo-substituted hydrocarbyl radicals, and
hydrocarbyl- and
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halohydrocarbyl-substituted organo-metalloid radicals, the
hydrocarbyl portion having from 1 to 20 carbons with the
proviso that in not more than one occurrence is Q halide;
G is a polyvalent hydrocarbon radical, having
r + 1 valencies, bonded to M' and T;
T is 0, S, NR, or PR, wherein R is a hydrocarbyl
radical, a trihydrocarbyl silyl radical, a trihydrocarbyl
germyl radical or hydrogen;
Pr is hydrogen H or a protecting group;
m is an integer from 1 to 7;
n is an integer from 0 to 7;
q is an integer of 0 or 1;
r is an integer from 1 to 3;
z is an integer from 1 to 8;
d is an integer from 1 to 7; and
n + z-m = d; and
a charge balancing cation;
in which complex compound the anion and cation are
contained in such relative quantities to provide a neutral
compound,
comprising the steps of combining in a suitable
solvent or diluent a compound M~m+Qm with a compound of the
formula Z1 (Gq (T-Pr) r) , wherein Z1 is [M*X**] + or [M**] + and M*
is a group 2 element, M** is a group 1 element and X is
halogen,
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G, T, Pr, q, and r have the same meaning as given for
Formula (I), optionally followed by recovering the product
complex.
According to one aspect of the present invention,
there is provided a supported catalyst component comprising:
a support material having a surface hydroxyl content less
than or equal to 5 mmol per gram, an organometal compound
comprising at least two substituents selected from the group
consisting of hydride, hydrocarbyl, trihydrocarbylsilyl, and
trihydrocarbylgermyl radicals, and wherein the metal is
magnesium, zinc, aluminum, tin, or lead, and an activator
compound comprising a ration which is a Bronsted acid
ration, carbonium ration, silylium ration, or cationic
oxidizing agent and a compatible anion having up to
100 nonhydrogen atoms and containing at least one
substituent comprising an active hydrogen moiety
corresponding to the formula: [Gq(T-H)r], wherein G is a
polyvalent hydrocarbon radical, T is 0, S, NR, or PR,
wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl
radical, a trihydrocarbyl germyl radical or hydrogen, H is
hydrogen, q is 0 or 1, and r is an integer from 1 to 3, the
quantity of activator compound being from 0.1 to 2000
micromoles of activator compound per gram of support and the
quantity of organometal compound being at least 0.1
micromoles per gram of support and up to a maximum (based on
metal weight to support weight) of 40 percent, and wherein
at least some of the organometal compound is reacted with
the activator compound to form a reaction product.
According to another aspect of the present
invention, there is provided a supported catalyst comprising
the supported catalyst component as described herein and a
transition metal compound corresponding
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64693-5214
to the formula:
Z _
Cp* \M(X)" (IV), (ACp)MX~X2 (UC), (ACp)MX' X'2 (X), (ACp)ML (XI), or
(Cp*)(CpR)MX~ (XII),
wherein for compound (IV), M is a Group 3-5 metal; Cp* is a
substituted cyclopentadienyl group bound to 2' and bound in
an r)5-bonding mode to M, wherein the substituents can
independently be one to four substituents selected from the
group consisting of hydrocarbyl, silyl, germyl, halo,
hydrocarbyloxy and amine, each substituent having up to 20
nonhydrogen atoms, or optionally, two such further
substituents together cause Cp* to have a fused ring
structure; Z' is a divalent moiety other than a cyclic or
noncyclic ~-bonded anionic ligand, said 2' comprising boron,
or a member of Group 14 of the Periodic Table of the
Elements, and optionally nitrogen, phosphorus, sulfur or
oxygen, said moiety having up to 20 non-hydrogen atoms, and
optionally Cp* and 2' together form a fused ring system; X
is hydrocarbyl, hydrocarbylene, hydrocarbyloxy, hydride,
halo, silyl, germyl, amide, halo-substituted hydrocarbyl,
organometalloid, or siloxy group having up to 50 non-
hydrogen atoms, with the proviso that at least one X is a
hydride, hydrocarbyl, halo-substituted-hydrocarbyl or
organometalloid radical, and n is 1, 2; and for compounds
(IX), (X), (XI), and (XII), M is a Group 4 metal; (ACp) is
either (Cp)(Cp*) or Cp-A'-Cp*, and Cp and Cp* are the same
or different cyclopentadienyl or substituted
cyclopentadienyl groups, and A' is a covalent bridging group
containing a Group 14 element; L is an olefin, diolefin or
aryne ligand; at least one of X1 and X2 is a hydride,
hydrocarbyl, halo- substituted hydrocarbyl or organo-
metalloid radical, the other of X1 and XZ being a hydride,
hydrocarbyl, halo- substituted hydrocarbyl, organo-
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metalloid, or hydrocarbyloxy radical; X'1 and X'2 are joined
and bound to the metal atom to form a metallocycle, in which
the metal, X'1 and X'2 form a ring containing from 3 to 20
carbon atoms; and R is a substituent having from 1 to 20
carbon atoms on one of the cyclopentadienyl radicals.
According to another aspect of the present
invention, there is provided a use of a supported catalyst
as described herein as a catalyst in an olefin
polymerization.
Detailed description of the invention
All references herein to elements or metals
belonging to a certain Group refer to the Periodic Table of
the Elements published and copyrighted by CRC Press, Inc.,
1989. Also any reference to the Group or Groups shall be to
the Group or Groups as reflected in this Periodic Table of
the Elements using the IUPAC system for numbering groups.
Surprisingly, it has been found that a complex
compound that contains at least one substituent comprising
an active hydrogen moiety as specified herein, can be
attached to the support and is capable of activating
transition metal catalysts typically employed in addition
polymerization processes. This is surprising, as it is
known, that active hydrogen-containing compounds tend to
deactivate typical transition metal catalysts, especially
those transition metal catalysts containing a
cyclopentadienyl moiety or a derivative thereof. The
present supported catalysts can be employed to produce
polymers at satisfactory catalyst efficiencies.
An additional benefit is that the formation of
polymer deposits at reactor walls and other moving parts in
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the reactor is avoided; and the polymers are in the form of
free flowing powder or particles, when a particle forming
polymerization process, such as a slurry or gas phase
polymerization process, is employed so that the polymers can
be easily transported, and that polymers of improved bulk
density are obtained in such particle forming
-5d-
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polymerization processes. According to the present invention improved bulk
densities, for
ethylene based polymers and interpolymers, are preferably bulk densities of at
least about O.ZO
g/cm3, and more preferably of at least about O.zS g/cm3. In the supported
catalyst components
and catalysts, the activating complexes are well dispersed throughout the pore
structure of the
porous support material, which is one of the important factors for maintaining
both an
extended period and a high level of catalyst efficiency. During the formation
of polymer on
the supported catalyst particles, the particles tend to fragment and thus make
fresh surface
available for polymer growth. The presence of catalytically active groups on
such fresh surface
is very desirable for providing good catalyst efficiencies and polymer
morphology.
Suitable support materials for use in the present invention include porous
resinous materials, for example, polyolefins such as polyethylenes and
polypropylenes or
copolymers of styrene-divinylbenzene, and solid inorganic oxides including
oxides of Group Z,
3, 4, 13, or 14 metals, such as silica, aiumina, magnesium oxide, titanium
oxide, thorium oxide,
as well as mixed oxides of silica. Suitable mixed oxides of silica include
those of silica and one or
more Group 2 or 13 metal oxides, such as silica-magnesia or silica-alumina
mixed oxides. Silica,
aiumina, and mixed oxides of silica and one or more Group Z or 13 metal oxides
are preferred
support materials. Preferred examples of such mixed oxides are the silica-
aluminas. The most
preferred support material is silica. The shape of the silica particles is not
critical and the silica
may be in granular, spherical, agglomerated, fumed or other form. Suitable
siiicas include
ZO those that are available from Grace Davison (division of W.R. Grace & Co.)
under the
designations SD 3216.30, SP-9-10046, Davison Syloid Z45, Davison 948 and
Davison 95Z, from
Degussa AG under the designation Aerosil 812, and from Crossfieid under the
designation ES
70X.
Support materials suitable for the present invention preferably have a surface
area as determined by nitrogen porosimetry using the B.E.T. method from 10 to
about 1000
mZ/g, and preferably from about 100 to 600 mZ/g. The pore volume of the
support, as
determined by nitrogen adsorption, is typically up to 5 cm3/g, advantageously
between 0.1 and
3 cm3/g, preferably from about 0.2 to Z cm3lg. The average particle size is
not critical but
typically is from 0.5 to 500 Nm, preferably from 1 to 200 Nm, more preferably
to 100 Nm.
The support material may be subjected to a heat treatment andlor chemical
treatment to reduce the water content or the hydroxyl content of the support
material. Both
dehydrated support materials and support materials containing small amounts of
water can be
used. Typical thermal pretreatments are carried out at a temperature from
30°C to 1000°C for a
duration of 10 minutes to 50 hours in an inert atmosphere or under reduced
pressure. Typical
support materials have a surface hydroxyl content of from 0.1 micromol,
preferably from 5
micromol, more preferably from 0.05 mmol to not more than 5 mmoi hydroxyl
groups per g of
solid support, more preferably from 0.5 to 2 mmol per gram. The hydroxyl
content can be
determined by known techniques, such as infrared spectroscopy and titration
techniques using
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a metal alkyl or metal hydroxide, for example, adding an excess of dialkyl
magnesium to a
slurry of the solid support and determining the amount of dialkyl magnesium
remaining in
solution via known technigues. This latter method is based on the reaction of
5-OH + MgR2-~
5-OMgR + RH, wherein 5 is the solid support.
The support material is treated with the organometal compound. Suitable
organometal compounds are those comprising metals of Groups 2-13, germanium,
tin, and
lead, and at least two substituents selected from hydride, hydrocarbyl
radicals, trihydrocarbyl
silyl radicals, and trihydrocarbyl germyl radicals. Additional substituents
preferably comprise
one or more substituents selected from hydride, hydrocarbyl radicals,
trihydrocarbyl
substituted silyl radicals, trihydrocarbyl substituted germyl radicals, and
hydrocarbyl-,
trihydrocarbyl silyl- or trihydrocarbyl germyl-substituted metalloid radicals.
The recitation "metalloid", as used herein, includes non-metals such as boron,
phosphorus and the like which exhibit semi-metallic characteristics.
Examples of such organometal compounds include organomagnesium,
organozinc, organoboron, organoaluminum, organogermanium, organotin, and
organolead
compounds, and mixtures thereof. Further suitable organometal compounds are al
umoxanes.
Preferred examples are alumoxanes and compounds represented by the following
formulae:
MgR'z, ZnR'z, BR'XRzy, AIR'xRZy, wherein R~ independently each occurrence is
hydride, a
hydrocarbyl radical, a trihydrocarbyl silyl radical, a trihydrocarbyl germyl
radical, or a
trihydrocarbyl-, trihydrocarbyl silyl-, or trihydrocarbyl germyl-substituted
metalloid radical, R2
independently is the same as R', x is 2 or 3, y is 0 or 1 and the sum of x and
y is 3, and mixtures
thereof. Examples of suitable hydrocarbyl moieties are those having from 1 to
20 carbon atoms
in the hydrocarbyl portion thereof, such as alkyl, aryl, alkaryl, or aralkyl.
Preferred radicals
include methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, phenyl, and benzyl.
Preferably, the
aluminum component is selected from the group consisting of alumoxane and
aluminum
compounds of the formula AIR~X wherein R~ in each occurrence independently is
hydride or a
hydrocarbyl radical having from 1 to 20 carbon atoms, and x is 3. Suitable
trihydrocarbyl
aluminum compounds are trialkyl or triaryl aluminum compounds wherein each
alkyl or aryl
group has from 1 to 10 carbon atoms, or mixtures thereof, and preferably
trialkyl aluminum
compounds such as trimethyl, triethyl, tri-isobutyl aluminum.
Alumoxanes (also referred to as aluminoxanes) are oligomeric or polymeric
aluminum oxy compounds containing chains of alternating aluminum and oxygen
atoms,
whereby the aluminum carries a substituent, preferably an alkyl group. The
structure of
alumoxane is believed to be represented by the following general formulae (-
AI(R)-O)m, for a
cyclic alumoxane, and RZAI-O(-AI(R)-O)rt; AIR2, for a linear compound, wherein
R
independently in each occurrence is a C~-Coo hydrocarbyl, preferably alkyl, or
halide and m is an
integer ranging from 1 to about 50, preferably at least about 4. Alumoxanes
are typically the
reaction products of water and an aluminum alkyl, which in addition to an
alkyl group may
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contain halide or alkoxide groups. Reacting several different aluminum alkyl
compounds, such
as, for example, trimethyl aluminum and tri-isobutyl aluminum, with water
yields so-called
modified or mixed alumoxanes. Preferred alumoxanes are methylalumoxane and
methylalumoxane modified with minor amounts of other lower alkyl groups such
as isobutyl.
Alumoxanes generally contain minor to substantial amounts of starting aluminum
alkyl
compound.
The way in which the alumoxane is prepared is not critical. When prepared by
the
reaction between water and aluminum alkyl, the water may be combined with the
aluminum
alkyl in various forms, such as liquid, vapor, or solid, for example in the
form of crystallization
water. Particular techniques for the preparation of alumoxane type compounds
by contacting
an aluminum alkyl compound with an inorganic salt containing water of
crystallization are
disclosed in U.S. Patent 4,542,199. In a particular preferred embodiment an
aluminum alkyl
compound is contacted with a regeneratable water-containing substance such as
hydrated
alumina, silica or other substance. This is disclosed in European Patent
Application No. 338,044.
