DESCRIPTION
SOLID POLYALUMINOXANE COMPOSITION, OLEFIN POLYMERIZATION
C~TALYST, OLEFIN POLYMER PRODUCTION METHOD AND SOLID
POLYALUMINOXANE COMPOSITION PRODUCTION METHOD
TECHNICAL FIELD
[0001]
The present invention relates to solid polyaluminoxane
compositions used in the oligomerization reaction or the
10 polymerization reaction of olefins, olefin polymerization
catalysts including the composition, and methods for producing
olefin polymers in the presence of the catalyst.
[0002]
The present invention also relates to solid
15 polyaluminoxane composition production methods and solid
polyaluminoxane compositions obtained.by the production
method.
20
BACKGROUND ART
[0003]
Polyaluminoxane compositions that are partial
hydrolyzates of alkylaluminums are known to serve as
cocatalysts that activate transition metal complexes as the
main catalysts in the production of olefin oligomers or olefin
polymers. In particular, it is widely known that
5
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polymethylaluminoxane compositions prepared from
trimethylaluminum as a raw material exhibit excellent
cocatalytic performance (Patent Literature 1).
[0004)
Polymethylaluminoxane compositions are produced by the
partial hydrolysis reaction of trimethylaluminum (Patent
Literatures 2 and 3) or by the pyrolysis reaction of
alkylaluminum compounds which have an aluminum-oxygen-carbon
bond formed by the reaction of trimethylaluminum with an
10 oxygen-containing organic compound such as a carboxylic acid
15
(Patent Literatures 4 and 5) . Such polymethylaluminoxane
·compositions are marketed in the form of solutions in aromatic
hydrocarbon solvents such as toluene.
[0005)
When an olefin polymer is produced in such a manner that
a solution of the polymethylaluminoxane composition is added
as such to the polymerization system as a cocatalyst in the
olefin polymerization reaction, it is impossible to control
the morphology of the obtainable olefin polymer. Further,
20 stable production is difficult because the process often
experiences fouling problems by the deposition of the olefin
polymer to apparatuses such as the polymerization reactor.
[0006)
To realize the stable production of olefin polymers with
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a good particulate shape, production methods have been
disclosed which involve a supported cocatalyst in which a
polymethylaluminoxane composition is supported on a solid
inorganic carrier such as silica, alumina, silica-alumina or
5 magnesium chloride (Patent Literatures 6 to 9). An advantage
in the use of a solid inorganic carrier is that the carrier
particle diameter may be selected. In the production of olefin
oligomers or olefin polymers, the carrier particle diameter
is selected in accordance with the types of processes, namely,
10 whether the process is liquid-phase polymerization such as
slurry polymerization or involves a gas-phase polymerization
apparatus.
[0007]
However, these supported cocatalysts which have a
15 polymethylaluminoxane composition supported on a solid
inorganic carrier exhibit a markedly lower cocatalytic
activity than when the polymethylaluminoxane composition is
used alone, thus causing economic disadvantages. Further, the
solid inorganic carriers tend to remain as foreign matters in
20 polymers obtained and deteriorate polymer properties.
[0008]
To solve the above problems, approaches have been
proposed in which polyaluminoxane compositions are obtained
as sol ids so that the polyaluminoxane compositions themselves
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can be used as carriers. Some of such production processes that
have been disclosed are a method in which a polyaluminoxane
composition in the form of a solution in an aromatic hydrocarbon
solvent such as toluene is brought into contact with a bad or
5 poor solvent and thereby a solid polyaluminoxane composition
is precipitated (Patent Literatures 10 and 11), a method in
which a solid slurry is obtained by the addition of a salt to
polymethylaluminoxane (Patent Literature 12), a method in
which a polymethylaluminoxane soluble in a bad or poor solvent
10 is prepared and an organic boroxine is reacted with the
polymethylaluminoxane (Patent Literature 13), a method similar
to the method described above in which an oxygen-containing
compound is reacted with a slurry that contains a solid
precipitated by the contact with a bad or poor solvent (Patent
15 Literature 14), and a method in which a polymethylaluminoxane
composition in the form of a special solution having a low
trimethylaluminum content is heated (Patent Literature 15).
[0009]
However, the production methods described in Patent
20 Literatures 10 to 14 are problematic from an economic viewpoint
in that the polyaluminoxane composition as the solid product
is recovered in a low rate relative to the polyaluminoxane
composition used as the raw material. Further, these
production methods do not specifically consider how to control
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the particle diameter of the polyaluminoxane composition or
do not specifically address the uniformity of particle
diameters. Furthermore, Patent Literatures 10 to 15 are
substantially silent on the polymer morphology such as bulk
5 specific gravity of olefin polymer particles obtained by the
combined use of the solid polyaluminoxane composition with a
transition metal compound. In particular, the production
method described in Patent Literature 14 cannot produce a
polyaluminoxane composition with a uniform particle diameter
10 due to the use of a slurry.
[0010]
That is, the aforementioned conventional techniques are
focused primarily on the superiority over the demerits in the
use of solid inorganic carriers and do not substantially reflect
15 the merits in using solid inorganic carriers. For example, the
use of silica carriers suppresses the dissolution of
polyaluminoxane components into solvents by virtue of the
formation of aluminum-oxygen covalent bonds by the reaction
of the hydroxyl groups on the silica surface with the
20 polymethylaluminoxane. As a result, the dissolution or the
so-called leaching of a cocatalyst component, a main catalyst
component or a reaction composition between a main catalyst
component and a cocatalyst component into a reaction solvent
is prevented from occurring during catalyst preparation steps
~/ SF-2750
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and/or polymerization (oligomerization) reaction steps.
Consequently, olefin polymers having a high bulk specific
gravity may be obtained while ensuring excellent operation
stability.
5 [0011]
When a solid polyaluminoxane composition is used as a
cocatalyst carrier in liquid-phase polymerization such as
olefin slurry polymerization or a gas-phase polymerization
process, it is necessary from the viewpoint of fouling
10 prevention that the occurrence of leaching be suppressed to
the minimum. In addition, while polymerization
(oligomerization) reaction steps generally involve the
addition of highly polar substances such as antistatic agents
having a high-polarity functional group such as an ionic
15 functional group or a polyether functional group in the molecule,
leaching should be suppressed to a sufficient extent even in
the presence of such highly polar substances.
