U.S. patent application number 12/078293 was filed with the patent office on 2008-08-07 for magnesium compound, solid catalyst component for olefin polymerization, catalyst for olefin polymerization and method for producing polyolefin.
This patent application is currently assigned to Idemitsu Kosan Co., Ltd.. Invention is credited to Hideo Funabashi, Masahiko Kuramoto, Takanori Sadashima, Shojiro Tanase.
Application Number | 20080188687 12/078293 |
Document ID | / |
Family ID | 29587775 |
Filed Date | 2008-08-07 |
United States Patent
Application |
20080188687 |
Kind Code |
A1 |
Tanase; Shojiro ; et
al. |
August 7, 2008 |
Magnesium compound, solid catalyst component for olefin
polymerization, catalyst for olefin polymerization and method for
producing polyolefin
Abstract
A magnesium compound obtained by reacting metallic magnesium
having a sphericity (S) of less than 4.00, the sphericity (S) being
represented by the following formula (I), an alcohol, and a halogen
and/or a halogen-containing compound containing halogen atoms in an
amount of 0.0001 gram atom or more relative to one gram atom of the
metallic magnesium, S=(L.sub.1/L.sub.2).sup.3 (I) wherein L.sub.1
represents the maximum diameter of projection views of metallic
magnesium determined by photographing with a scanning electron
microscope and thereafter an image processing, and L.sub.2
represents a diameter of a circle having an area equal to the area
of the projection view of metallic magnesium. A solid catalyst
component is obtained from the magnesium compound and a titanium
compound, and a catalyst for olefin polymerization is obtained
using the solid catalyst component.
Inventors: |
Tanase; Shojiro;
(Ichihara-shi, JP) ; Sadashima; Takanori;
(Ichihara-shi, JP) ; Funabashi; Hideo;
(Ichihara-shi, JP) ; Kuramoto; Masahiko;
(Ichihara-shi, JP) |
Correspondence
Address: |
STEPTOE & JOHNSON LLP
1330 CONNECTICUT AVENUE, N.W.
WASHINGTON
DC
20036
US
|
Assignee: |
Idemitsu Kosan Co., Ltd.
Tokyo
JP
|
Family ID: |
29587775 |
Appl. No.: |
12/078293 |
Filed: |
March 28, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10515766 |
Nov 24, 2004 |
7387979 |
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PCT/JP2003/006195 |
May 19, 2003 |
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12078293 |
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Current U.S.
Class: |
568/300 |
Current CPC
Class: |
C08F 110/06 20130101;
C08F 10/00 20130101; C08F 10/00 20130101; C07C 29/70 20130101; C08F
10/06 20130101; C08F 10/06 20130101; C08F 110/06 20130101; C08F
110/06 20130101; C08F 110/06 20130101; C07C 29/70 20130101; C08F
110/06 20130101; C08F 2500/24 20130101; C08F 4/6565 20130101; C08F
4/6543 20130101; C08F 2500/15 20130101; C08F 4/6548 20130101; C08F
2500/15 20130101; C07C 31/30 20130101; C08F 4/651 20130101 |
Class at
Publication: |
568/300 |
International
Class: |
C07F 3/02 20060101
C07F003/02 |
Foreign Application Data
Date |
Code |
Application Number |
May 24, 2002 |
JP |
2002-150279 |
May 24, 2002 |
JP |
2002-150280 |
May 24, 2002 |
JP |
2002-151091 |
May 24, 2002 |
JP |
2002-1512092 |
Claims
1.-20. (canceled)
21. A method for producing a magnesium compound, comprising
reacting metallic magnesium having an oxidized coating film with a
thickness of 1 .mu.m or less, an alcohol, and a halogen and/or a
halogen-containing compound containing halogen atoms in an amount
of 0.0001 gram atom or more relative to one gram atom of the
metallic magnesium, wherein the metallic magnesium is formed into
particles having an average diameter of 1 cm or less in an
atmosphere of an inert gas.
Description
TECHNICAL FIELD
[0001] The invention relates to a magnesium compound, a solid
catalyst component for olefin polymerization, a catalyst for olefin
polymerization and a method for producing a polyolefin.
TECHNICAL BACKGROUND
[0002] Hitherto, magnesium compounds such as magnesium chloride and
magnesium alkoxides have been widely used as a support material
without being milled in the field of catalysts for olefin
polymerization, specifically the monopolymerization or
copolymerization of olefins such as ethylene and propylene. This
may improve the catalyst activity and the morphology of polyolefin
powder.