The supported catalyst component and supported catalyst of the present
invention generally comprise a support material combined or treated with the
organometal
compound, preferably an aluminum component, and containing at least 0.1
micromol of
organometal compound per g of support material, typically at least S micromole
per g support
material, advantageously at least 0.5 weight percent of the metal, preferably
aluminum,
expressed in gram of metal, preferably aluminum, atoms per g of support
material. Preferably,
the amount of metal, advantageously aluminum, is at least 2 weight percent,
and generally not
more than 40 weight percent, and more preferably not more than 30 weight
percent. At too
high amounts of metal, preferably aluminum, the supported catalyst becomes
expensive. At
too low amounts the catalyst efficiency goes down to drop below acceptable
levels.
The supported catalyst component and supported catalyst of the present
invention preferably contain a treated support material (a) comprising a
support material and
an alumoxane wherein not more than about 10 percent aluminum present in the
treated
support material is extractable in a one hour extraction with toluene of
90°C using about 10 mL
toluene per gram of pretreated support material. More preferably, not more
than about 9
Percent aluminum present in the supported catalyst component is extractable,
and most
preferably not more than about 8 percent. This is especially advantageous when
the supported
catalyst component or catalyst prepared therefrom is used in a polymerization
process where a
diluent or solvent is used which may extract non-fixed alumoxane from the
support material. It
has been found that when the amount of extractables is below the levels given
above, the
amount of alumoxane that can diffuse into the polymerization solvent or
diluent, if used, is so
low that no appreciable amount of polymer will be formed in the diluent, as
compared to
polymer formed on the~support material. If too much polymer is formed in the
diluent the
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CA 02214885 1997-09-09
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polymer bulk density will decrease below acceptable levels and reactor fouling
problems may
occu r.
The toluene extraction test is carried out as follows: About 1 g of supported
catalyst component or supported catalyst, with a known aluminum content, is
added to 10 mL
toluene and the mixture is then heated to 90°C under an inert
atmosphere. The suspension is
stirred well at this temperature for 1 hour. Then the suspension is filtered
applying reduced
pressure to assist in the filtration step. The solids are washed twice with
about 3 to 5 ml
toluene of 90°C per gram of solids. The solids are then dried at
120°C for 1 hour, and
subsequently the aluminum content of the solids is measured. The difference
between the
initial aluminum content and the aluminum content after the extraction divided
by the initial
aluminum content and multiplied by 100°/ , gives the amount of
extractable aluminum.
The aluminum content can be determined by slurrying about 0.5 g of supported
catalyst component or supported catalyst in 10 mL hexane. The slurry is
treated with 10 to 15
mL 6N sulfuric acid, followed by addition of a known excess of EDTA. The
excess amount of
EDTA is then back-titrated with zinc chloride.
Without wishing to be bound by any theory, it is believed that the activator
compound used in the present invention reacts with the organometal compound,
preferably
aluminum component, through the active hydrogen-containing substituent. It is
believed that
a group R' of the organometal compound, preferably aluminum component,
combines with
the active hydrogen moiety of the activator compound to release a neutral
organic compound,
for example an alkane, or hydrogen gas thereby chemically coupling the metal,
preferably
aluminum atom with the activator compound residue. Thus the activator is
believed to become
chemically attached to the support material once the support material has been
treated with
the organometal compound or adduct of organometal compound and activator
compound.
Z5 Upon addition of the transition metal compound a supported catalyst is
formed having
improved properties.
The activator compound useful in the present invention contains a compatible
anion having up to 100, and preferably up to 50 nonhydrogen atoms and having
at least one
substituent comprising an active hydrogen moiety. Preferred substituents
comprising an active
hydrogen mojety correspond to the formula
Gq(T-H)~
wherein G is a polyvalent hydrocarbon radical, T is O, S, NR, or PR, wherein R
is a hydrocarbyl
radical, a trihydrocarbyl silyl radical, a trihydrocarbyl germyl radical, or
hydrogen, H is
hydrogen, q is 0 or 1, and preferably 1, and r is an integer from 1 to 3,
preferably 1. Polyvalent
hydrocarbon radical G has r+ 1 valencies, one valency being with a metal or
metalloid of the
Groups 5-15 of the Periodic Table of the Elements in the compatible anion, the
other valency or
valencies of G being attached to r groups T-H. Preferred examples of G include
divalent
hydrocarbon radicals such as: alkylene, arylene, aralkylene, or alkarylene
radicals containing
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from 1 to 20 carbon atoms, more preferably from 2 to 1 Z carbon atoms.
Suitable examples of G
include phenylene, biphenylene, naphthylene, methylene, ethylene, 1,3-
propylene, 1,4-
butylene, phenylmethylene (-C6H4-CHZ-). The polyvalent hydrocarbyl portion G
may be further
substituted with radicals that do not interfere with the coupling function of
the active
hydrogen moiety. Preferred examples of such non-interfering substituents are
alkyl, aryl, alkyl-
or aryl-substituted silyl and germyl radicals, and fluoro substituents.
The group T-H in the previous formula thus may be an -OH, -SH, -NRH, or -PRH
group, wherein R preferably is a C~-~8, preferably a C~_~p hydrocarbyl radical
or hydrogen, and
H is hydrogen. Preferred R groups are alkyls, cycloalkyls, aryls, arylalkyls,
or alkylaryls of 1 to 18
carbon atoms, more preferably those of 1 to 12 carbon atoms. The-OH,-SH,-NRH,
or-PRH
groups may be part of a larger functionality such as, for example, C(O)-OH,
C(S)-SH, C(O)-NRH,
and C(O)-PRH. Most preferably, the group T-H is a hydroxy group, -OH, or an
amino group, -
NRH.
Very preferred substituents Gq(T-H)~ comprising an active hydrogen moiety
include hydroxy- and amino-substituted aryl, aralkyl, alkaryl or alkyl groups,
and most
preferred are the hydroxyphenyls, especially the 3- and 4-hydroxyphenyl
groups, hydroxytolyls,
hydroxy benzyls (hydroxymethylphenyl), hydroxybiphenyls, hydroxynaphthyls,
hydroxycyclohexyls, hydroxymethyls, and hydroxypropyls, and the corresponding
amino-
substituted groups, especially those substituted with -NRH wherein R is an
alkyl or aryl radical
having from 1 to 10 carbon atoms, such as for example methyl, ethyl, propyl, i-
propyl, n-, i-, or t
butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, phenyl, benzyl, tolyl,
xylyl, naphthyl, and
biphenyl.
The compatible anion containing the substituent which contains an active
hydrogen moiety, may further comprise a single Group 5-15 element or a
plurality of Group 5-
15 elements, but is preferably a single coordination complex comprising a
charge-bearing
metal or metalloid core, which anion is bulky. A compatible anion specifically
refers to an
anion which when functioning as a charge balancing anion in the catalyst
system of this
invention, does not transfer an anionic substituent or fragment thereof to the
transition metal
cation thereby forming a neutral transition metal compound and a neutral metal
by-product.
~~Compatible anions" are anions which are not degraded to neutrality when the
initially
formed complex decomposes and are noninterfering with desired subsequent
polymerizations.
Preferred anions are those containing a single coordination complex comprising
a charge-
bearing metal or metalloid core carrying a substituent containing an active
hydrogen moiety
which anion is relatively large (bulky), capable of stabilizing the active
catalyst species (the
transition metal cation) which is formed when the activator compound and
transition metal
compound are combined and said anion will be sufficiently labile to be
displaced by olefinic,
diolefinic and acetylenically unsaturated compounds or other neutral Lewis
bases such as
ethers, nitrites and the like. Suitable metals for the anions of activator
compounds include, but
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are not limited to, aluminum, gold, platinum and the like. Suitable metalloids
iriclude, but are
not limited to, boron, phosphorus, silicon and the like. Activator compounds
which contain
anions comprising a coordination complex containing a single boron atom and a
substituent
comprising an active hydrogen moiety are preferred.
- 5 Preferably, compatible anions containing a substituent comprising an
active
hydrogen moiety may be represented by the following general Formula (I):
~M~m+Qn(Gq(-~ H)r)z~d (I)
wherein:
M' is a metal or metalloid selected from Groups 5-15 of the Periodic Table of
the
Elements;
Q independently in each occurrence is selected from the group consisting of
hydride, dihydrocarbylamido, preferably dialkylamido, halide,
hydrocarbyloxide, preferably
alkoxide and aryloxide, hydrocarbyl, and substituted-hydrocarbyl radicals,
including halo-
substituted hydrocarbyl radicals, and hydrocarbyl- and halohydrocarbyl-
substituted organo-
metalloid radicals, the hydrocarbyl portion having from 1 to 20 carbons with
the proviso that in
not more than one occurrence is Q halide;
G is a polyvalent, having r+ 1 valencies and preferably divalent hydrocarbon
radical bonded to M' and T;
T is O, S, NR, or PR, wherein R is a hydrocarbon radical, a trihydrocarbyl
silyl
radical, a trihydrocarbyl germyl radical, or hydrogen;
m is an integer from 1 to 7, preferably 3;
n is an integer from 0 to 7, preferably 3;
q is an integer 0 or 1, preferably 1;
r is an integer from 1 to 3, preferably 1;
Z5 z is an integer from 1 to 8, preferably 1;
d is an integer from 1 to 7, preferably 1; and
n+z-m = d.
Preferred boron-containing anions which are particularly useful in this
invention
may be represented by the following general Formula (II):
IBQQ_Z,(Gq(T-H),)Z,ld~ (II)
wherein:
B is boron in a valence state of 3;
z' is an integer from 1-4, preferably 1;
d is 1; and
Q, G, T, H, q, and r are as defined for Formula (I). Preferably, z' is 1, q is
1, and r is
1.
Illustrative, but not limiting, examples of anions of activator compounds to
be
used in the present invention are boron-containing anions such as
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triphenyl(hydroxyphenyl)borate, Biphenyl-di(hydroxyphenyl)borate,
triphenyl(2,4-
dihydroxyphenyl)borate, tri(p-tolyl)(hydroxyphenyl)borate, tris-
(pentafluorophenyl)(hydroxyphenyl)borate, tris-(2,4-
dimethylphenyl)(hydroxyphenyl)borate,
tris-(3,5-dimethylphenyl)(hydroxyphenyl)borate, tris-(3,5-di-trifluoromethyl-
phenyl)(hydroxyphenyl)borate, tris(pentafluorophenyl)(2-hydroxyethyl)borate,
tris(pentafluorophenyl)(4-hydroxybutyl)borate, tris(pentafluorophenyl)(4-
hydroxycyclohexyl)borate, tris(pentafluorophenyl)(4-(4'-
hydroxyphenyl)phenyl)borate,
tris(pentafluorophenyl)(6-hydroxy-2-naphthyl)borate, and the like. A highly
preferred
activator complex is tris(pentafluorophenyl)(4-hydroxyphenyl) borate. Other
preferred anions
of activator compounds are those above mentioned borates wherein the hydroxy
functionality
is replaced by an amino NHR functionality wherein R preferably is methyl,
ethyl, or t-butyl.
The cationic portion b.1 ) of the activator compound to be used in association
with
the compatible anion b.2) can be any cation which is capable of reacting with
the transition
metal compound to form a catalytically active transition metal complex,
especially a cationic
transition metal complex. The cations b.1) and the anions b.2) are used in
such ratios as to give
a neutral activator compound. Preferably the cation is selected from the group
consisting of
Bronsted acidic cations, carbonium cations, silylium cations, and cationic
oxidizing agents.
Bronsted acidic cations may be represented by the following general formula:
CL-H)+
wherein:
L is a neutral Lewis base, preferably a nitrogen, phosphorus, or sulfur
containing
Lewis base; and (L-H)+ is a Bronsted acid. The Bronsted acidic cations are
believed to react with
the transition metal compound by transfer of a proton of said cation, which
proton combines
with one of the ligands on the transition metal compound to release a neutral
compound.
Illustrative, but not limiting, examples of Bronsted acidic cations of
activator
compounds to be used in the present invention are trialkyl-substituted
ammonium cations such
as triethylammonium, tripropylammonium, tri(n-butyl)ammonium,
trimethylammonium,
tributylammonium, and tri(n-octyl)ammonium. Also suitable are N,N-dialkyl
anilinium cations
such as N,N-dimethylanilinium, N,N-diethylanilinium, N,N-2,4,6-
pentamethylanilinium, N,N-
dimethylbenzylammonium and the like; dialkylammonium cations such as di-(i-
propyl)ammonium, dicyclohexylammonium and the like; and triarylphosphonium
cations such
as triphenylphosphonium, tri(methylphenyl)phosphonium,
tri(dimethylphenyl)phosphonium,
dimethylsulphonium, diethylsulphonium, and diphenylsulphonium.
A second type of suitable cations corresponds to the formula: ~+, wherein ~+
is a
stable carbonium or silylium ion containing up to 30 nonhydrogen atoms, the
cation being
capable of reacting with a substituent of the transition metal compound and
converting it into
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WO 9612848a PCTIUB96I02891
a catalytically active transition metal complex, especially a cationic
transition metal complex.
Suitable examples of cations include tropyllium, triphenylmethylium,
benzene(diazonium).
Silylium salts have been previously generically disclosed in J. Chem. Soc.
Chem. Comm., 1993,
383-384, as well as Lambert, J.B., et. al., Organometallics, 1994, 13, 2430-
2443. Preferred
silylium cations are triethylsilylium, and trimethylsilylium and ether
substituted adducts
thereof.
Another suitable type of cation comprises a cationic oxidizing agent
represented
by the formula:
Oxe+
wherein Ox~+ is a cationic oxidizing agent having a charge of a+; and a is an
integer from 1 to
3.
Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-
substituted ferrocenium, Ag+, and Pbz+
The quantity of activator compound in the supported catalyst component and the
supported catalyst is not critical, but typically ranges from 0.1, preferably
from 1 to 2,000
micromoles of activator compound per gram of treated support material.
Preferably, the
supported catalyst or component contains from 10 to 1,000 micromoles of
activator compound
per gram of treated support material.
The supported catalyst component of the present invention as such or slurried
in a
diluent can be stored or shipped under inert conditions, or can be used to
generate the
supported catalyst of the present invention.
Suitable transition metal compounds for use in the supported catalyst of the
present invention are those that contain a substituent capable to react with
activator
compound (b) to thereby form a catalytically active transition metal complex.
The transition
metal compounds may be derivatives of any transition metal including
Lanthanides, preferably
from Groups 3, 4, 5, and 6, more preferably of the Group 3 or 4 transition
metals or the
Lanthanides, which transition metals are in the +2, +3, or +4 formal oxidation
state. The
transition metals preferably contain at least one n-bonded anionic ligand
group which can be a
cyclic or noncyclic delocalized n-bonded anionic ligand group. Exemplary of
such n-bonded
anionic ligand group are conjugated or non-conjugated, cyclic or non-cyclic
dienyl groups, allyl
groups, aryl groups, as well as substituted derivatives of such groups.
By the term "derivative" when used to describe the above-substituted,
delocalized n-bonded groups is meant that each atom in the delocalized n-
bonded group may
independently be substituted with a radical selected from the group consisting
of halogen,
hydrocarbyl, halohydrocarbyl, and hydrocarbyl-substituted metalloid radicals
wherein the
metalloid is selected from Group 14 of the Periodic Table of the Elements.
Included within the
term "hydrocarbyl" are C~_2p straight, branched and cyclic alkyl radicals, C6-
2o aromatic radicals,
C~_ZO alkyl-substituted aromatic radicals, and C~_Zp aryl-substituted alkyl
radicals. In addition
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two or more such radicals may together form a fused ring system or a
hydrogenated fused ring
system. Suitable hydrocarbyl-substituted organo-metalloid radicals include
mono-, di- and tri-
substituted organo-metalloid radicals of Group 14 elements wherein each of the
hydrocarby)
groups contains from 1 to 20 carbon atoms. More particularly, suitable
hydrocarbyl-substituted
organo-metalloid radicals include trimethylsilyl, triethylsilyl,
ethyldimethylsilyl, methyldiethyl-
silyl, triphenylgermyl, trimethylgermyl and the like.
Preferred anionic, delocalized n-bonded groups include cyclopentadienyl and
substituted cyclopentadienyl groups. Especially preferred are
cyclopentadienyl, indenyl,
fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, and octahydrofluorenyl.
Other examples of
preferred anionic ligand groups are pentadienyl, cyclohexadienyl,
dihydroanthracenyl,
hexahydroanthracenyl, and decahydroanthracenyl groups, and methyl-substituted
derivatives
thereof.
Suitable transition metal compounds (c) may be a cyclopentadienyl or
substituted
cyclopentadienyl derivative of any transition metal including Lanthanides, but
preferably of
the Group 3, 4, or Lanthanide transition metals. Suitable transition metal
compounds for use in
the present invention are the bridged or unbridged mono-, bis-, and tri-
cyclopentadienyl or
substituted cyclopentadienyl transition metal compounds.
Suitable unbridged monocyclopentadienyl or mono(substituted
cyclopentadienyl) transition metal derivatives are represented by general
Formula (3):
CpMX" (3)
wherein Cp is cyclopentadienyl or a derivative thereof, M is a Group 3, 4, or
5 transition metal
having a formal oxidation state of +2, +3 or +4, X independently in each
occurrence
represents an anionic ligand group (other than a cyclic, aromatic n-bonded
anionic ligand
group) selected from the group of hydrocarbyl, hydrocarbylene (including
hydrocarbadienyl),
hydrocarbyloxy, hydride, halo, silyl, germyl, amide, and siloxy radicals
having up to 50
nonhydrogen atoms, with the proviso that at least one X is selected from the
group of a
hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, or
organo-metalloid
radical, and n, a number equal to one less than the formal oxidation state of
M, is 1, 2 or 3,
preferably 3. Preferably, at least one of X is a hydrocarbyl radical having
from 1 to about 20
carbon atoms, a substituted-hydrocarbyl radical having from 1 to about 20
carbon atoms
wherein one or more of the hydrogen atoms are replaced with a halogen atom, or
an organo-
metalloid radical comprising a Group 14 element wherein each of the
hydrocarbyl substituents
contained in the organo portion of said organo-metalloid, independently,
contain from 1 to
about 20 carbon atoms.
Suitable bridged monocyclopentadienyl or mono(substituted cyclopentadienyl)
transition metal compounds include the so-called constrained geometry
complexes. Examples
of such complexes and methods for their preparation are disclosed in U.S.
Application Serial No.
545,403, filed July 3, 1990 (corresponding to EP-A-416,815), U.S. Application
Serial No. 241,523,
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CA 02214885 2005-08-26
64693-5214
filed May 12, 1994 (corresponding to WO-95/00526), as well as U.S. Patents
5,055,438,
5,057,475, 5,096,867, 5,064,802 5,132,380, and 5,374,696.
More particularly, preferred bridged monocydopentadienyl or mono(substituted
cyclopentadienyl) transition metal compounds correspond to the Formula (I~:
Z'
M (IV)
(X)n
wherein:
M is a metal of Group 3-5, especially a Group 4 metal, particularly titanium;
Cp* is a substituted cydopentadienyl group bound to Z' and, in an r15 bonding
mode, to M or such a group is further substituted with from one to four
substituents selected
from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy,
amine, and
mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or
optionally, two such
further substituents together cause Cp* to have a fused ring structure;
Z' is a divalent moiety other than a cydic or noncydic n-bonded anionic
Iigand,
said Z' comprising boron, or a member of Group 14 of the Periodic Table of the
Elements, and
optionally nitrogen, phosphorus, sulfur or oxygen, said moiety having up to 20
non-hydrogen
atoms, and optionally Cp* and Z' together form a fused ring system;
X has the same meaning as in Formula (III); and
n is 1 or 2 depending on the valence of M.
In consonance with the previous explanation, M is preferably a Group 4 metal,
especially titanium; n is 1 or2; and X is monovalent ligand group of up to 30
nonhydrogen
atoms, more preferably, C~-zo hydrocarbyl.
When n is 1 and the Group 3-5 metal (preferably the Group 4 metal) is in the
+3
formal oxidation state, X is preferably a stabilizing ligand.
By the term "stabilizing ligand" is meant that the ligand group Stabilizes the
metal complex through either:
1 ) a nitrogen, phosphorus, oxygen or sulfur chelating bond, or
2) an r13 bond with a resonant, delocaiized
n-electronic structure.
Examples of stabilizing ligands of group 1 ) include silyl, hydrocarbyl, amido
or
phosphido ligands substituted with one or more aliphatic or aromatic ether,
thioether, amine
or phosphine functional groups, especially such amine or phosphine groups that
are tertiary-
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substituted, said stabilizing ligand having from 3 to 30 nonhydrogen atoms.
Most preferred .
group 1) stabilizing ligands are 2-dialkylaminobenzyl or Z-
(dialkylaminomethyl)phenyl groups
containing from 1 to 4 carbons in the alkyl groups.
Examples of stabilizing ligands of group 2) include C3_~p hydrocarbyl groups
containing ethylenic unsaturation, such as allyl,1-methylallyl, Z-methylallyl,
1,1-dimethylallyl, .
or 1,2,3-trimethylallyl groups.
More preferably still, such metal coordination complexes correspond to the .
Formula (V):
R'
Y
R M~ CV)
R~ ~X)n
R'
""herein R' in each occurrence is independently selected from the group
consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and
combinations thereof
having up to 20 nonhydrogen atoms, or two R' groups together form a divalent
derivative
thereof;
X has the same meaning as defined for Formula (III);
z0 Y is a divalent anionic li and rou com risin vitro en hos horns ox en or
g 9 P P 9 9 ,P P , yg
sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M
through said
nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a
fused ring
system;
M is a Group 4 metal, especially titanium;
z5 Z is SiR* CR* SiR* SiR* CR* CR* CR*=CR* CR* SiR* GeR*2 BR*, or BR*2~
2. 2. 2 2~ 2 2, ~ 2 2, . ,
wherein:
R* in each occurrence is independently selected from the group consisting of
hydrogen, hydrocarbyl, silyl, halogenated alkyl, halogenated aryl groups
having up to 20 non-
hydrogen atoms, and mixtures thereof, or two or more R* groups from Z, or an
R* group from
30 Z together with Y form a fused ring system; and
nis1or2.
Further more preferably, Y is-O-, -S-, -NR*-, -PR*-. Highly preferably Y is a
nitrogen or phosphorus containing group corresponding to the formula -N(R')-
or -P(R')-,
wherein R' is as previously described, ie., an amido or phosphido group.
35 Most highly preferred metal coordination complexes correspond to the
Formula
(VI):
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WO 96128480 PC7YUS96I02893
Rr (ERf2)~~ r
N-R
Rr M/ (VI)
- 5
Rr Rr (X)n
wherein:
M is titanium;
R' each occurrence is independently selected from the group consisting of
hydrogen, silyl, hydrocarbyl and combinations thereof having up to 10 carbon
or silicon atoms,
or two R' groups of the substituted cyclopentadienyl moiety are joined
together;
E is silicon or carbon;
X independently each occurrence is hydride, alkyl, aryl, of up to 10 carbons;
m is 1 or 2; and
nis1or2.
Examples of the above most highly preferred metal coordination compounds
include compounds wherein the R' on the amido group is methyl, ethyl, propyl,
butyl, pentyl,
hexyl, (including isomers), norbornyl, benzyl, phenyl, and cyclododecyl;
(ER'2)r" is dimethyl
silane or 1,2-ethylene; R' on the cyclic n-bonded group independently each
occurrence is
hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, norbornyl, benzyl, and
phenyl, or two R'
groups are joined forming an indenyl, tetrahydroindenyl, fluorenyl or
octahydrofluorenyl
moiety; and X is methyl, ethyl, propyl, butyl, pentyl, hexyl, norbornyl,
benzyl, and phenyl.
Transition metal compounds wherein the transition metal is in the + 2 formal
z5 oxidation state include those complexes containing one and only one cyclic,
delocalized,
anionic, n-bonded group, said complexes corresponding to the Formula (VII):
/ Z
\ (VII)
L - M- X*
wherein:
M is titanium or zirconium in the +2 formal oxidation state;
L is a group containing a cyclic, delocalized, anionic, n-system through which
the
group is bonded to M, and which group is also bonded to Z;
Z is a moiety bonded to M via a o-bond, comprising boron, or a member of Group
- 35 14 of the Periodic Table of the Elements, and also comprising nitrogen,
phosphorus, sulfur or
oxygen, said moiety having up to 60 non-hydrogen atoms; and
X* is a neutral, conjugated or nonconjugated diene, optionally substituted
with
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one or more hydrocarbyl groups, said X having up to 40 carbon atoms and
forming a n-complex
with M.
Preferred transition metal compounds of Formula (VII) include those wherein Z,
M
and X* are as previously defined; and L is a C5H4 group bonded to Z and bound
in an r)5
bonding mode to M or is such an rls bound group substituted with from one to
four
substituents independently selected from hydrocarbyl, silyl, germyl, halo,
cyano, and
combinations thereof, said substituent having up to 20 nonhydrogen atoms, and
optionally,
two such substituents (except cyano or halo) together cause a fused ring
structure.
More preferred transition metal +2 compounds according to the present
invention correspond to the Formula (VIII):
R t Z'~
Y
R
R~ X*
R
wherein:
R' in each occurrence is independently selected from hydrogen, hydrocarbyl,
silyl,
germyl, halo, cyano, and combinations thereof, said R' having up to 20
nonhydrogen atoms,
and optionally, two R' groups (where R' is not hydrogen, halo or cyano)
together form a
divalent derivative thereof connected to adjacent positions of the
cyclopentadienyl ring to
form a fused ring structure;
X* is a neutral r)4-bonded diene group having up to 30 nonhydrogen atoms,
which forms a n-complex with M;
Y is -O-, -S-, -NR*-, -PR*-;
M is titanium or zirconium in the + 2 formal oxidation state;
Z* is SiR*z, CR*z, SiR*ZSiR*z, CR*ZCR*Z, CR*=CR*, CR*zSiR*z, or GeR*z;
wherein:
R* each occurrence is independently hydrogen, or a member selected from
hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations
thereof, said R*
having up to 10 nonhydrogen atoms, and optionally, two R* groups from Z* (when
R* is not
hydrogen), or an R* group from Z* and an R* group from Y form a ring system.
Preferably, R' independently each occurrence is hydrogen, hydrocarbyl, silyl,
halo
and combinations thereof said R' having up to 1,0 nonhydrogen atoms, or two R'
groups (when
R' is not hydrogen or halo) together form a divalent derivative thereof; most
preferably, R' is
hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, (including where
appropriate all isomers),
cyclopentyl, cyclohexyl, norbornyl, benzyl, or phenyl or two R' groups (except
hydrogen) are
linked together, the entire C5R'4 group thereby being, for example, an
indenyl,
tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl
group.
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Further preferably, at least one of R' or R* is an electron donating moiety.
By the
term "electron donating" is meant that the moiety is more electron donating
than hydrogen.
Thus, highly preferably Y is a nitrogen or phosphorus containing group
corresponding to the
formula-N(R")-or-P(R")-,wherein R" is C~_~o hydrocarbyl.