[0012]
Patent Literature 11 discloses that a solid
20 polymethylaluminoxane composition described in Examples has
a solubility inn-hexane of 1. 0 mol% or more. Further, Patent
Literature 15 discloses that a solid polymethylaluminoxane
composition described in Examples has a 12 mol% or less molar
fraction of methyl groups derived from trimethylaluminum
Fi(/ SF-2750
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moieties relative to the total number of moles of the methyl
groups and this measurement is feasible by 1H-NMR in
tetrahydrofuran-d8 that is a highly polar compound. Namely,
it is described that the tetrahydrofuran-d8 soluble components
5 in the solid polymethylaluminoxane composition have a high
content of polymethylaluminoxane and a lo1v content of
trimethylaluminum.
[0013]
Patent Literature 15 discloses a method for producing a
10 solid polymethylaluminoxane composition while enhancing the
uniformity of particle diameters. However, there is no
specific description as to ho1v to control the particle diameter
of the solid polymethylaluminoxane composition. According to
the disclosure, it is necessary that a polymethylaluminoxane
15 composition in the form of a special solution be used as a raw
material in order to obtain a solid polymethylaluminoxane
composition with a high recovery rate relative to the amount
of the polymethylaluminoxane composition used as the ra1v
material. However, the raw material has a low
20 trimethylaluminum content and this fact causes a problem in
the storage stability of the raw material itself (Patent
Literature 8). In addition, the production of the special
polymethylaluminoxane composition solution entails the use of
a high concentration of dangerous trimethylaluminum as a raw
~v· ~/ SF-2750
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material. Thus, severe constrains are imposed on production
facilities in order to realize commercial-scale production.
[0014]
Patent Literature 15 uses a polymethylaluminoxane
5 composition solution prepared by the reaction of
trimethylaluminum with an oxygen-containing organic compound.
Because of this configuration, the technique is incapable of
controlling as desired the particle diameter of the solid
polyaluminoxane produced from the polyaluminoxane composition
10 sol uti on. Usually, solid polyal uminoxane compositions used in
liquid-phase polymerization processes such as slurry
polymerization or gas-phase polymerization processes
desirably have a carrier particle diameter that is optimum for
the production process, and this is the case particularly when
15 the compositions are applied to existing facilities for such
polymerization processes. On the other hand, from an economic
viewpoint, it is desired that a solid polyaluminoxane
composition be produced with a high recovery rate relative to
the amount of a polyaluminoxane composition used as a raw
20 material in view of the expensiveness of the polyaluminoxane
composition used as the raw material. However, no method has
been reported which can easily produce a solid polyaluminoxane
composition having a uniform particle diameter from a
commercially available polyaluminoxane composition solution
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as a raw material while allowing the particle diameter to be
varied as desired and also achieving a high recovery rate.
CITATION LIST
PATENT LITERATURE
5 [0015]
Patent Literature 1: US Patent No. 4960878
Patent Literature 2: JP-A-H06-329680
Patent Literature 3: JP-A-2000-509040
Patent Literature 4: JP-A-2005-263749
10 Patent Literature 5: JP-A-2000-505785
Patent Literature 6: JP-A-2002-179721
Patent Literature 7: JP-A-2003-327611
Patent Literature 8: JP-A-2008-069361
Patent Literature 9: JP-A-2009-001829
15 Patent Literature 10: JP-B-H07-42301
Patent Literature 11: JP-A-2000-95810
Patent Literature 12: JP-A-H08-319309
Patent Literature 13: JP-A-H07-70144
Patent Literature 14: JP-A-H07-300486
20 Patent Literature 15: WO 2010/055652
SUMMARY OF INVENTION
TECHNICAL PROBLEM
[0016]
An object of the present invention is to provide a solid
·"·
~/ SF-2750
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po1ya1uminoxane composition suitably used as a cocatalyst and
a catalyst carrier in combination with an olefin
oligomerization or polymerization catalyst, without the use
of solid inorganic carriers such as silica. Another object is
5 to provide a solid polyaluminoxane composition whose particle
diameters are controlled to be relatively uniform and which
can be applied to existing liquid-phase polymerization
processes such as olefin slurry polymerization or gas-phase
polymerization processes. A further object is to provide a
10 solid polyaluminoxane composition Nhich is such that the
leaching of a cocatalyst component, a main catalyst component
or a reaction composition bet\'leen a main catalyst component
and a cocatalyst component is suppressed to the minimum during
olefin polymerization (oligomerization) reaction steps and/or
15 catalyst preparation steps; namely, to provide a solid
polyaluminoxane composition exhibiting a minimized solubility
Nith respect to solvents.
[0017]
A still further object is to provide an olefin
20 polymerization (oligomerization) catalyst including the solid
polyaluminoxane composition and a transition metal compound,
and a method for producing olefin polymers in the presence of
the catalyst.
[0018]
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Another object is to provide a method for producing a solid
polyaluminoxane composition while ensuring a high recovery
rate and a uniform particle diameter. A further object is to
provide such a production method which does not require the
5 use of a special polyaluminoxane composition solution as a raw
material, namely, to provide a method which can produce a solid
polyaluminoxane composition from a commercially available
polyaluminoxane composition solution as a raw material.
SOLUTION TO PROBLEM
10 [0019]
The present inventors have carried out extensive studies
in order to achieve the above objects. As a result, the present
inventors have found that leaching that occurs during steps
for the preparation of olefin polymerization (oligomerization)
15 catalysts may be suppressed by decreasing as much as possible
the solubility of solid polyaluminoxane compositions with
respect to solvents. The present invention has been completed
based on the finding.
20
[0020]
Further, the present inventors have found that the
contact of a specific polyaluminoxane composition solution (A)
with a specific organic compound (B) described later followed
by a reaction between compounds with an aluminum-carbon bond
present in the polyaluminoxane composition solution (A) and
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the organic compound (B) under heating conditions results in
a solid polyaluminoxane composition that is precipitated with
a high recovery rate relative to the polyaluminoxane
composition used as the raw material while ensuring that the
5 composition has a highly uniform particle diameter that is
controlled to any desired particle diameter.