[0003] For example, for improving an olefin polymer in the
morphology including a particle size, form, etc., JP-A-S63-280707
discloses a method in which a magnesium compound is supported on an
inorganic oxide such as silica, or JP-A-S58-000811 discloses a
method in which a magnesium compound is once dissolved in a solvent
such as an alcohol and then precipitate again, which precipitate is
used.
[0004] However, these methods include very complicated steps, since
they require the procedures of supporting, dissolving and
precipitating a magnesium compound. Further, these methods have a
defect that the catalyst is poor in stability of performance since
the catalytic activity is high only at an early stage of the
polymerization.
[0005] JP-A-H4-130107 discloses to use as a support of catalysts a
magnesium compound obtained by reacting metallic magnesium, an
alcohol and a certain amount of halogen. However, the sphericity or
particle size distribution of support and polymer powder obtained
may not be satisfactory dependently on the particulate properties
of metallic magnesium or conditions under which a magnesium
compound is produced.
[0006] In view of the foregoing the invention has been made and an
object thereof is to provide a magnesium compound, a solid catalyst
component for olefin polymerization, a catalyst for olefin
polymerization and a method for producing a polyolefin, which can
give a polyolefin with a narrow particle size distribution and/or a
nearly spherical form without reducing stereoregularity and
catalyst properties such as polymerization activity.
[0007] The inventors made efforts to find that the above subject
can be solved by producing a solid catalyst component for olefin
polymerization by reacting a magnesium compound and a titanium
compound, the magnesium compound being obtained from metallic
magnesium with a specified sphericity or particle size distribution
index, or metallic magnesium with an oxidized coating film having a
specified thickness; or obtained by reacting metallic magnesium
with a specified average particle size, a specified amount of an
alcohol and a halogen and/or a halogen-containing compound under
specified stirring conditions. The invention has been completed by
the finding.
DISCLOSURE OF THE INVENTION
[0008] The invention provides the following magnesium compound and
the like.
[1] A magnesium compound obtained by reacting
[0009] metallic magnesium having a sphericity (S) of less than
4.00, the sphericity (S) being represented by the following formula
(I),
[0010] an alcohol, and
[0011] a halogen and/or a halogen-containing compound containing
halogen atoms in an amount of 0.0001 gram atom or more relative to
one gram atom of the metallic magnesium,
S=(L.sub.1/L.sub.2).sup.3 (I)
[0012] wherein L.sub.1 represents the maximum diameter of
projection views of metallic magnesium determined by photographing
with a scanning electron microscope and thereafter an image
processing, and L.sub.2 represents a diameter of a circle having an
area equal to the area of the projection view of metallic
magnesium.
[2] A magnesium compound obtained by reacting
[0013] metallic magnesium having a particle size distribution index
(P) of less than 4.0, the index (P) being represented by the
following formula (II),
[0014] an alcohol, and
[0015] a halogen and/or a halogen-containing compound containing
halogen atoms in an amount of 0.0001 gram atom or more relative to
one gram atom of the metallic magnesium,
P=(D.sub.90/D.sub.10) (II)
[0016] wherein D.sub.90 represents a particle size of the metallic
magnesium corresponding to 90% of cumulative weight percentage, and
D.sub.10 represents a particle size of the metallic magnesium
corresponding to 10% of cumulative weight percentage.
[3] A magnesium compound obtained by reacting with stirring
[0017] metallic magnesium, an average particle size (D.sub.50)
corresponding to 50% of cumulative weight percentage of the
metallic magnesium being from 50 to 2,000 .mu.m,
[0018] an alcohol at a molar ratio relative to one mol of the
metallic magnesium (ROH/Mg) of from 4 to 40, and
[0019] a halogen and/or a halogen-containing compound containing
halogen atoms in an amount of 0.0001 gram atom or more relative to
one gram atom of the metallic magnesium,
[0020] in a stirring vessel with a stirring axis provided with a
stirring blade having a blade diameter d(m) at a speed of rotation
n (number of revolution per minute) under conditions of
n.sup.3d.sup.2 being from 4.3.times.10.sup.3 to
4.0.times.10.sup.6.
[4] A magnesium compound obtained by reacting
[0021] metallic magnesium having an oxidized coating film with a
thickness of 1 .mu.m or less, an alcohol, and
[0022] a halogen and/or a halogen-containing compound containing
halogen atoms in an amount of 0.0001 gram atom or more relative to
one gram atom of the metallic magnesium.