Examples of suitable X* groups include: s-traps-rl4-1,4-diphenyl-1,3-
butadiene; s-
trans-r)4-3-methyl-1,3-pentadiene; s-traps-n4-1,4-dibenzyl-1,3-butadiene; s-
traps-n4-Z,4-
hexadiene; s-traps-rI4-1,3-pentadiene; s-traps-r14-1,4-ditolyl-1,3-butadiene;
s-traps-r)4-1,4-
bis(trimethylsilyl)-1,3-butadiene; s-cis-r)4-1,4-diphenyl-1,3-butadiene; s-cis-
r14-3-methyl-1,3-
pentadiene; s-cis-rl4-1,4-dibenzyl-1,3-butadiene; s-cis-r)4-2,4-hexadiene; s-
cis-r14-1,3-
pentadiene; s-cis-r)4-1,4-ditolyl-1,3-butadiene; and s-cis-r)4-1,4-
bis(trimethylsilyl)-1,3-
butadiene, said s-cis diene group forming a n-complex as defined herein with
the metal.
Most highly preferred transition metal +2 compounds are amidosilane- or
amidoalkanediyl- compounds of Formula VIII) wherein:
-Z*-Y- is-(ER"'z),r; N(R")-, and R' each occurrence is independently selected
from
hydrogen, silyl, hydrocarbyl and combinations thereof, said R' having up to 10
carbon or silicon
atoms, or two such R' groups on the substituted cyclopentadienyl group (when
R' is not
hydrogen) together form a divalent derivative thereof connected to adjacent
positions of the
cyclopentadienyl ring;
R" is C~_~o hydrocarbyl;
R"' is inde endentl each occurrence h dro en or C y ,
P Y y g ~_io hydrocarb I'
E is independently each occurrence silicon or carbon; and
mist or2.
Examples of the metal complexes according to the present invention include
compounds wherein R" is methyl, ethyl, propyl, butyl, pentyl, hexyl,
(including all isomers of
the foregoing where applicable), cyclododecyl, norbornyl, benzyl, or phenyl;
(ER"'Z)m is
dimethylsilane, or ethanediyl; and the cyclic delocalized n-bonded group is
cyclopentadienyl,
tetramethylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl,
tetrahydrofluorenyl or
octahydrofluorenyl.
Suitable bis(cyclopentadienyl) derivatives of transition metals include those
of
titanium, zirconium and hafnium compounds and may be represented by the
following
general Formulae (IX)-(XII):
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64693-5214
(A-Cp)MX1X2 (IX)
(A-Cp)MX X'2 (X)
(A-Cp)ML (XI)
(Cp*)(CpR)MX1 (XII)
wherein: M is a Group 4 metal namely titanium (Ti), zirconium (Zr) and hafnium
(Hf); (A-Cp) is
~ 0 either (Cp)(Cp*) or Cp-A'-Cp* and Cp and Cp* are the same or different
cyclopentadienyl
radicals, as well as substituted derivatives of cydopentadienyl radicals, and
A' is a covalent
bridging group containing a Group 14 element; L is an olefin, diolefin or
aryne ligand; at least
one of Xi and XZ is a hydride radical, hydrocarbyl radical, substituted-
hydrocarbyl radical, or
organo-metalloid radical, the other of Xi and XZ being a hydride radical,
hydrocarbyl radical,
15 substituted-hydrocarbyl radical, organo-metalloid radical, or a
hydrocarbyloxy radical;
preferably one or both of X~ and Xz is a hydrocarbyl radical having from 1 to
about 20 carbon
atoms, substituted-hydrocarbyl radical having from 1 to about 20 carbon atoms
wherein one or
more of the hydrogen atoms are replaced with a halogen atom, organo-metalloid
radical
comprising a Group 14 element wherein each of the hydrocarbyl substituents
contained in the
20 organo portion of said organo-metalloid, independently, contain from 1 to
about 20 carbon
atoms; X'i and X'z are joined and bound to the metal atom to farm a
metallacyde, in which the
metal, X'~ and X'z form a hydrocarbocydic ring containing from about 3 to
about ZO carbon
atoms; and R is a substituent, preferably a hydrocarbyl substituent, having
from 1 to 20 carbon
atoms on one of the cyclopentadienyl radicals, which is also bound to the
metal atom.
25 When not both Xi and Xz are a hydride radical, hydrocarbyl radical,
substituted-
hydrocarbyl radical, or organo-metalloid radical one of these can be a
hydrocarbyloxy radical
having from 1 to 20 carbon atoms. Suitable examples of hydrocarbyfoxy radicals
include
alkyloxy, aryloxy, aralkyloxy, and alkaryloxy radicals having from 1 to 20
carbon atoms, more
preferably alkyl radicals having from 1 to 6 carbon atoms, and aryl, aralkyl
and alkaryl radicals
30 having from 6 to 10 carbon atoms, even more preferably isopropyloxy, n-
butyloxy, or t-
butyloxy.
Examples of such bis(cydopentadienyl) derivatives of transition metals and
methods for their preparation are disclosed in U.S. Patent 5,384,299
(corresponding to EP-A-
277,004) and WO-91/09882.
Suitable tri-cydopentadienyl or substituted cyclopentadienyl transition metal
compounds include those containing a bridging group finking two
cyclopentadienyl groups
and those without such bridging groups.
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WU 96f28480 PCTlUS96102891
Suitable unbridged tri-cyclopentadienyl transition metal derivatives are
represented by general Formula (X111):
Cp3MXn" (X111)
wherein Cp, M and X are as defined for Formula (III) and n" is three less than
the formal
. 5 oxidation state of M and is 0 or 1, preferably 1. Preferred ligand groups
X are hydrocarbyl,
hydrocarbyloxy, hydride, halo, silyl, germyl, amide, and siloxy.
Generally, the ratio of moles of activator compound (b) to gramatoms of
transition metal in compound (c) in the supported catalyst is from 0.05:1 to
100:1, preferably
from 0.5:1 to 20:1 and most preferably from 1:1 to 5:1 mote activator compound
per
9ramatom of transition metal in the transition metal compound. At too low
ratios the
supported catalyst will not be very active, whereas at too high ratios the
catalyst becomes less
economic due to the relatively high cost associated with the use of large
quantities of activator
compound.
The supported catalyst component of the present invention can be prepared by
combining the support material with the organometal compound, preferably an
aluminum
component, and the activator compound. The order of addition is not critical.
The
organometal compound may be either first combined with the support material or
with the
activator compound, and subsequently the activator compound or the support
material may be
added. One preferred embodiment comprises treating the support material first
with the
organometal compound, preferably aluminum component by combining the
organometal
compound in a suitable solvent, such as a hydrocarbon solvent, with the
support material. The
temperature, pressure, and contact time for this treatment are not critical,
but generally vary
from -20°C to about 150°C, from subatmospheric to 10 bar, more
preferably at atmospheric
pressure, for 5 minutes to 48 hours. Usually the slurry is agitated. After
this treatment the
solids are typically separated from the solvent. Any excess of organometal
compound could
then be removed by techniques known in the art. This method is especially
suitable for
obtaining support material with relatively low metal, preferably aluminum,
loadings.
According to a preferred embodiment, the support material is first subjected
to a
thermal treatment at 100°C to 1000°C, preferably at about
200°C to about 850°C. Typically, this
treatment is carried out for about 10 minutes to about 72 hours, preferably
from about 0.5
hours to 24 hours. Then the thermally treated support material is combined
with the
organometal compound, preferabIyAIR'3wherein R' has the meaning defined
hereinbefore in
a suitable diluent or solvent, preferably one in which the organometal
compound is soluble.
Typical solvents are hydrocarbon solvents having from 5 to 12~carbon atoms,
preferably
aromatic solvents such as toluene and xylenes, or aliphatic solvents of 6 to
10 carbon atoms,
such as hexane, heptane, octane, nonane, decane, and isomers thereof,
cycloaliphatic solvents
of 6 to 12 carbon atoms such as cyclohexane, or mixtures of any of these.
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The support material is combined with the organometal compound at a
temperature of-20°C to 150°C, preferably at 20°C to
100°C. The contact time is not critical and
can vary from 5 minutes to 72 hours, and is preferably from 0.5 hours to 36
hours. Agitation is
preferably applied. The thus treated support material is then preferably
contacted with the
activator compound. ,
An alternative treatment of the support material, suitable for obtaining
alumoxane loadings attached to the support material, involves one or both of
the following
steps A and B:
A. heating a support material containing alumoxane under an inert
atmosphere for a period and at a temperature sufficient to fix alumoxane to
the support
material;
B. subjecting the support material containing alumoxane to one or more
wash steps to remove alumoxane not fixed to the support material;
thereby selecting the conditions in heating step A and washing step B so as to
form a treated support material wherein not more than about 10 percent
aluminum present in
the treated support material cis extractable in a one hour extraction with
toluene of 90°C using
about 10 mL toluene per gram of supported catalyst component. High amounts of
alumoxane
attached to the support material are obtained using first heating step A.,
optionally followed
by wash step B.
In this process the alumoxane treated support material may be obtained by
combining in a diluent an alumoxane with a support material containing from
zero to not
more than 20 weight percent of water, preferably from zero to not more than 6
weight percent
of water, based on the total weight of support material and water. Although
support
materials containing substantially no water give good results with respect to
catalytic
properties of the supported catalyst, it has been found that support materials
containing
relatively small amounts of water can be used without problem in the present
process. The
water containing support materials when combined under identical conditions
with the same
amount of alumoxane gives in the present process a supported catalyst
component having a
slightly higher aluminum content than the substantially water-free support
material. It is
believed that the water reacts with the residual amounts of aluminum alkyl
present in the
alumoxane to convert the aluminum alkyl to extra alumoxane. An additional
advantage is that
in this way less aluminum alkyl will be lost to waste or recycle streams. The
alumoxane
desirably is used in a dissolved form.
Alternatively, the alumoxane pretreated support material may be obtained by
combining in a diluent, a support material containing from 0.5 to 50 weight
percent water,
preferably from 1 to 20 weight percent water, based on the total weight of
support material
and water, with a compound of the formula R"~*AIX"3_~* wherein R" in
independently each
occurrence is a hydrocarbyl radical, X" is halogen or hydrocarbyloxy, and n*
is an integer from 1
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WO 96/28480 PGT/US96/02891
to 3. Preferably, n* is 3. R" in independently each occurrence is preferably
an alkyl radical,
advantageously one containing from 1 to 12 carbon atoms. Preferred alkyl
radicals are methyl,
ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, iso-pentyl,
hexyl, iso-hexyl, heptyl,
octyl, and cyclohexyl. Highly preferred compounds of formula R"~*AIX"3_~* are
trimethylaluminum, triethylaluminum and tri-isobutylaluminum. When the
alumoxane is
prepared in situ by reacting the compound of the formula R"~*AIX"3_~* with
water, the mole
ratio of R"~*AIX"3_~* to water is typically 10:1 to 1:1, preferably from 5:1
to 1:1.
The support material is added to the alumoxane or compound of the formula
R"~*AIX"3_~*, preferably dissolved in a solvent, most preferably a hydrocarbon
solvent, or the
solution of alumoxane or compound of the formula R"~*AIX"3-~* is added to the
support
material. The support material can be used as such in dry form or slurried in
a hydrocarbon
diluent. Both aliphatic and aromatic hydrocarbons can be used. Suitable
aliphatic
hydrocarbons include, for example, pentane, isopentane, hexane, heptane,
octane, iso-octane,
nonane, isononane, decane, cyclohexane, methylcyclohexane and combinations of
two or
more of such diluents. Suitable examples of aromatic diluents are benzene,
toluene, xylene,
and other alkyl or halogen-substituted aromatic compounds. Most preferably,
the diluent is an
aromatic hydrocarbon, especially toluene. Suitable concentrations of solid
support in the
hydrocarbon medium range from about 0.1 to about 15, preferably from about 0.5
to about
10, more preferably from about 1 to about 7 weight percent. The contact time
and
ZO temperature are not critical. Preferably the temperature is from 0°C
to 60°C, more preferably
from 10°C to 40°C. The contact time is from 15 minutes to 40
hours, preferably from 1 to 20
hours.
Before subjecting the alumoxane-treated support material to the heating step
or
washing step, the diluent or solvent is preferably removed to obtain a free
flowing powder.
z5 This is preferably done by applying a technique which only removes the
liquid and leaves the
aluminum compounds on the solids, such as by applying heat, reduced pressure,
evaporation,
or a combination thereof. If desired, the removal of diluent can be combined
with the heating
step, although care should be taken that the diluent is removed gradually.
The heating step and/or the washing step are conducted in such a way that a
very
30 large proportion (more than about 90 percent by weight) of the alumoxane
which remains on
the support material is fixed. Preferably, a heating step is used, more
preferably a heating step
is used followed by a washing step. When used in the preferred combination
both steps
cooperate such that in the heating step the alumoxane is fixed to the support
material,
whereas in the washing step the alumoxane which is not fixed is removed to a
substantial
35 degree. The upper temperature for the heat-treatment is preferably below
the temperature at
which the support material begins to agglomerate and form lumps which are
difficult to
redisperse, and below the alumoxane decomposition temperature. When the
transition metal
compound c) is added before the heat treatment, the heating temperature should
be below
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WO 96/28480 PCT/US96/02891
the decomposition temperature of the transition metal compound. Preferably,
the heat-
treatment is carried out at a temperature from 75°C to 250°C for
a period from 15 minutes to 24
hours. More preferably, the heat treatment is carried out at a temperature
from 160°C to 200°C
for a period from 30 minutes to 4 hours. Good results have been obtained while
heating for 8
hours at 100°C as well as while heating for Z hours at 175°C. By
means of preliminary
experiments, a person skilled in the art will be able to define the heat-
treatment conditions
that will provide the desired result. It is also noted, that the longer the
heat treatment takes,
the higher the amount of alumoxane fixed to the support material will be. The
heat-treatment
is carried out at reduced pressure or under an inert atmosphere, such as
nitrogen gas, or both
but preferably at reduced pressure. Depending on the conditions in the heating
step, the
alumoxane may be fixed to the support material to such a high degree that a
wash step may be
omitted.