[0021]
A solid polyaluminoxane composition according to the
present invention includes a polyalkylaluminoxane and a
10 trialkylaluminum,
the composition having a solubility inn-hexane at 25°C
of less than 0.50 mol% as measured by a method (i) described
below,
the composition having a solubility in toluene at 25°C
15 of less than 1.0 mol% as measured by a method (ii) described
below,
the molar fraction of alkyl groups derived from the
trialkylaluminum moieties being 13 mol% or more relative to
the total number of moles of alkyl groups derived from the
20 polyalkylaluminoxane moieties and the alkyl groups derived
from the trialkylaluminum moieties as measured with respect
to tetrahydrofuran-d8 soluble components by a method (iii)
described below.
[0022]
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[Method (i)]
2 g of the solid polyaluminoxane composition is added to
50 mL of n-hexane held at 25°C; the mixture is stirred for 2
hours and is filtered to give a filtrate and a residue; and
5 the aluminum concentration in the filtrate is measured by ICP
atomic emission spectroscopy (ICP-AES) to determine the
solubility as the ratio of aluminum atoms present in the
filtrate relative to the amount of aluminum atoms corresponding
to 2 g of the solid polyaluminoxane composition.
10 [0023]
[Method ( ii) ]
The solubility is measured in a similar manner to the
method (i) except that toluene is used in place of n-hexane.
[0024]
15 [Method (iii) J
0.5 mL of tetrahydrofuran (THF)-d8 (a heavy solvent) is
added to 10 mg of the solid polyaluminoxane composition; the
mixture is stirred at 25°C for 2 hours; and the molar fraction
is determined by analyzing the THF soluble components by 1H-NMR
20 at a measurement temperature of 24°C.
[0025]
The solid polyaluminoxane composition of the invention
preferably has a solubility in tetrahydrofuran at 25°C of 95
mol% or less as measured by a method (iv) described below.
"
~/ SF-2750
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[0026]
[Method (iv)]
The solubility is measured in a similar manner to the
method (i) except that tetrahydrofuran is used in place of
5 n-hexane.
[0027]
An olefin polymerization catalyst according to the
present invention is obtained by bringing the solid
polyaluminoxane composition of the invention into contact with
10 a transition metal compound (H) having a transition metal atom
selected from Groups 3 to 10 in the periodic table, the
transition metal compound being represented by General Formula
(8) below:
[0028]
15 ( 8 )
(in the formula, M is a transition metal atom selected
from Groups 3 to 10 in the periodic table, and R31
, R32
, R33 and
R34 may be the same as or different from one another and each
indicate a cyclopentadienyl skeleton-containing group, an
20 alkyl, a cycloalkyl, an aryl, an aralkyl, an alkoxy, an aryloxy,
a halogen atom, an alkylsilyl, an alkylamide, an alkylimide,
-S03R or a hydrogen atom) .
An olefin polymer production method according to the
present invention includes a step of polymerizing one or more
i/ SF-2750
15
olefins selected from a-olefins having 2 to 20 carbon atoms,
cycloolefins having 3 to 20 carbon atoms and diene compounds
having 4 to 20 carbon atoms in the presence of the olefin
polymerization catalyst of the invention.
5 [0029]
A solid polyaluminoxane composition production method
according to the present invention includes:
a step of contacting a polyaluminoxane composition
solution (A) including a polyalkylaluminoxane, a
10 trialkylaluminum and a hydrocarbon solvent, with at least one
organic compound (B) containing a Group 15-17 element in the
periodic table, and
a step of precipitating a solid polyaluminoxane
composition by reacting the compounds with an aluminum-carbon
15 bond present in the polyaluminoxane composition solution (A)
with the organic compound (B) under heating conditions.
[0030]
Preferably, the production method further includes a step
of thermally aging the precipitate after the precipitation
20 step.
ADVANTAGEOUS EFFECTS OF INVENTION
[0031]
According to the present invention, it is possible to
provide solid polyaluminoxane compositions suitably used as
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cocatalysts and catalyst carriers in combination with olefin
oligomerization or polymerization catalysts without the use
of solid inorganic carriers such as silica, the solid
polyaluminoxane compositions exhibiting very low solubility
5 in sol vents. With the solid polyal uminoxane composition of the
invention, the leaching of a cocatalyst component, a main
catalyst component or a reaction composition between a main
catalyst component and a cocatalyst component is suppressed
to the minimum during olefin polymerization (oligomerization)
10 reaction steps and/or catalyst preparation steps. The use of
the solid polyaluminoxane composition of the invention as a
cocatalyst allows polymerization to proceed 1vith very high
activity as compared to when a supported cocatalyst which has
a polymethylaluminoxane composition supported on a silica
15 carrier is used.
[0032]
Further, the solid polyaluminoxane composition of the
invention has relatively uniform particle diameters and is
suitably used for existing liquid-phase polymerization
20 processes such as olefin slurry polymerization or gas-phase
polymerization processes.
[0033]
According to the production method of the invention, a
solid polyaluminoxane composition may be produced with a very
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high recovery rate while ensuring that the composition has a
highly uniform particle diameter that is controlled to any
desired particle diameter. Further, the production method of
the invention may produce a solid polyaluminoxane composition
5 in a favorable manner using a commercially available
polyaluminoxane composition solution as a raw material.
BRIEF DESCRIPTION OF DRAWINGS
[0034]
[Fig. 1] Fig. 1 is an electron micrograph (xlOOO) of a
10 dried solid polyaluminoxane composition obtained in Test
Example Al (Test Example Dl) .
15
20
[Fig. 2] Fig. 2 is an electron micrograph (xlOOO) of a
dried solid polyaluminoxane composition obtained in Test
Example A7 (Test Example Dl4).
[Fig. 3] Fig. 3 is an electron micrograph (x200) of a dried
solid polyaluminoxane composition obtained in Test Example D9.
[Fig. 4] Fig. 4 illustrates a grain size distribution
evaluated with Microtrack MT3300EX II 1vith respect to the dried
solid polyaluminoxane composition obtained in Test Example D9.
[Fig. 5] Fig. 5 is an electron micrograph (x20 0) of a dried
solid polyaluminoxane composition obtained in Test Example
D3l.
[Fig. 6] Fig. 6 illustrates a grain size distribution
evaluated with Microtrack MT3300EX II with respect to the dried
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18
solid polyaluminoxane composition obtained in Test Example
D31.
[Fig. 7] Fig. 7 is an electron micrograph (x2 00) of a dried
solid polyaluminoxane composition obtained in Test Example
S D33.
10
[Fig. 8] Fig. 8 illustrates a grain size distribution
evaluated Nith Microtrack MT3300EX II Nith respect to the dried
solid polyaluminoxane composition obtained in Test Example
D33.
[Fig. 9] Fig. 9 is an electron micrograph (xlOOO) of a
dried solid polyaluminoxane composition obtained in Test
Example al.
[Fig. 10] Fig. 10 is an electron micrograph (xlOOO) of
a dried solid polyaluminoxane composition obtained in Test
lS Example a2.
[Fig. 11] Fig. 11 is an electron micrograph (xlOOO) of
a dried solid polyaluminoxane composition obtained in Test
Example a3.
[Fig. 12] Fig. 12 is an electron micrograph (x200) of a
20 dried solid polyaluminoxane composition obtained in Test
Example aS (Test Example d4).
[Fig. 13] Fig. 13 illustrates a grain size distribution
evaluated Nith Microtrack MT3300EX II Nith respect to the dried
solid polyaluminoxane composition obtained in Test Example aS
5
10
SF-2750
19
(Test Example d4).
[Fig. 14] Fig. 14 is an electron micrograph (xlOOO) of
a dried olefin polymerization catalyst obtained in Test Example
Bl.
[Fig. 15] Fig. 15 is an electron micrograph (xlOOO) of
a dried olefin polymerization catalyst obtained in Test Example
B5.
[Fig. 16] Fig. 16 is an electron micrograph (xlOOO) of
dried particles obtained in Test Example b1.
[Fig. 17] Fig. 17 is an electron micrograph (xlOOO) of
dried particles obtained in Test Example b2.
[Fig. 18] Fig. 18 is an electron micrograph (xlOOO) of
dried particles obtained in Test Example b3.
DESCRIPTION OF EMBODIMENTS
15 [0035]
[Solid polyaluminoxane compositions]
A solid polyaluminoxane composition of the invention
includes a polyalkylaluminoxane and a trialkylaluminum. For
the reason that the composition shows excellent cocatalytic
20 performance when used in combination with an olefin
oligomerization or polymerization catalyst, the composition
preferably includes a polyalkylaluminoxane which contains a
structural unit represented by General Formula (1) below (in
the invention, also written as the ''polyaluminoxane which
SF-2750
20
contains a structural unit represented by General Formula ( 1) ")
and trimethylaluminum, and more preferably includes
polymethylaluminoxane and trimethylaluminum. In the
invention, the solid polyaluminoxane composition including
5 polymethylaluminoxane and trimethylaluminum is also written
as the "solid polymethylaluminoxane composition".
[0036]
[Chern. 1]
• • • ( 1 )
10 In the invention, Me indicates a methyl group.
[0037]
The polyalkylaluminoxane usually includes units
represented by General Formula (1) and/or General Formula (2).
The structure of the polyalkylaluminoxane is not fully
15 identified but is assumed to contain usually about 2 to 50
repeating units represented by General Formula (1) and/or
General Formula (2) below. However, the configuration is not
limited thereto as long as the advantageous effects of the
invention may be obtained. The manner in which the units are
20 connected together is any of various forms such as, for example,
linear forms, cyclic forms and cluster forms. The
polyalkylaluminoxane is assumed to be usually any one of such
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21
structures or a mixture of such structures. The
polyalkylaluminoxane may be composed solely of the units
represented by General Formula (1) or General Formula (2)
[0038]
5 [Chern. 2]
• a • ( 2)
In General Formula (2), R1 is usually a hydrocarbon group
having 2 to 20 carbon atoms, preferably a hydrocarbon group
having 2 to 15 carbon atoms, and more preferably a hydrocarbon
10 group having 2 to 10 carbon atoms. Specific examples of the
hydrocarbon groups include ethyl, propyl, n-butyl, pentyl,
hexyl, octyl, decyl, isopropyl, isobutyl, sec-butyl,
tert-butyl, 2-methylbutyl, 3-methylbutyl, 2-methylpentyl,
3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl,
15 2-ethylhexyl, cyclohexyl, cyclooctyl, phenyl and tolyl.
[0039]
Examples of the trialkylaluminums include
trimethylaluminum having methyl groups, and trialkylaluminums
and triarylaluminums having hydrocarbon groups with 2 to 20
20 carbon atoms.
[0040]
Specific examples of the trialkylaluminums include
r;f/ SF-2750
22
tri(n-alkyl)aluminums such as triethylaluminum,
tri(n-butyl)aluminum, tripropylaluminum, tripentylaluminum,
trihexylaluminum, trioctylaluminum and tridecylaluminum;
tri(branched-alkyl)aluminums such as triisopropylaluminum,
5 triisobutylaluminum, tri(sec-butyl)aluminum,
tri(tert-butyl)aluminum, tri(2-methylbutyl)aluminum,
tri(3-methylbutyl)aluminum, tri(2-methylpentyl)aluminum,
tri(3-methylpentyl)aluminum, tri(4-methylpentyl)aluminum,
tri(2-methylhexyl)aluminum, tri(3-methylhexyl)aluminum and
10 tri (2-ethylhexyl) aluminum; and tricycloalkylaluminums such as
tricyclohexylaluminum and tricyclooctylaluminum.
[0041]
Specific examples of the triarylaluminums include
triphenylaluminum and tritolylaluminum. Trimethylaluminum
15 is preferable.
[0042]
The polyalkylaluminoxane present in the solid
polyaluminoxane composition of the invention appropriately
contains structural units represented by General Formula (1)
20 and/or General Formula (2).
[0043]
That is, the configuration of the polyalkylaluminoxane
is usually such that:
(a) the polyalkylaluminoxane is composed solely of
5
SF-2750
23
structural units represented by General Formula (1);
(b) the polyalkylaluminoxane is composed solely of
structural units represented by General Formula (2) in which
R1s are identical;
(c) the polyalkylaluminoxane is composed of structural
units represented by General Formula (2) in which R1s indicate
two or more kinds of substituents; or
(d) the polyalkylaluminoxane contains both structural
units represented by General Formula (1) and structural units
10 represented by General Formula (2) (in which R1s are identical
or indicate two or more kinds of substituents) .