In the wash step, the number of washes and the solvent used are such that
sufficient amounts of non-fixed alumoxane are removed. The washing conditions
should be
such that non-fixed afumoxane is soluble in the wash solvent. The support
material containing
alumoxane, preferably already subjected to a heat-treatment, is preferably
subjected to one to
five wash steps using an aromatic hydrocarbon solvent at a temperature from
0°C to 110°C.
More preferably, the temperature is from 20°C to 100°C.
Preferred examples of aromatic
solvents include toluene, benzene and xylenes. More preferably, the aromatic
hydrocarbon
Zp solvent is toluene. At the end of the wash treatment, the solvent is
removed by a technique
that also removes the alumoxane dissolved in the solvent, such as by
filtration or decantation.
Preferably, the wash solvent is removed to provide a free flowing powder.
The organometal compound treated support material is then typically reslurried
in a suitable diluent and combined with the activator compound. The activator
compound is
Z5 preferably used in a diluent. Suitable diluents include hydrocarbon and
halogenated
hydrocarbon diluents. Any type of solvent or diluent can be used which does
not react with the
catalyst components in such a way as to negatively impact the catalytic
properties. Preferred
diluents are aromatic hydrocarbons, such as toluene, benzene, and xylenes, and
aliphatic
hydrocarbons such as hexane, heptane, and cyclohexane. Preferred halogenated
hydrocarbons
30 include methylene chloride and carbon tetrachloride. The temperature is not
critical but
generally varies between -20°C and the decomposition temperature of the
activator. Typical
contact times vary from a few minutes to several days. Agitation of the
reaction mixture is
preferred. Advantageously, the activator compound is dissolved, using heat to
assist in
dissolution where desired. It may be desirable to carry out the contacting
between the
35 organometal-treated support material and the activator compound at elevated
temperatures.
Preferably, such elevated temperatures are from 45°C to 1
ZO°C.
Instead of first treating the support material with the organometal compound,
preferably aluminum component, and subsequently adding the activator compound,
the
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organometal compound, preferably aluminum component, and activator compound
may be
combined in a suitable diluent prior to adding Or combining the reaction
mixture to or with the
support material.
Without wishing to be bound by any theory, it is believed that an organo group
of the organometal compound reacts with the active hydrogen moiety contained
in the
activator anion b.2) to form a reaction product (hereinafter also referred to
as "adduct"). For
example, when the organometal compound is trialkylaluminum AIRS and the active
hydrogen-
containing moiety is represented by G-OH, the reaction product is believed to
comprise G-O-
AIRz whereas further an alkane by-product RH is formed. This adduct G-O-AIRZ
when combined
with the support material containing hydroxyl groups, Si-OH in case of a
silica support material,
is believed to form Si-O-AI(R)-O-G together with alkane RH as by-product. This
method of
preparing the supported catalyst component has been found to run very smoothly
and to
provide catalysts and catalyst precursors or components having desirable
properties. Typical
ratios to be used in this reaction are from about 1:1 to about 20:1 moles of
organometal
~ 5 compound to mole equivalents of active hydrogen moieties contained in the
activator anion
b. Z).
The amount of adduct, formed by combining the organometal compound with
the activator compound, to be combined with the support material is not
critical. Preferably,
the amount is not higher than can be fixed to the support material. Typically,
this is
determined by the amount of support material hydroxyls. The amount of adduct
to be
employed is preferably not more than the equivalent amount of such hydroxyl
groups. Less
than the equivalent amount is preferably used, more preferably the ratio
between moles of
adduct to moles of surface reactive groups such as hydroxyls is between 0.01
and 1, even more
preferably between 0.02 and 0.8. Prior to adding the transition metal compound
it is
preferred, especially when less than an equivalent amount of adduct is added
with respect to
surface reactive groups, to add an additional amount of organometal compound
to the
reaction product of support material and the adduct to remove any remaining
surface reactive
groups which otherwise may react with the transition metal and thus require
higher amounts
thereof to achieve equal catalytic activity. Prior to combining it with the
transition metal
compound, the supported catalyst component can be washed, if desired, to
remove any excess
of adduct or organometal compound.
The supported catalyst component comprising the support material, organometal
compound, and the activator may be isolated to obtain a free flowing powder by
removing the
liquid medium using preferablyfiltration or evaporation techniques.
Although the transition metal compound may be combined with the activator
compound, or the adduct of the organometal compound and the activator
compound, prior to
combining the activator compound or its adduct with the support material, this
results in
reduced catalyst efficiencies. Preferably, the transition metal is first
combined with the support
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WO 96/28480 PCT/US96/02891
material treated with the organometal component and before adding the
activator _
compound, or the transition metal is added after the treated support material
and activator
have been combined, or after the activator adduct and the support material
have been
combined. Most preferably, the transition metal compound (c) is added to the
reaction
product of the support material treated with the organometal compound and
activator
compound, or after the activator adduct and the support material have been
combined.
The transition metal compound is preferably used dissolved in a suitable
solvent,
such as a hydrocarbon solvent, advantageously a CS-~o aliphatic or
cycloaliphatic hydrocarbon
or a C6_~ p aromatic hydrocarbon. The contact temperature is not critical
provided it is below
the decomposition temperature of the transition metal and of the activator.
Good results are
obtained in a temperature range of 0°C to 100°C. All steps in
the present process should be
conducted in the absence of oxygen and moisture.
Upon combining the transition metal compound with the supported catalyst
component, the supernatant liquid typically is colorless indicating that the
transition metal
compound, which solution typically is colored, substantially remains with the
solid supported
catalyst.
The supported catalyst obtained by combining the support material, the
organometal compound, the activator, and the transition metal may be stored or
shipped in
free flowing form under inert conditions after removal of the solvent.
The supported catalysts of the present invention may be used in an addition
polymerization process wherein one or more addition polymerizable monomers are
contacted
with the supported catalyst of the invention under addition polymerization
conditions.
Suitable addition polymerizable monomers include ethylenically unsaturated
monomers, acetyl epic compounds, conjugated or non-conjugated dienes,
polyenes, and
carbon monoxide. Preferred monomers include olefins, for examples alpha-
olefins having
from 2 to about Z0, preferably from about 2 to about 12, more preferably from
about 2 to
about 8 carbon atoms and combinations of two or more of such alpha-olefins.
Particularly
suitable alpha-olefins include, for example, ethylene, propylene, 1-butene, 1-
pentene,
4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-
undecene,
1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, or combinations
thereof. Preferably,
the alpha-olefins are ethylene, propene, 1-butene, 4-methyl-pentene-1, 1-
pentene, 1-hexene,
1-octene, and combinations of ethylene and/or propene with one or more of such
other alpha-
olefins. Suitable dienes include those having from 4 to 30 carbon atoms,
especially those
having 5 to 18 carbon atoms. Typical of these are a,w-dienes, a-internal
dienes, including
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CA 02214885 1997-09-09
WO 96!28480 PCTIUS96102892
those dienes which are typically used for preparing EPDM type elastomers.
Typical examples
include 1,3-butadiene, 1,3-and 1,4-pentadiene, 1,3-, 1,4-, and 1,5-hexadiene,
1,7-octadiene,
1,9-decadiene, and lower alkyl substituted analogues of any of these. Other
preferred
monomers include styrene, halo- or alkyl substituted styrenes,
tetrafluoroethylene,
vinylcyclobutene, dicyclopentadiene, and ethylidene norbornenes. Suitable
addition
polymerizable monomers include also any mixtures of the above-mentioned
monomers.
r The supported catalyst can be formed in situ in the polymerization mixture
by
introducing into said mixture both a supported catalyst component of the
present invention, or
its components, as well as a suitable transition metal compound (c).
The supported catalyst can be used as such or after being subjected to
prepolymerization. The prepolymerization can be carried out by any known
methods such as
by bringing a small amount of monomers, preferably alpha-olefins, into contact
with the
supported catalyst.
The catalyst may be used in the polymerization reaction in a concentration of
10-9
to 10-3 moles, based on transition metal, per liter diluent or reaction
volume, but is preferably
used in a concentration of less than 10-S, preferably from 10-$ to 9x10-6
moles per liter diluent
or reaction volume.
The supported catalyst can be advantageously employed in a high pressure,
solution, slurry or gas phase polymerization process. A high pressure process
is usually carried
out at temperatures from 100°C to 400°C and at pressures above
S00 bar. A slurry process
typically uses an inert hydrocarbon diluent and temperatures of from about
0°C up to a
temperature just below the temperature at which the resulting polymer becomes
substantially
soluble in the inert polymerization medium. Preferred temperatures are from
about 30°C,
preferably from about 60°C to about 115°C, preferably to about
100°C. The solution process is
carried out at temperatures from the temperature at which the resulting
polymer is soluble in
an inert solvent up to about 275°C. Generally, solubility of the
polymer depends on its density.
For ethylene copolymers having densities of 0.86 g/cm3, solution
polymerization may be
achieved at temperatures as low as about 60°C. Preferably, solution
polymerization
temperatures range from about 75°C , more preferably from about
80°C, and typically from
about 130°C to about 260°C, more preferably to about
170°C. Most preferably, temperatures in
a solution process are between about 80°C and 150°C. As inert
solvents typically hydrocarbons
and preferably aliphatic hydrocarbons are used. The solution and slurry
processes are usually
carried out at pressures between about 1 to 100 bar. Typical operating
conditions for gas phase
polymerizations are from 20°C to 100°C, more preferably from
40°C to 80°C. In gas phase
processes the pressure is typically from subatmospheric to 100 bar.
Preferably for use in gas phase polymerization processes, the support has a
median particle diameter from about 20 to about 200 Nm, more preferably from
about 30 Nm
to about 150 Nm, and most preferably from about 50 Nm to about 100 Nm.
Preferably for use in
_27_
CA 02214885 2005-08-26
64693-5214
slurry polymerization processes, the support has a median particle diameter
from about 1 Nm
to about 200 Nm, more preferably from about 5 Nm to about 100 Nm, and most
preferably from
about 20 Nm to about 80 Nm. Preferably for use in solution or high pressure
polymerization
processes, the support has a median particle diameter from about 1 Nm to about
40 pm, more
preferably from about 2 Nm to about 30 Nm, and most preferably from about 3 Nm
to about ZO
pm.
Further details for polymerization conditions in a gas phase polymerization
process can be found in U.S. Patents 4,588,790, 4,543,399, 5,352,749,
5,405,922; WO-94/03509
and WO-95/07942. Gas phase processes wherein condensed monomer or inert
dituent is present
are preferred.
The supported catalysts of the present invention, also when used in a slurry
process or gas phase process, not only are able to produce ethylene copolymers
of densities
typical for high density polyethylene, in the range of 0.970 to 0.940 glcm3,
but surprisingly, also
enable the production of copolymers having substantially lower densities.
Copolymers of
densities lower than 0.940 g/cm3 and especially lower than 0.930 glcm3 down to
0.880 gicm= or
lower can be made while retaining good bulk density properties and while
preventing or
substantially eliminating reactor fouling. The present invention is capable of
producing olefin
Polymers and copolymers having weight average molecular weights of more than
30,000,
preferably more than 50,000, most preferably more than 100,000 up to 1,000,000
and even
higher. Typical molecular weight distributions MW/M" range from 1.5 to 15, or
even higher,
preferably between 2.0 and 8Ø
In the polymerization process of the present invention impurity scavengers may
be used which serve to protect the supported catalyst from catalyst poisons
such as water,
oxygen, and polar compounds. These scavengers can generally be used in amounts
depending
on the amounts of impurities. Typical scavengers include organometal
compounds, and
preferably triaikylaluminum or boron compounds and alumoxanes.
In the present polymerization process also molecular weight control agents can
be used, such as hydrogen or other chain transfer agents. The polymers that
are prepared
according to such polymerization process may be combined with any conventional
additives,
such as UV stabilizers, antioxidants, anti-slip or anti-blocking agents, which
may be added in
conventional ways, for example, downstream of the polymerization reactor, or
in an extrusion
or molding step.
Upon or after removal of the polymerization mixture or product of from the
polymerization reactor, the supported catalyst may be deactivated by exposure
to air or water,
or through any other catalyst deactivating agent or procedure.
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In the complex compounds of the present invention, preferably the compatible
anion portion b.2) corresponds to general Formula (I):
[M~m+Qn(Gq(T-Pr)r)z]d_ (I)
wherein:
M', Q, G, T, m, n, q, r, z, and d have the same definitions as in formula 1,
and
Pr is hydrogen H or a protecting group. Preferred protecting groups and charge
balancing cations are illustrated hereinafter.
The complex compounds containing anions b.2) can be prepared by combining a
neutral compound, such as M'"'+Qm, wherein M', Q, and m have the same meaning
as in
Formula (I), with an active metal derivative of the substituent comprising an
active hydrogen
moiety, such as a lithium or Grignard derivative thereof, for example Z(Gq(T
H)~), wherein Z is
Li+, MgCI+, MgBr+, or Mgl+, and G, T, H, q, and r have the same meanings as in
Formula (I).
The group T-H can be protected during the preparation by methods which are
well known by
those skilled in the art. For example, a hydroxy moiety may be protected by a
trimethylsilyl
group. The method for preparing the complex compounds thus comprises combining
in a
suitable solvent or diluent a compound M~"'+Qm with a compound of the formula
Z'(Gq(T Pr)~),
wherein Z' is [M'X"]+ or [M"]+ and M' is a Group 2 element, M" is a Group 1
element and X is
halogen, G, T, Pr, q, and r have the same meaning as given for Formula (I),
optionally followed
by recovering the product complex.
Suitable examples of protecting groups Pr include: trialkylsilyl,
triarylsilyl, and
mixtures thereof, preferably trimethylsilyl, t-butyldimethylsilyl, tri-
isopropyl silyl, t-
butyldiphenyl silyl, and phenyldimethylsilyl; preferably the protective group
contains a bulky
substituent, such as t-butyl or phenyl, to stabilize the resulting protected
group during the
subsequent metalation reaction.
Z5 The reaction between the compound M''"+Qm and Z~(Gq(T-Pr)~) is typically
carried
out in an ether or any other organic diluent that does not negatively impact
the desired
reaction, and mixtures thereof. Preferred ethers are tetrahydrofuran and
diethylether. The
temperature is not critical and is typically in the range of -20°C to
100°C. The reaction mixture is
preferably stirred and reacted for a period of between 5 minutes and 72 hours.
It has been found advantageous to use a molar excess of the compound Z'(Gq(T-
Pr)~) with respect to the compound M~'"+Qm. Such excess is preferably 1.1 to 3
mole equivalents,
more preferably 1.5 to 2.5 mole equivalents of Z'(Gq(T-Pr)~) per mole of
M~"'+Qm. Preferably, the
reaction mixture is heated to a temperature between 40°C and
100°C, more preferably
between 50°C and 95°C. Using such process conditions were found
to increase the conversion
based on the compound M~"'+Qm up to 90% and higher. As the compound M''"+Qm is
usually
the more expensive reactant, it is highly desirable to increase the yield of
the reaction with
respect to this compound.
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The product complex is then preferably recovered, for example by decantation,
filtration, advantageously followed by washing, preferably with a hydrocarbon,
and drying.
The protective group Pr when present in the product complex is preferably
removed by conventional methods, such as reacting the product complex with
water, alcohol,
organic acids like acetic acid, organic anhydride compounds such as acetic
anhydride
containing iron trichloride, and tetra-hydrocarbyl ammonium fluorides, such as
Bu4NF. It has
been found advantageous to use the hydrogen fluoride adduct of a tertiary
amine. This adduct
is capable of removing protecting groups, also those containing bulky ligands,
such as t-butyl
or phenyl, and thereby give a by-product ammonium cation which is a cation
that can react
with the transition metal compound to give a catalytically active complex.
Using this adduct is
preferred over using a compound such as Bu4NF, because the Bu4N cation which
remains as by-
product may render the activator anion less effective. Most preferably the HF
adduct of such a
tertiary amine is used which corresponds to the desired ammonium ion of the
activator
compound. For example, triethylamine would give a triethylammonium cation.
Typically, the
adduct comprises from 1 to 3 mole of HF per mole of amine, preferably 2.
The product complex is preferably subjected to a cation exchange reaction with
a
further complex compound comprising a cation capable of reacting with a
transition metal
compound to form a catalytically active transition metal complex, and a charge
balancing
anion, wherein the cation and anion are contained in such relative quantities
to provide a
neutral complex compound. The cation capable of reacting with a transition
metal compound
to form a catalytically active transition metal complex is preferably selected
from the group of
Bronsted acidic cations, carbonium cations, silylium cations, and cationic
oxidizing agents. The
charge balancing anion preferably is a halide, sulphate, nitrate, or
phosphate.
The complex compounds used in the cation exchange reaction are known
compounds or can be prepared according to conventional processes. The cation
exchange may
be carried out in a suspension or solution or over a cation exchange column.
The cation
exchange reaction and the removal of the optional protective groups Pr may be
carried out
simultaneously.
The product of the cation exchange reaction is recovered, for example by
decantation or filtration, and washed with preferably a hydrocarbon.
Subsequently, the
product complex may be dried using conventional methods, such as applying
reduced pressure,
heat, employing solvent absorbents, or a combination of these.
All reactions are preferably carried out under an inert atmosphere in the
absence
of oxygen and moisture.
. The compounds M~'"+Qm are known compounds, or can be prepared according to
conventional methods. The compounds of formula Z'(Gq(T-Pr)~) are typically
prepared by
reacting X"(Gq(T-Pr)~ or H(Gq(T-Pr)~), wherein X" has the same definition as
given
hereinbefore, H is hydrogen and T-Pr is T-H or a protected T-H group, with M"
or M',
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respectively, wherein M" and M' are a Group 2 element and Group 1 element,
respectively. _
The starting compounds X"(Gq(T-Pr)~) and H(Gq(T-Pr)~) can be prepared
according to
conventional organic synthesis methods.
Having described the invention the following examples are provided as further
illustration thereof and are not to be construed as limiting. Unless stated to
the contrary all
parts and percentages are expressed on a weight basis.
EXAMPLES
The bulk density of the polymers produced in the present examples was
determined according to ASTM 1895. The aluminum content on the support
material was
determined by treatment with sulfuric acid, followed by EDTA addition and back-
titration with
zinc chloride, as described above.
Example 1 - Preparation of activator
A. To a solution of 4-BrMg(C6H4)OSiMe3 (ca. 20 mmol, prepared accordinct to
the
procedure described in J. Org. Chem., 25, 1063, (1960), but using 1,2-
dibromoethane instead of
methyl iodide to initiate the reaction) in tetrahydrofuran (20 mL) was added
slowly, with
vigorous stirring, a solution of tris(pentafluorophenyl)borane (4.3 grams, 8.4
mmol) in hexane
(200 mL). A viscous solid separated, and the mixture was stirred for 16 hours.
The top layer was
then decanted from the solid and the residue washed with two 200 mL portions
of hexane. The
residue was dried under vacuum for 16 hours to yield a pale yellow
microcrystalline solid. The
ZO solid was quenched with a solution of triethylammonium chloride in
distilled water (85 mmol
in 200 mL) and the mixture stirred for 1 hour. The solution was decanted from
the solid and the
residue treated with a second portion of triethylammonium chloride in
distilled water (85
mmol iri 200 mL). After stirring 1 hour the solution was decanted and the
solid washed with
two z00 mL portions of distilled water. The residue was dissolved in a mixture
of methanol (80
mL) and water (4 mL) and stirred for 16 hours. The solvents were then removed
under reduced
pressure and the solid dried under vacuum for 16 hours to yield 3.6 grams (60%
yield based on
tris(pentafluorophenyl)borane) of a very pale yellow microcrystalline solid.
The solid as
analyzed by ~3C and ~9F NMR spectroscopy was found to be triethylammonium
tris(pentafluorophenyl)(4-hydroxyphenyl)borate [NEt3HJ[(HOCsH4)B(C6F5)3]. The
NMR data
indicated the compound to be 95% pure. ~9F NMR (tetrahydrofuran, ppm): -127.1
(doublet, zF,
ortho); -163.8 (triplet, 1F, para); -165.9 (triplet, 2F, meta). ~3C NMR
(tetrahydrofuran d-8, ppm):
150.5, J = 235 Hz; 138.7, J = 230 Hz; 140.0, J = z45 Hz; 130, broad; 155.8;
135.8; 115.0; 49.0;
11Ø
B. To a solution of 28.7 g (0.16 mol) p-bromophenol and 25.0 g (0.17 mol) t-
butyldimethylsilyl chloride in THF was added 35 mL (0.25 mol) triethylamine. A
white
precipitate was formed and the mixture was refluxed. After 4 hours a sample
was analyzed by
GCMS (Gas Chromatography Mass Spectroscopy) and this indicated that the
reaction was
complete. The precipitate was removed by filtration and washed with THF. The
THF was
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evaporated from the filtrate and the resulting orange-brown oil distilled
under vacuum to yield
44.1 g (93%) of a colorless liquid having a boiling point of 75°C to
76°C at 0.15 mm Hg. GCMS
showed the product 4-bromophenoxy-t-butyldimethylsilane to be over 99% pure.
A solution containing 92 mmol t-BuMe2SiOC6H4MgBr was prepared from 26.4
gram (92 mmol) t-BuMe25iOC6H4Br and 2.7 gram (110 mmol) Mg in 100 mL THF. The
Grignard
solution was decanted from the excess Mg. About 37 mmol of B(C6F5)3 was
dissolved in THF
(100 mL) and the resulting solution added to the solution of the Grignard
reagent. The clear
homogeneous solution was warmed for 40 minutes on an 80°C waterbath.
~9F NMR analysis
indicated a quantitative conversion to the desired borate.
The reaction mixture was cooled to room temperature and a solution of 33 gram
(250 mmol) Et3NHCl in water was added. The THF was evaporated until the water
began to
distill. Then, dichloromethane (200 mL) was added and the water phase
separated. The
dichloromethane phase was washed with two 100 mL portions of water and two 100
mL
portions of water containing COZ (solid COZ was added to the two phase system
until the pH
was 7). The dichloromethane solution was dried over sodium sulphate, filtered
and
evaporated, resulting in an oil. Yield 45 gram. A ~H NMR spectrum of this
material showed the
presence of t-BuMeZSiOC6H4B(C6F5)3.Et3NH and t-BuMeZSiOCsHs in about a 1:1
molar ratio.
The oil was stirred with pentane (100 mL) for 15 minutes. The pentane was
decanted and the
procedure repeated with another three 100 mL portions of pentane. The
resulting oil was
dried in vacuo (0.1 mbar) to yield a beige foam. The yield was 33 gram
(quantitative). ~ H and
~9F NMR spectra indicated the material to be almost pure t-
BuMe2SiOC6H4B(C6F5)3.Et3NH.
17 gram (20.7 mmol) of this product was dissolved in THF (100 mL). To this
solution, a mixture of Et3N.3HF (5 gram, 31.3 mmol) and Et3N (3.1 gram, 31.3
mmol) was added
(effectively Et3N.2HF). After 14 hours ~H and ~9F NMR of the whole mixture
showed that
deprotection was complete and that no side products were formed. The THF was
evaporated
and to the residue was added 100 mL of 0.5 M NaOH and 200 mL of diethyfether.
The aqueous
phase was separated and the ether washed with three 50 mL portions of 0.5 M
NaOH, two 50
mL portions of water and two 50 mL portions of water containing COz. The ether
was dried
over sodium sulphate, filtered and evaporated. The residue was dissolved in 50
mL of
dichforomethane and again evaporated (repeated three times). The resulting
beige foam was
dried in vacuo (0.1 mbar) overnight which yielded 12.8 g of
HOC6H4B(C6F5)3.Et3NH (about 90%
yield based on B(CsFS)3). 'H and'9F NMR spectra showed the compound to be
pure. 19F NMR
(solvent THF-de) ppm: -126.5 (doublet, 2F, ortho); -163.0 (triplet, 1 F,
para); -165.5 (doublet, 2F,
meta). 'H NMR (solvent THF-de): 1.25 (triplet, 9H); 3.15 (quartet, 6H); 6.35;
7.05 (AB, 4H); 7.05
(broad, 2H).
C. The starting compound 4-bromo-N-methylaminobenzene was synthesized from
N-methyl-aminobenzene according to Organic Syntheses, Vol. 55, p. 20-24
(Springer-Verlag)
(1971).
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The next step in the synthesis method is a modified version of that given in
~. Org.
Chem., 40, 1090, 1975. To a solution of 18.6 g (0.1 mole) 4-bromo-N-
methylaminobenzene in
200 mL THF was added at 0°C a solution of 67 mL of 1.5 molar n-
butyllithium in hexane. A pale
yellow precipitate was formed. After 10 minutes a solution of 15.1 g (0.1
mole) of t-
butyldimethylsilyl chloride in 20 mL THF was added. The temperature of the
reaction mixture
was allowed to rise to room temperature and the mixture was then refluxed for
6 hours. The
solvents were evaporated and distillation of the residue gave 2.0 g (93%) of a
yellow liquid 4-
bromo-N-t-butyldimethylsilyl-N-methylaminobenzene at a distillation
temperature of 100°C to
110°C at 0.3 mm Hg. The purity as determined by GCMS was at least
99.5%.
To 2.4 g (0.1 mole) magnesium turnings was added approximately 10% of a
solution of 28.0 g (93 mmole) of4-bromo-N-t-butyldimethylsilyl-N-
methylaminobenzene in 100
mL THF. 1,2-dibromoethane (100 NI) was added and the reaction was started by
warming up to
reflux temperature. The rest of the aniline solution was added in 40 minutes
and the mixture
was heated at regular times to keep the reaction going. After addition was
complete the
mixture was refluxed during 2 hours. A sample was quenched with water and
analyzed by
GCMS: main peak: M = 221 (N-t-butyl-dimethylsilyl-N-methylaminobenzene).
To the THF solution of Grignard reagent was added at room temperature with
vigorous stirring 780 mL of a solution containing 31.2 mmole
tris(pentafluorophenyl) boron in
heptane. The reaction mixture was stirred for 16 hours at room temperature. A
viscous
material separated. The top layer was decanted and the precipitate was washed
with three
portions of 100 mL hexane. The residue was dried under vacuum (0.1 mm Hg) for
a few hours
to yield a white foam. This product magnesiumbromide(4-N-t-butyldimethylsilyl-
N-
methylaminophenyl)-tris(pentafluorophenyl)borate was used for the next step
without further
purification.