[0044]
Of these configurations, the polyalkylaluminoxane
preferably contains structural units represented by General
15 Formula ( 1) as is the case in (a) or (d) from the vie1vpoint
of the cocatalytic performance in combination with an olefin
oligomerization or polymerization catalyst. From a further
viewpoint of the availability of the raw material, the
configuration (a), namely, polymethylaluminoxane composed
20 solely of structural units represented by General Formula (1)
is more preferable.
[0045]
The trialkylaluminum present in the solid
polyaluminoxane composition of the invention may have any alkyl
Ei/ j/
SF-2750
24
groups regardless of the type of the polyalkylaluminoxane.
From the viewpoints of cocatalytic activity and raw material
availability, in particular, trimethylaluminum is preferably
used.
5 [0046]
The solid polyaluminoxane composition of the invention
satisfies the following requirements (i) to (iii), and
preferably satisfies the following requirements (i) to (iv).
[0047]
10 Requirement (i): The solubility in n-hexane at 25°C is
less than 0. 50 mol% as measured by a method (i) described below.
[0048]
Requirement (ii): The solubility in toluene at 25°C is
less than 1. 0 mol% as measured by a method ( ii) described below.
15 [0049]
Requirement (iii): The molar fraction of alkyl groups
derived from the trial kylaluminum moieties (hereinafter, also
written as the "molar fraction (1) ") is 13 mol% or more relative
to the total number of moles of alkyl groups derived from the
20 polyalkylaluminoxane moieties and the alkyl groups derived
from the trialkylaluminum moieties as measured with respect
to tetrahydrofuran-d8 soluble components by a method (iii)
described below.
[0050]
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25
[Method (i)]
2 g of the solid polyaluminoxane composition is added to
50 mL of n-hexane held at 25°C. The mixture is stirred for 2
hours and is filtered to give a filtrate and a residue. The
5 aluminum concentration in the filtrate is measured by ICP atomic
emission spectroscopy (ICP-AES) to determine the solubility
as the ratio of aluminum atoms present in the filtrate relative
to the amount of aluminum atoms corresponding to 2 g of the
solid polyaluminoxane composition.
10 [0051]
[Method (ii)]
The solubility is measured in a similar manner to the
method (i) except that toluene is used in place of n-hexane.
Specifically, 2 g of the solid polyaluminoxane composition is
15 added to 50 mL of toluene held at 25°C; the mixture is stirred
for 2 hours and is filtered to give a filtrate and a residue;
and the aluminum concentration in the filtrate is measured by
ICP atomic emission spectroscopy (ICP-AES) to determine the
solubility as the ratio of aluminum atoms present in the
20 filtrate relative to the amount of aluminum atoms corresponding
to 2 g of the solid polyaluminoxane composition.
[0052]
[Method (iii) J
0.5 mL of tetrahydrofuran (THF)-d8 (a heavy solvent) is
SF-2750
26
added to 10 mg of the solid polyaluminoxane composition. The
mixture is stirred at 25°C for 2 hours. The molar fraction is
determined by analyzing the THF soluble components by 1H-NMR
at a measurement temperature of 24°C,
5 [0053]
When the polyalkyla1uminoxane present in the composition
is a polyalkylaluminoxane containing a structural unit
represented by General Formula (1) and the trialky1aluminums
include trimethylaluminum, the molar fraction of alkyl groups
10 derived from the trialkylaluminum moieties including
trimethylaluminum (hereinafter, also written as the ''molar
fraction ( 2) ") is 13 mol% or more relative to the total number
of moles of alkyl groups derived from the polyalky1aluminoxane
moieties and the alkyl groups derived from the trialkylaluminum
15 moieties including trimethylaluminum as measured with respect
to tetrahydrofuran-d8 soluble components by the method (iii).
[0054]
Themolarfractions (1) and (2) ofthealkylgroupsinclude
the number of moles of methyl groups.
20 [0055]
When the polyalkylaluminoxane present in the composition
is polymethyla1uminoxane and the trialkylaluminum is
trimethylaluminum, the molar fraction of methyl groups derived
from the trimethy1aluminum moieties (hereinafter, also written
SF-2750
27
as the ''molar fraction (3)'') is 13 mol% or more relative to
the total number of moles of methyl groups derived from the
polymethylaluminoxane moieties and the methyl groups derived
from the trimethylaluminum moieties as measured with respect
5 to tetrahydrofuran-d8 soluble components by the method (iii).
[0056]
In the invention, it is preferable that the composition
include a polyalkylaluminoxane containing a structural unit
represented by General Formula (1) and trimethylaluminum, or
10 include polymethylaluminoxane and trimethylaluminum.
[0057]
The solid polyaluminoxane composition of the invention
may be used as a catalyst carrier and is particularly suited
for use as a cocatalyst and a catalyst carrier in combination
15 with an olefin oligomerization or polymerization catalyst.
20
However, the use of the composition is not limited thereto and
the composition may be applied to other purposes that will enjoy
the advantageous effects of the invention.
[0058]
Preferably, the composition of the invention exhibits
very low solubility with respect to n-hexane and toluene held
at 25°C. In olefin polymerization (oligomerization) reaction
steps and/or catalyst preparation steps, the leaching of a
cocatalyst component, a main catalyst component or a reaction
-~....-. ··-·-··d. - v···· SF-2750
28
composition bet1~een a main catalyst component and a cocatalyst
component leads to the formation of amorphous olefin polymers
and is a cause of the fouling of apparatuses such as a
polymerization reactor. Thus, the composition advantageously
5 exhibits as 101~ solubility as possible with respect to aliphatic
hydrocarbon solvents represented by n-hexane and aromatic
hydrocarbon solvents represented by toluene that are used in
the olefin polymerization (oligomerization) reaction steps
and/or the catalyst preparation steps.