To the reaction product of the previous step was added a solution of 60 g
triethylammonium chloride in 100 mL demineralized water. The mixture was
stirred for 2 hours
and a homogeneous emulsion formed. The reaction mixture was extracted with
four portions
of 50 mL dichloromethane and the combined dichloromethane extracts were washed
three
times with 50 mL demineralized water. The dichloromethane was dried over
magnesium
sulphate. Filtration and evaporation of the solvent gave the product
triethylammonium (4-N-t-
butyldimethylsilyl-N-methylaminophenyl)-tris(pentafluorophenyl)borate.
The product of the previous reaction step was dissolved in a mixture of 150 mL
methanol, 50 mL water and 2 g triethylammonium chloride and was stirred for 16
hours at
room temperature. The methanol was evaporated and 100 mL demineralized water
was added
to the residue. The suspension was extracted with four portions of 30 mL
dichloromethane and
the combined dichloromethane extracts were dried over magnesium sulphate.
After filtration
and evaporation of the solvent 19.6 g (76% ) of a dark brown powder remained.
For further
purification the product was washed three times with toluene. To remove the
last traces of
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toluene the material was mixed two times with 40 mL dichloromethane and the
solvent was
evaporated. In the course of this treatment the material became less soluble
in this solvent. For
the last purification step the product was mixed with 100 mL dichloromethane
and heated.
After cooling, the material was filtered over a Biichner funnel to give after
drying in vacuo 12.8
g (50%) of the pure producttriethylammonium (4-N-methylaminophenyl)tris-
(pentafluorophenyl)borate.
'H-NMR (THF-d$ and acetone-ds): 1.20 (triplet, 9H); 2.70 (singlet, 3H); 3.10
(quartet, 6H); 5.90 (broad, 2H); 6.35; 7.15 (AB, 4H).
'3C-NMR (THF-d8): 148.9 (J=238); 138.3 (J=233); 136.9 (J=263); 129.0 (broad);
146.5; 134.2; 111.8; 47.1; 31.0; 9Ø
'9F-NMR (THF-d8 + benzene-ds): -127.0 (doublet, 2F, ortho); -163.0 (triplet, 1
F,
para); -165.5 (triplet, 2F, meta).
Analogous to the procedure in Example 1A, triethylammonium
tris(pentafluorophenyl) (4-hydroxymethylphenyl) borate was prepared using 4-
MgBr(C6H4)CH205i(t-Bu)Mez prepared by reacting 4-bromobenzylalcohol with t-
BuMezSiCl,
and converting the reaction product with magnesium into the Grignard reagent.
E. HCI salts of the amines trioctylamine, dimethyl-n-octylamine,
dimethylphenylamine, and benzyldimethylamine were quantitatively prepared by
leading
hydrogen chloride gas through a diethylether solution of the amine until the
pH remained
2p acidic (approximately 5 minutes). The solid material was, in each case
isolated by filtration,
washed with diethylether and dried under vacuum.
Triethylammonium tris(pentafluorophenyl)(4-hydroxylphenyl)borate (1.4 gram, 2
mmol) was dissolved in 25 mL of dichloromethane. An ion exchange reaction was
performed .
by shaking this solution six times with a solution of 4 mmol of the respective
HCI salt of the
above amines in 20 mL water. The dichloromethane solution was washed five
times with
portions of 20 mL water and then dried over magnesium sulphate. The mixture
was filtered,
and the filtrate evaporated to dryness under vacuum to afford the appropriate
ammonium salt.
The yield in each case was 90% and multinuclear NMR spectroscopy was in full
agreement with
the proposed structures.
Example 2 - Preparation of Support Material Treated With Aluminum Component
A. A 250 mL flask was charged with 5 g of granular silica SD 3216.30 (having a
specific surface area of about 300 mz/g, a pore volume of about 1.5 cc/g, and
an average
particle size of 45 micrometers) available from Grace GmbH, which had been
heated at 250°C
for 3 hours under vacuum to give a final water content of less than 0.1
percent by weight as
determined by differential scanning calorimetry. 101 g of a 10 weight percent
solution of
methylalumoxane (MAO) in toluene, available from Witco GmbH, was added and the
mixture
stirred for 16 hours at room temperature. After this time the toluene was
removed under
reduced pressure at 20°C, and the solids were dried under vacuum for 16
hours at 20°C to yield a
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free flowing powder. The powder was heated at 175°C for two hours under
vacuum. The
powder was reslurried in toluene (130 mL) and the mixture heated to
90°C and stirred for 1
hour. The m fixture was filtered and the resulting solid washed with two 50 mL
portions of fresh
toluene at 90°C. The support was then dried under vacuum at
120°C for 1 hour. 11.1 g of
support was obtained having an aluminum content of 23.8%.
B. A 250 mL flask was charged with 5 g of granular silica SD 3216.30 available
from
Grace GmbH which had been heated at 250°C for 3 hours under vacuum to
give a final water
content of less than 0.1 percent by weight as determined by differential
scanning calorimetry.
101 g of a 10 weight percent solution of MAO in toluene was added and the
mixture stirred for
16 hours, The solid material was isolated by filtration and then reslurried in
toluene (80 mL)
and the mixture heated to 90°C and stirred for 1 hour. The mixture was
filtered and the
resulting solid washed with two 50 mL portions of fresh toluene at
90°C. The support was then
dried under vacuum at 120°C for 1 hour. 6.7 g of support was obtained
having an aluminum
content of 13.6%.
C~ A 250 mL flask was charged with 5 g of granular silica SD 3216.30 available
from
Grace GmbH, containing 2.8% of water, and 101 g of a 10 weight percent
solution of MAO in
toluene was added and the mixture stirred for 16 hours. The solid material was
isolated by
decantation and then reslurried in toluene (80 mL) and the mixture heated to
90°C and stirred
for 1 hour. The mixture was filtered and the resulting solid washed with two
50 mL portions of
fresh toluene at 90°C. The support was then dried under vacuum at
120°C for 1 hour. 7.3 g of
support was obtained having an aluminum content of 15.4%.
D. A 250 mL flask was charged with 10 g of granular silica SD 3216.30
available from
Grace GmbH which had been heated at 250°C for 3 hours under vacuum to
give a final water
content of less than 0.1 percent by weight as determined by differential
scanning calorimetry.
36 g of a 10 weight percent solution of MAO in toluene was added and the
mixture stirred for
16 hours. The solid material was isolated byfiltration and then reslurried in
toluene (100 mL)
and the mixture heated to 90°C and stirred for 1 hour. The mixture was
filtered and the
resulting solid washed with two 50 mL portions of fresh toluene at
90°C. The support was then
dried under vacuum at 120°C for 1 hour. 13.1 g of support was obtained
having an aluminum
content of 12.3%.
E. A 250 mL flask was charged with 10 g of granular silica SD 3216.30
available from
Grace GmbH which had been heated at 250°C for 3 hours under vacuum to
give a final water
content of less than 0.1 percent by weight as determined by differential
scanning calorimetry.
72 g of a 10 weight percent solution of MAO in toluene was added and the
mixture stirred for
16 hours. The solid material was isolated by filtration and then reslurried in
toluene (100 mL)
and the mixture heated to 90°C and stirred for 1 hour. The mixture was
filtered and the
resulting solid washed with two 50 mL portions of fresh toluene at
90°C. The support was then
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dried under vacuum at 120°C for 1 hour. 13.3 g of support was obtained
having an aluminum
content of 11.4%.
F. A 250 mL flask was charged with toluene (50 mL) and trimethylaluminum (13.5
mL, 0.141 mol). 5 Gram of silica SP-9-10046 (available from Grace Davison)
having a water
content of 4.5% by weight, based on the combined weights of water and support,
was added .
and the mixture stirred 16 hours. The mixture was filtered and the support
washed with
toluene (50 mL, about 100°C) and dried under high vacuum. 5.2 Gram of
support was obtained -
of an aluminum content 7.3°/ by weight.
G. A 250 mL flask was charged with toluene (50 mL) and triethylaluminum (11
mL,
0.08 mol). 6.3 Gram of silica SP-9-10046 having a water content 4.5°/
by weight was added and
the mixture stirred 1 hour. The mixture was filtered and the support washed
with toluene (50
mL, about 100°C) and dried under high vacuum. 6.3 Gram of support was
obtained of an
aluminum content of 5.3°/ by weight.
H. A 250 mL flask was charged with toluene (50 mL) and triethylaluminum (7 mL,
0.051 mol). 5 Gram of silica SP-9-10046 which had been treated at 250°C
for 3 hours under
vacuum was added and the mixture stirred 16 hours. The mixture was filtered
and the support
washed with toluene (50 mL, about 100°C) and dried under high vacuum.
5.1 Gram of support
was obtained of an aluminum content 4.7% by weight.
Preparation of Supported Catalyst
Example 3:
Two gram of the support treated as described in Example 2A was slurried in
toluene (20 mL) and to this was added triethylammonium
tris(pentafluorophenyl)(4-
hydroxyphenyl)borate prepared in Example 1 (0.224 g, 0.32 mmol) in toluene (10
mL). The
mixture was stirred for 16 hours and then filtered and washed with toluene
(3x10 mL) and
dried under vacuum at 20°C. 1 g of the solid was slurried in toluene
(15 ml) and the mixture
stirred for a few minutes. A 0.56 mL aliquot of a dark orange-brown 0.0714 M
solution (40
micromol) of [(tert-butylamido)(dimethyl)(tetramethyl-ns-
cyclopentadienyl)silane]dimethyl
titanium (hereinafter MCpTi) in ISOPAR'" E (trademark of Exxon Chemical
Company) solution
was added and the mixture stirred for a few minutes, filtered, washed with
toluene (2x10 mL)
and dried under vacuum to give a bright yellow colored supported catalyst. The
supported
catalyst was reslurried in 10 mL of hexane for use in a slurry polymerization
reaction.
Example 4
0.5 gram of the support treated as described in Example 2A was slurried in
toluene (10 mL) and stirred for a few minutes. This slurry was added to a
mixture of
triethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate prepared in
Example 1
(0.042 g, 60 micromol) in toluene (10 mL) and the mixture stirred for 16
hours. The solids were -
filtered and washed with 2x10 mL toluene and reslurried in toluene (10 mL). 20
Micromol of
MCpTi in ISOPAR E was added to give a yellow-brown colored solid phase and a
colorless
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WO 96128480 PC7YUS96102891
supernatant. The mixture was stirred for a few minutes before use in a
polymerization
reaction.
Example 5
The procedure of Example 4 was repeated except that 0.028 gram (40 micromol)
of triethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate was
employed. A
supported catalyst consisting of a yellow-brown solid phase and a colorless
supernatant was
- obtained.
Example 6
The procedure of Example 4 was repeated except that 0.014 gram (20 micromol)
of triethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate was
employed. A
supported catalyst consisting of a yellow-brown solid phase and a colorless
supernatant was
obtained.
Example 7
0.25 gram of the support treated as described in Example 2B was slurried in
toluene (5 mL) and stirred for a few minutes. This slurry was added to a
mixture of
triethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate (0.014 g, ZO
micromol) in
toluene (5 mL) and the mixture stirred for 16 hours. The toluene was removed
by filtration and
the solids were washed with 2x10 mL toluene and reslurried in toluene (10 mL).
10 Micromol of
MCpTi in ISOPAR'" E was added and the mixture stirred for a few minutes before
use in a
Zp polymerization reaction. A supported catalyst consisting of a yellow-brown
solid phase and a
colorless supernatant was obtained.
Example 8
The procedure of Example 7 was repeated except that prior to addition of the
transition metal compound the supported catalyst component comprising the
treated silica
z5 and the triethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate was
not washed
with toluene.
Example 9
The procedure of Example 7 was repeated except that prior to the addition of
the
transition metal compound the supported catalyst component comprising the
treated silica
30 and the triethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate was
not washed
with toluene. Also 0.028 g (40 micromol) instead of 0.014 g of
triethylammonium
tris(pentafluorophenyl)(4-hydroxyphenyl)borate was used.
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WO 96/28480 PCT/US96/02891
Example 10
The procedure of Example 9 was repeated except that half of the amount of the
final supported catalyst, containing about 5 micromol of MCpTi, was used in a
polymerization
reaction.
Example 11
The procedure of Example 9 was repeated except that the support treated as in
Example 2C was used.
Example 12
The procedure of Example 9 was repeated except that the support treated as in
Example 2D was used.
Examples 13 and 14
The procedure of Example 9 was repeated except that the support treated as in
Example 2E was used.
Examples 15 and 16
The procedure of Example 9 was repeated except that the support treated as in
Example 2E was used and 0.021 g (30 micromol) of triethylammonium
tris(pentafluorophenyl)(4-hydroxyphenyl)borate was used.
Example 17
0.25 Gram of the support treated as described in Example 2E was slurried in
toluene (5 mL) and stirred for a few minutes. 10 micromol of MCpTi in ISOPAR E
was added and
the mixture stirred for 15 minutes. The mixture was added to 0.028 g (40
micromol) of
triethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate in toluene (10
mL) and the
mixture stirred 16 hours to yield a supported catalyst comprising a yellow-
brown solid phase
and a colorless supernatant.
Example 18
0.014 g (20 micromol) of triethylammonium tris(pentafluorophenyl)(4-
hydroxyphenyl)borate was added to toluene (10 mL) and the mixture stirred for
a few minutes.
20 micromol of MCpTi in ISOPAR E was added and the mixture stirred for 30
minutes. The color
changed from yellow to red. 0.5 Gram of the support treated as described in
Example 2A in
toluene (10 mL) was added and the mixture stirred for 16 hours.
Example 19 - Preparation of Supported Catalysts
1.5 gram of the supported catalyst components prepared in Examples 2F (Example
19A), 2.G (Example 19B), and 2.H (Example 19C) was slurried in toluene (20 mL)
and the mixture
stirred for a few minutes to disperse the support. The slurry was added to a
solution of
triethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate (0.084 g,
0.120 mmol) in
toluene (60 mL) which had been preheated to a temperature of 65°C to
70°C. The mixture was
stirred for 30 minutes at this temperature and then the heating was
discontinued and the
mixture allowed to cool to ambient temperature. Stirring was continued for an
additional 16
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WO 96/28480 PCTlI1S96/02891
hours. A 0.84 mL aliquot of a dark violet 0.0714 M solution (60 micromol) of
titanium, (N-1,1-
dimethylethyl)dimethyl(1-(1,2,3,4,5; eta)-Z,3,4,5-tetramethyl-2,4-
cyclopentadien-1-
yl)silanaminato))(Z-)N)-(n°-1,3-pentadiene) (hereinafter MCpTi(II)) in
ISOPAR'" E (trademark of
Exxon Chemical Company) was added and the mixture stirred for about 1 hour to
yield a green
colored supported catalyst. The catalyst was used as such in a slurry
polymerization.
Example 20 - Preparation of Supported Catalyst
Triethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate (0.0707 g,
0.1 mmol) was dissolved in toluene (100 mL) by heating the mixture at
70°C for 15 minutes. A
solution of triethylaluminum (50 mL of a 0.002 M solution in toluene, 0.1
mmol) was added and
the mixture stirred for 5 minutes. 1 Gram of silica SP-9-10046 which had been
treated at 250°C
for 3 hours under vacuum was slurried in toluene (20 mL) for 15 minutes and
then this slurry
was added to the borate/triethylaluminum adduct solution and the mixture was
stirred for 5
minutes at a temperature of 70°C. Triethylaluminum (0.24 mL, 2 mmol)
was added and the
mixture stirred for an additional 5 minutes at 70°C. The mixture was
filtered and the support
washed once with toluene (100 mL, 70°C) and twice with 100 mL of
boiling hexane. The
support was then dried under reduced pressure. 0.25 Gram of the support was
slurried in
hexane (10 mL) and 0.14 mL of a 0.0714 M solution of MCpTi(II) (10 micromol)
in hexane was
added. The mixture was stirred for 16 hours to yield a supported catalyst
consisting of a green
solid phase and a colorless supernatant. The catalyst was used as such in a
slurry
ZO polymerization.
Example 21 - Preparation of Supported Catalyst
1.5 Gram of a pretreated support prepared as in Example 2H was slurried in
toluene (20 mL) for a few minutes to disperse the support. The slurry was
added to a mixture of
triethylammonium tris(pentafluorophenyl)(4-((N-methyl)amino)phenyl)borate
(0.087 g, 0.120
mmol) in toluene (40 mL) which was preheated to a temperature of 65°C
to 70°C. The mixture
was stirred for 30 minutes at this temperature and then the heating was
removed and the
mixture allowed to cool to ambient temperature. Stirring was continued a
further 16 hours. A
0.84 mL aliquot of a 0.0714 M solution (60 micromol) of MCpTi(II) in hexane
was added and the
mixture stirred for about 16 hours to yield a green/brown colored supported
catalyst. The
catalyst was used as such in a slurry polymerization.
Example 22 - Preparation of Supported Catalyst
30 Gram of SiOz SP-9-10046 treated at 250°C for 2 hours under vacuum
was
slurried in toluene (300 mL) and a solution of triethylaluminum (30 mL, 0.22
mol) in toluene
(200 mL) was added. The mixture was stirred for 1 hour, filtered, washed with
two 100 mL
Portions of fresh toluene and dried under vacuum. To 20 gram of the resulting
powder was
added toluene (200 ml). The mixture was stirred for a few minutes to disperse
the support.
This slurry was added to a solution of triethylammonium
tris(pentafluorophenyl)(4-
hydroxyphenyl)borate (1.125 gram, 1.6 mmol) in toluene (200 mL) which had been
heated to
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WO 96/28480 PC'T/US96/02891
70°C and kept at 70°C for 30 minutes. Upon addition, the heating
was removed and the
mixture stirred at ambient temperature for 16 hour.
A 40 mL aliquot of the resulting slurry (containing approximately 1 gram of
the
support) was withdrawn and to this was added 0.47 mL of a 0.0855 M solution of
bis(indenyl)zirconium dimethyl (Witco GmbH) (40 micromol of Zr). The mixture
was stirred for
a few minutes to yield an orange colored supported catalyst. An aliquot of
this supported
catalyst containing 14 micromol of zirconium was used as such in a slurry
polymerization.
Example 23 - Preparation of Supported catalyst
20 gram of Si02 (SP-9-10046) treated at 250°C for 2 hours under vacuum
was slurried in toluene
(300 mL) and triethylaluminum (ZO mL, 0.147 mol) was added. The mixture was
stirred for 1
hour, filtered, washed with two 100 mL portions of fresh toluene and dried
under vacuum. To
1.5 gram of the resulting powder was added toluene (20 mL). The mixture was
stirred for a few
minutes to disperse the support. This slurry was added to a solution of
triethylammonium
tris(pentafluorophenyl)(4-hydroxymethylphenyl)borate (0.086 gram 0.12 mmol) in
toluene (40
mL), which had been heated to 70°C, and kept at 70°C for 1 hour.
Upon addition, the heating
was removed and the mixture stirred at ambient temperature for 16 hours. 0.84
mL of a 0.0714
M solution of MCpTi(II) (60 micromol Ti) was added and the mixture was stirred
for a 1 hour to
yield a green-brown colored supported catalyst. An aliquot of this supported
catalyst
containing 10 micromol of titanium was used as such in a slurry
polymerization.
Example 24- Slurry Phase Ethylene/1-octene Copolymerization
A catalyst was prepared as in Example 19C. 20 Micromol of catalyst, based on
titanium, was used in a slurry polymerization. 250 mL of 1-octene was added to
the reactor. An
ethylene/1-octene copolymer of density 0.9376 g/cm3 was prepared.
Example 25-26 - Preparation of supported catalyst
30 Gram of Si02 (SP-9-10046) treated at 250°C for 2 hours under vacuum
was
slurried in toluene (300 mL) and triethylaluminum (30 mL, 0.22 mol) was added.
The mixture
was stirred for 1 hour, filtered, washed with two 100 mL portions of fresh
toluene and dried
under vacuum.
To 3 gram of the resulting powder was added toluene (20 mL). The mixture was
stirred for a few minutes to disperse the support. This slurry was added to a
solution of
triethylammonium Iris(pentafluorophenyl)(4-hydroxyphenyl)borate (0.126 g, 0.18
mmol) in
toluene (40 mL) which had been heated to 80°C and kept at 80°C
for 1 hour. Upon addition,
the heating was discontinued and the mixture stirred at ambient temperature
for 16 hours.
1.68 mL of 0.0714 M solution of MCpTi(II) was added and the mixture was
stirred for 1 hour to
Yield a green colored supported catalyst.
Another 3 gram portion of the resulting powder was treated according to the
same procedure, yet using 0.105 gram, 0.15 mmol of borate which had been
heated to 70°C
and kept at 70°C for 1 hour.
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WO 96!28480 PCTlUS96/0289!
Aliquots of the resulting supported catalysts containing 10 micromol of
titanium
were used as such in a slurry polymerization.
Comparative Example 1
0.5 gram of silica SD 3216.30 (dehydrated for 3 hours at 250°C under
vacuum) was
slurried in toluene (10 mL), stirred for a few minutes and then added to
triethylammonium
tris(pentafluorophenyl)(4-hydroxyphenyl)borate (0.028 gram, 40 micromol) in
toluene (10 mL)
and the mixture stirred for 16 hours. 20 micromol of MCpTi in ISOPAR E was
added to give a
pale yellow solid phase and a colorless supernatant.
Comparative Example 2
Triethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate (0.014 gram,
micromol) in 10 mL of toluene was treated with 20 micromol of MCpTi in ISOPAR
E. The
resulting red colored mixture was stirred for a few minutes and then used as
such in a
polymerization reaction.
Example 27 - Polymerization Runs
15 A 10 liter autoclave reactor was charged with 6 liter anhydrous hexane, 1
liter of
hydrogen gas, and the reactor contents heated to 80°C, unless indicated
otherwise, at which
temperature the polymerization mixture was maintained during polymerization.
Ethylene was
then added in order to raise the pressure to the desired operating level of 10
bar, unless
indicated otherwise. A sample of supported catalyst as prepared in the
previous examples and
2p comparative examples was added to the reactor through a pressurized
addition cylinder in the
amounts indicated in the table below. Ethylene was supplied to the reactor
continuously to
keep the pressure constant. After the desired reaction time the ethylene line
was blocked and
the reactor contents were dumped to a sample container. The hexane was removed
from the
polymer and the polymer dried overnight and then weighed to determine catalyst
efficiencies.
In none of the inventive examples did substantial reactor fouling occur and
all examples gave a
polymer in a free flowing powder form.
The table summarizes the specific conditions and the results of slurry
polymerizations with the above prepared supported catalyst.
Example 28 - Continuous Slurry Phase Polymerizations
20 gram of triethylaluminum treated SiOz (prepared as in Example 22) was
slurried in toluene (200 mL) and the mixture heated to 80°C. In a
separate vessel,
triethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate (1.125 gram,
1.6 mmol)
was added to toluene (400 mL) and the mixture heated to 80°C and kept
at 80°C for 1 hour. The
borate solution was added to the support slurry and the mixture stirred and
kept at 80°C for 2
hours. The mixture was cooled and stirred overnight. The toluene was decanted
from the
support and replaced with hexane (800 mL). This procedure was repeated. 8 mmol
of MMAO
type 3A (20 weight percent solution in heptane from AKZO) was added and the
mixture stirred
for 15 minutes. 11.2 mL of a 0.0714 M solution of MCpTi(II) was added and the
mixture stirred
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WO 96/28480 PCT/US96/02891
for 2 hours before use. The support contained a boron loading of 80 micromol/g
and a
titanium loading of 40 micromol/g.
Isopentane, ethylene, 1-butene (if required), hydrogen, and supported catalyst
were continuously fed into a 10 L jacketed, continuously stirred tank reactor
and the slurry
product formed was removed continuously. The total pressure in all
polymerization runs was
bar and the temperature was maintained at 70°C. The slurry withdrawn
was fed to a flash
tank to remove the diluent and the dry, free-flowing polymer powder was
collected. In a first
run the following conditions were used: isopentane flow of 2,500 g/hour;
ethylene flow of
1,200 g/hour; hydrogen flow of 0.4 I/hour; temperature of 70°C to
produce a product having a
10 bulk density of 0.354 g/cm3, and a melt flow index, measured at
190°C and a load of 21.6 kg of
1.4 g/10 minutes, with an efficiency of 1,500,000 g PE/g Ti. In a second run
the following
conditions were used: isopentane flow of 2,500 g/hr; ethylene flow of 800
g/hour; butene flow
of 42.5 g/hr; hydrogen flow of 0.45 I/hour; temperature of 70°C to
produce a product having a
bulk density of 0.300 g/cm3, a density of 0.9278 g/cm3, a butene content of
1.42 mol %, and a
15 melt flow index, measured at 190°C and a load of 2.16 kg of 0.85
g/10 minutes, with an
efficiency of 650,000 g PE/g Ti.
Example 29 - Solution Phase Polymerizations
30 gram of SiOz (SP-9-10046) treated at 250°C for 3 hr under vacuum was
slurried
in toluene (300 mL) and triethylaluminum (30 mL, 0.22 mol) was added. The
mixture was
stirred for 1 hour, filtered, washed with two 100 mL portions of fresh toluene
and dried under
vacuum. To 10 gram of the resulting powder was added toluene (150 mL). The
mixture was
stirred for a few minutes to disperse the support. This slurry was added to a
solution of
triethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate (0.565 gram,
0.8 mmol) in
toluene (250 mL) which had been heated to 70°C and kept at 70°C
for 1 hour. Upon addition,
the heating was removed and the mixture stirred at ambient temperature for 16
hours. A 50
mL aliquot of the slurry was treated with 0.7 mL of a 0.0714 M solution of
MCpTi(II) (50
micromol Ti) followed by 500 micromol of MMAO and the mixture was stirred for
1 hour to
yield a green-brown colored supported catalyst. Aliquots of this supported
catalyst containing
2 and 1.25 micromol of titanium, respectively, were used.
A 3 liter autoclave reactor was charged with the desired amount of 1-octene
followed by an amount of ISOPAR'" E sufficient to give a total volume of 1500
mL. 300 mL of
hydrogen gas was added and the reactor contents were heated to the desired
temperature.
Ethylene was then added sufficient to bring the pressure of the system to 30
bar. A supported
catalyst was added to initiate the polymerization and ethylene was supplied to
the reactor
continuously on demand. After 10 minutes the ethylene line was blocked and the
reactor
contents were dumped into a sample container. The polymer was dried overnight
and then
weighed to determine catalyst efficiencies. The specific conditions were: Run
1: 121 mL
octene; temperature of 130°C; to give 82 g of product (efficiency
854,000 based on g PE/g Ti) of
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CA 02214885 1997-09-09
WO 96128480 PCTlUS96/0289~
a melt index (at 190°C/2.16 kg load).of 3.8 and a density of 0.9137.
Run 2: 450 mL octene;
temperature of 80°C; to give 47 g of product (efficiency 785,000 based
on g PE/g Ti) of a melt
index (190°C/2.16 kg) of 1.66 g/10 minutes and a density of 0.8725
g/cm3.
> 5
15
25
35
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CA 02214885 1997-09-09
WO 96/28480 PCT/US96/02891
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