10 [0059]
From the above viewpoints and in consideration of the
application of the composition to an olefin polymerization
(oligomerization) reaction, the solubility with respect to
n-hexane at 25°C as measured by the method {i) is usually less
15 than 0. 50 mol%, preferably not more than 0. 30 mol%, and more
preferably not more than 0.10 mol%, and the solubility with
respect to toluene at 25°C as measured by the method (ii) is
usually less than 1.0 mol%, preferably not more than 0.50 mol%,
and more preferably not more than 0.30 mol%. As mentioned
20 earlier, the solubility is preferably as low as possible. Thus,
there is no significant point in specifying the lower limit
of the solubility in n-hexane and toluene. Preferably, the
lower limit is 0 mol%. The solubility may be measured in
accordance with a method described in JP-B-H07-42301. The
SF-2750
29
measurement method will be described in detail in Test Examples.
[0060]
The molar fractions ( 1) and ( 2) in the tetrahydrofuran -d8
soluble components of the solid polyaluminoxane composition
5 may be measured by a method similar to the MMAO analysis method
described in TOSOH Research & Technology Review, 2003, Vol.
47, pp. 55-60. Specifically, the molar fractions (1) and (2)
may be determined based on the ratios of the respective areas
assigned to the polyalkylaluminoxane having the structure of
10 General Formula (1), the polyalkylaluminoxane having the
structure of General Formula (2), trimethylaluminum and the
trialkylaluminums (except trimethylaluminum) according to
1H-NMR measurement.
[0061]
15 When the polyalkylaluminoxane in the solid
polyaluminoxane composition is polymethylaluminoxane and the
trialkylaluminum is trimethylaluminum, the molar fraction (3)
may be measured by 1H-NMR in accordance with a method described
in WO 2010/055652, specifically, may be determined based on
20 the ratios of the respective areas assigned to
polymethylaluminoxane and trimethylaluminum. The
measurement method will be described in detail in Test Examples.
[ 0 0 62]
In the composition, the molar fractions (1) and (2)
SF-2750
30
measured by the method (iii) are 13 mol% or more. That is, the
tetrahydrofuran-d8 soluble components preferably have a higher
molar fraction of the trialkylaluminum(s). Similarly, the
composition preferably has a molar fraction (3) measured by
5 the method (iii) of 13 mol% or more, namely, the
tetrahydrofuran-d8 soluble components preferably have a higher
molar fraction of trimethylaluminum.
[ 0 0 63]
It is generally known that a polyaluminoxane composition
10 solution comes to contain gel components which are insoluble
in sol vents when the molar fraction of a trial kylal uminum such
as trimethylaluminum is decreased. Therefore, it may be
considered that a solid polyaluminoxane composition will
similarly exhibit a lower solubility with respect to solvents
15 and consequently the occurrence of leaching will be prevented
to a greater extent with decreasing molar fraction of a
trialkylaluminum. Thus, the invention may seem to be
inconsistent with this reasoning.
20
[0064]
In an olefin polymerization reaction using a single-site
catalyst such as a metallocene catalyst or a postmetallocene
catalyst, it is widely known that the catalytic activity that
is exhibited when a trialkylaluminum is used alone as a
cocatalyst is very low and therefore the cocatalytic
SF-2750
31
performance of a polyaluminoxane composition solution is
essentially dependent on a polyalkylaluminoxane component.
Thus, the essence in the prevention of fouling due to the
leaching of components from a solid polyaluminoxane
5 composition will reside in the suppression of the leaching of
a polyalkylaluminoxane rather than a trialkylaluminum.
[0065]
In general slurry polymerization (oligomerization)
reactions or gas-phase polymerization reactions, antistatic
10 agents are added for the purpose of preventing the occurrence
of fouling due to an electrostatic interaction between
resultant polymer particles. Antistatic agents generally have
a high-polarity functional group such as an ionic functional
group or a polyether functional group in the molecule. To
15 ensure that the occurrence of fouling due to leaching will be
sufficiently prevented, it is necessary that a
polyalkylaluminoxane that is an effective cocatalyst component
be sufficiently restrained from leaching into a reaction
solvent even in the presence of highly polar substances such
20 as antistatic agents.
[0066]
The occurrence of leaching is sometimes facilitated also
by the contact with a single-site catalyst such as a metallocene
catalyst or a postmetallocene catalyst, specifically, by the
----§// ={/ SF-2750
32
intramolecular polarization inherent to the transition metal
complex that is the main catalyst.
[ 0 0 67]
In the solid polyaluminoxane composition of the invention,
5 it is desirable from the above viewpoints that the components
soluble in polar tetrahydrofuran-d8 contain the
polyalkylaluminoxane in a lower proportion, namely, contain
the trialkylaluminum in a higher content; specifically, the
molar fraction ( 1) in the tetrahydrofuran-d8 soluble components
10 is not less than 13 mol%, preferably not less than 14 mol%,
and more preferably not less than 15 mol%. Similarly, it is
desirable that the tetrahydrofuran-d8 soluble components
contain the polyalkylaluminoxane in a lower proportion, namely,
contain the trialkylaluminums including trimethylaluminum in
15 a higher content; specifically, the molar fraction (2) in the
tetrahydrofuran-d8 soluble components is not less than 13 mol%,
preferably not less than 14 mol%, and more preferably not less
than 15 mol%. Similarly, it is desirable that the
tetrahydrofuran-d8 soluble components contain
20 polymethylaluminoxane in a lo1ver proportion, namely, contain
trimethylaluminum in a higher content; specifically, the molar
fraction (3) in the tetrahydrofuran-d8 soluble components is
not less than 13 mol%, preferably not less than 14 mol%, and
more preferably not less than 15 mol%.
SF-2750
33
[ 0 0 68]
If the molar fraction is less than 13 mol%, the leaching
of the polyalkylaluminoxanes such as polymethylaluminoxane
occurs in an increased proportion and consequently the solid
5 polyaluminoxane composition is prone to breakage by the contact
1~i th a transition metal complex as a main catalyst. Further,
such an excessively low fraction leads to phenomena such as
the decrease in bulk specific gravity of olefin polymers
obtained by an olefin polymerization (oligomerization)
10 reaction, and increases the probability of the occurrence of
fouling. While the upper limit of the molar fraction (1) in
the tetrahydrofuran-d8 soluble components is not particularly
limited, the upper limit is, for example, 99 mol% in view of
the fact that a lower proportion of the leaching of the
15 polyaluminoxane is more preferable. The same applies to the
upper limits of the molar fractions (2) and (3) in the
tetrahydrofuran-d8 soluble components.
[0069]
In order to suppress the leaching of the
20 polyalkylaluminoxane into a reaction solvent in the presence
of polar compounds, it is preferable that the composition of
the invention further satisfy the following requirement (iv).
[0070]
Requirement (iv): The solubility in tetrahydrofuran at
SF-2750
34
25°C as measured by a method (iv) described belo1~ is preferably
95 mol% or less, more preferably 90 mol% or less, and still
more preferably 85 mol% or less. The lower limit of the
solubility in tetrahydrofuran is not particularly limited as
5 long as the advantageous effects of the invention may be
obtained. From the viewpoint of leaching, the lower limit may
be, for example, 1 mol%.
10
[0071]
[Method ( i v) ]
The solubility is measured in a similar manner to the
method (i) except that tetrahydrofuran is used in place of
n-hexane. Specifically, 2 g of the solid polyaluminoxane
composition is added to 50 mL of tetrahydrofuran held at 25°C;
the mixture is stirred for 2 hours and is filtered to give a
15 filtrate and a residue; and the aluminum concentration in the
filtrate is measured by ICP atomic emission spectroscopy
(ICP-AES) to determine the solubility as the ratio of aluminum
atoms present in the filtrate relative to the amount of aluminum
atoms corresponding to 2 g of the solid polyaluminoxane
20 composition.
[0072]
The tetrahydrofuran used in the method (iv) is free from
stabilizers (such as dibutylhydroxytoluene (BHT)) and has a
water content of less than 2.0 ppm. The deaeration and
SF-2750
35
dehydration may be performed by a method described in
Organometallics, 1996, Vol. 15, pp. 1518-1520.
[0073]
The solid polyaluminoxane composition of the invention
5 is usually in the form of particles and preferably has a specific
surface area in the range of 400 to 800m2/g. It is known that
the specific surface area of a carrier significantly affects
the catalytic activity in an olefin polymerization reaction.
If the specific surface area is small, a transition metal
10 complex that is a main catalyst may not be activated efficiently
and may exhibit low catalytic activity as a result. On the
other hand, a carrier having an excessively large specific
surface area generally has a small pore diameter and
consequently a transition metal complex that is a main catalyst
15 may not be supported on the carrier uniformly. In view of these
facts, the specific surface area is preferably in the range
of 400 to 800 m2/g, and more preferably in the range of 420 to
700m2/g.
20
[0074]
The specific surface area of the solid polyaluminoxane
composition of the invention may be measured using the BET
adsorption isotherm equation based on the adsorption and
desorption phenomena of a gas on the surface of the solid. The
measurement method will be described in detail in Test Examples.
SF-2750
36
[0075]
The solid polyaluminoxane composition of the invention
preferably has a median diameter D50 in the cumulative volume
in the range of 0.1 to 100 ~m. If the mean particle diameter
5 exceeds 100 ~m, the use of such a composition as an olefin
polymerization (oligomerization) catalyst component results
in the generation of a large amount of coarse polymer particles
and may give rise to the occurrence of troubles such as the
clogging of polymer discharge outlets or polymer transfer lines.
10 If, on the other hand, the mean particle diameter is less than
0.1 ~m, the catalyzed reaction will produce a large amount of
micro polymer particles to facilitate the occurrence of
problems associated with electrostatic attraction and further
the production efficiency may be decreased due to the difficulty
15 to settle or filter such minute particles. In view of these
problems, the median diameter D50 in the cumulative volume is
preferably in the range of 0.1 to 100 ~m, more preferably in
the range of 0.5 to 80 ~m, and still more preferably in the
range of 1.0 to 60 ~m. For example, the median diameter 050
20 in the cumulative volume may be determined by a laser
diffraction scattering method using MT3300EX II manufactured
by Microtrack. The measurement method will be described in
detail in Test Examples.
[0076]
SF-2750
37
As an index of the uniformity of the particle diameters
of solid polyaluminoxane compositions, WO 2010/055652
discloses a definition represented by the following equation
( 1) .
5 [0077]
Uniformity= LXiiD50 - Dii/D50LXi (1)
Here, Xi is the histogram value of a particle i, D50 is
the volume-based median diameter, and Di is the volume-based
diameter of the particle i. A larger value of this index
10 indicates a broader distribution.
[0078]
When the solid polyaluminoxane composition of the
invention is applied to an olefin polymerization
(oligomerization) process, it is preferable from the viewpoint
15 of stable operation that the grain size distribution of the
solid polyaluminoxane composition be narrow. Specifically,
the uniformity represented by the above equation (1) is usually
not more than 0.40, preferably not more than 0.30, more
preferably not more than 0.27, and still more preferably not
20 more than 0. 25. In particular in view of the use as an
alternative to a supported cocatalyst in which a
polyaluminoxane composition is supported on silica, the
above-defined uniformity is desirably equal to or higher than
the uniformity of such a supported catalyst. In view of the
SF-2750
38
fact that the solid polyaluminoxane composition forms
particles by self-association, the lower limit of the
uniformity may be, for example, 0.15.
[0079]
5 The solid polyaluminoxane composition of the invention
may be in the form of a slurry dispersion in a solvent, or may
be in a desolvated state or in a dry state as required.
[0080]
The solid polyaluminoxane composition of the invention
10 contains no solid carriers. Here, the term solid carriers may
refer to, for example, solid inorganic carriers such as silica,
alumina, silica-alumina and magnesium chloride, and solid
organic carriers such as polystyrene beads. The freedom from
solid carriers makes it possible to avoid defects possessed
15 by polyaluminoxane compositions containing solid carriers.
[0081]
[Solid polyaluminoxane composition production methods]
Methods for producing the solid polyaluminoxane
compositions of the invention will be described in detail.
20 However, the production methods are not limited thereto as long
as the advantageous effects of the invention may be obtained.

AMENDED CLAIMS
[Received by t h e I n t e r n a t i o n a l Bureau on A p r i l 23, 2014
(23 .04 . 2 0 1 4 )]
[Claim 1J
A solid polyaluminoxane composition comprising a
polyalkylaluminoxane and a trialkylaluminum,
the composition having a solubility in n-hexane at 25°C
of less than 0.50 mol% as measured by a method (i) described
below,
the composition having a solubility in toluene at 25°C
of less than 1^.0 mol% as measured by a method (ii) described
below,
the molar fraction of alkyl groups derived from the
trialkylaluminum moieties being 13 mol% or more relative to
the total number of moles of alkyl groups derived from the
polyalkylaluminoxane moieties and the alkyl groups derived
from the • trialkylaluminum moieties as measured with respect
to tetrahydrofuran-ds soluble components by a method (iii)
described below:
[Method (i)] ;
2 g of the solid polyaluminoxane composition is added to
50 mL of n-hexane held at 25°C; the mixture is stirred for 2
hours and is filtered to give a filtrate and a residue; and
the aluminum concentration in the filtrate is measured by ICP
atomic emission spectroscopy (ICP-AES) to determine the
solubility as the ratio of aluminum atoms present in the
filtrate relative to the amount of aluminum atoms corresponding
to 2 g of the solid polyaluminoxane composition;
[Method (ii)]
the solubility is measured in a similar manner to the
method (i) except that toluene is used in place of n-hexane;
[Method (iii)]
0.5 mL of tetrahydrofuran (THF)-d8 (a heavy solvent) is
added to 10 mg of the solid polyaluminoxane composition; the
mixture is stirred at 25°C for 2 hours; and the molar fraction
is determined by analyzing the THF soluble components by 1H-NMR
at a measurement temperature of 24°C.
[Claim 2]
The solid polyaluminoxane composition according to claim
1, wherein the composition has a solubility in tetrahydrofuran
at 25°C of 95 mol% or less as measured by a method (iv) described
below:
[Method (iv)]
the solubility is measured in a similar manner to the
method (i) except that tetrahydrofuran is used in place of
n-hexane.
[Claim 3]
The solid polyaluminoxane composition according to claim
1 or 2, wherein the polyalkylaluminoxane contains a structural
unit represented by General Formula (1) below and the
trialkylaluminums include trimethylaluminum
[Chem. 1]
[Claim 4] -
The solid polyaluminoxane composition according to claim
1 or 2, wherein the polyalkylaluminoxane is
polymethylaluminoxane and the trialkylaluminum is
trimethylaluminum, and
the molar fraction of methyl groups derived from the
trimethylaluminum moieties is 13 mol% or more relative to the
total number of moles of methyl groups derived from the
polymethylaluminoxane moieties and the methyl groups derived
from the trimethylaluminum moieties as measured with respect
to tetrahydrofuran-ds soluble components by the method (iii).
[Claim 5]
The solid polyaluminoxane composition according to any
one of claims 1 to 4, wherein the composition has a specific
surface area in the range of 400 to 800 m2/g.
[Claim 6]
The solid polyaluminoxane composition according to any
one of claims 1 to 5, wherein the composition is particles having
a median diameter D50 in the cumulative volume in the range
of 0.1 to 100 Jim.
[Claim 7]
The solid polyaluminoxane composition according to any
one of claims 1 to 6, wherein the uniformity represented by
the following equation is not more than 0,21,
(Equation) Uniformity = £Xi|D50 - Di|/D50ZXi
wherein Xi is the histogram value of a particle i, D50
is the volume-based median diameter, and Di is the volume-based
diameter of the particle i.
[Claim 8]
An olefin polymerization catalyst obtained by bringing
the solid polyaluminoxane composition described in any one of
claims 1 to 7 into contact with a transition metal compound
(H) having a transition metal atom selected from Groups 3 to
10 in the periodic table, the transition metal compound being
represented by General Formula (8) below:
R 3 1 R 3 2 R 3 3 R 3 4 M . . . ( g}
(in the formula, M is a transition metal atom selected
from Groups 3 to 10 in the periodic table, and R31, R32, R33 and
R34 may be the same as or different from one another and each
indicate a cyclopentadienyl skeleton-containing group, an
alkyl, a cycloalkyl, anaryl, an aralkyl, an alkoxy, an aryloxy,
a halogen atom, an alkylsilyl, an alkylamide, an alkylimide,
-SO3R or a hydrogen atom).
[Claim 9]
An olefin polymer production method comprising a step of
polymerizing one or more olefins selected from a-olefins having
2 to'20 carbon atoms, cycloolefins having 3 to 20 carbon atoms
and d.iene.'compounds having 4 to 20 carbon atoms in the presence
of the olefin polymerization catalyst described in claim 8.
[Claim 10]
(Amended) A solid polyaluminoxane composition
production- method comprising:
a step of contacting a polyaluminoxane'composition
solution (A) including a polyalkylaluminoxane, a
trialkylaluminum and a hydrocarbon solvent, with at least one
organic compound (B) containing a Group 15-17 element in the
periodic table;
a step of precipitating a solid polyaluminoxane
composition by reacting the compounds with an aluminum-carbon
bond present in the polyaluminoxane composition solution (A)
with the organic compound (B) under heating conditions at 40 °C
or above; and
a step of thermally aging the precipitate at 90 to 200°C
after the precipitation step.
[Claim '14] \(Amended) The solid polyaluminoxane composition
production" method according to claim 10, wherein the organic
.compound (B) is an oxygen-containing organic compound (C).
[Claim 1$J
The solid polyaluminoxane composition production method
according to claim 14,. wherein the oxygen-containing organic
compound (C) is one or more selected from the group consisting
of aldehyde-containing organic compounds (D),
ketone-containing organic compounds (E), alcohol—containing
organic compounds (F) and carboxylic acid-containing organic
compounds (G).
[Claim U&\-
(Amended) The solid polyaluminoxane composition
production method according to claim 10, 14" or 1-5, wherein the
polyalkylaluminoxane in the polyaluminoxane composition
•solution (A) includes a polyaluminoxane containing a
structural unit represented by General Formula (1) below:
[Chem. 2] •
[Claim 1JT\ • ' '
(Amended) The solid polyaluminoxane.- composition
production method according to claim 10, VA, %5 or 1-6, wherein
the.trialkylaluminums in the polyaluminoxane composition
solution (A) include trimethylaluminum.
[Claim 1&] • = , .
(Amended) The.solid polyaluminoxane composition
.production method according to claim 10, lr4,
wherein the polyalkylaluminoxane m the.polyaluminoxane
composition solution (A) is polymethylaluminoxane and the
trialkylaluminum in the.polyaluminoxane composition solution
(A).is trimethylaluminum.