[5] The magnesium compound according to any one of [1] to [4],
wherein the halogen is iodine. [6] The magnesium compound according
to any one of [1] to [5], wherein the halogen-containing compound
is magnesium chloride. [7] The magnesium compound according to any
one of [1] to [6], wherein the temperature of the reaction of the
metallic magnesium, the alcohol and the halogen and/or the
halogen-containing compound is from 30 to 90.degree. C. [8] The
magnesium compound according to [1], which has a sphericity (S') of
less than 1.30, the sphericity (S') being represented by the
following formula (III),
S'=(L.sub.3/L.sub.4).sup.3 (III)
[0023] wherein L.sub.3 represents the maximum diameter of
projection views of the magnesium compound determined by
photographing with a scanning electron microscope and thereafter an
image processing, and L.sub.4 represents a diameter of a circle
having an area equal to the area of the projection view of
magnesium compound.
[9] The magnesium compound according to [2] or [4], which has a
particle size distribution index (P') of less than 3.4, the index
(P') being represented by the following formula (IV),
P'=(D.sub.90/D.sub.10) (IV)
[0024] wherein D.sub.90 represents a particle size of the magnesium
compound corresponding to 90% of cumulative weight percentage, and
D.sub.10 represents a particle size of the magnesium compound
corresponding to 10% of cumulative weight percentage.
[10] The magnesium compound according to [3], which has a particle
size distribution index (P') of less than 3.4, the index (P') being
represented by the formula (IV), and has a sphericity (S') of less
than 1.30, the sphericity (S') being represented by the formula
(III). [11] The magnesium compound according to [4], which is
metallic magnesium formed into particles in an atmosphere of an
inert gas with an average diameter of 1 cm or less. [12] A solid
catalyst component for olefin polymerization, which is obtained by
reacting
[0025] (a) the magnesium compound according to any one of [1] to
[11] and
[0026] (b) a titanium compound.
[13] The solid catalyst component for olefin polymerization
according to [12], which is obtained by reacting further (c) a
halogenated compound and/or (d) an electron donating compound with
the compounds (a) and (b). [14] The solid catalyst component for
olefin polymerization according to [13], wherein the halogenated
compound (c) is silicon tetrachloride. [15] A catalyst for olefin
polymerization comprising the following compounds [A] and [B], or
the following compounds [A], [B] and [C]:
[0027] [A] the solid catalyst component for olefin polymerization
according to any one of [12] to [14];
[0028] [B] an organic aluminum compound;
[0029] [C] an electron donating compound.
[16] A method for producing a polyolefin using the catalyst for
olefin polymerization according to [15]. [17] A method for
producing a magnesium compound, comprising reacting
[0030] metallic magnesium having a sphericity (S) of less than
4.00, the sphericity (S) being represented by the following formula
(I),
[0031] an alcohol, and
[0032] a halogen and/or a halogen-containing compound containing
halogen atoms in an amount of 0.0001 gram atom or more relative to
one gram atom of the metallic magnesium,
S=(L.sub.1/L.sub.2).sup.3 (I)
[0033] wherein L.sub.1 represents the maximum diameter of
projection views of metallic magnesium determined by photographing
with a scanning electron microscope and thereafter an image
processing, and L.sub.2 represents a diameter of a circle having an
area equal to the area of the projection view of metallic
magnesium.
[18] A method for producing a magnesium compound, comprising
reacting
[0034] metallic magnesium having a particle size distribution index
(P) of less than 4.0, the index (P) being represented by the
following formula (II),
[0035] an alcohol, and
[0036] a halogen and/or a halogen-containing compound containing
halogen atoms in an amount of 0.0001 gram atom or more relative to
one gram atom of the metallic magnesium,
P=(D.sub.90/D.sub.10) (II)
[0037] wherein D.sub.90 represents a particle size of the metallic
magnesium corresponding to 90% of cumulative weight percentage, and
D.sub.10 represents a particle size of the metallic magnesium
corresponding to 10% of cumulative weight percentage.
[19] A method for producing a magnesium compound, comprising
reacting with stirring
[0038] metallic magnesium, an average particle size (D.sub.50)
corresponding to 50% of cumulative weight percentage of the
metallic magnesium being from 50 to 2,000 .mu.m,
[0039] an alcohol at a molar ratio relative to one mol of the
metallic magnesium (ROH/Mg) of from 4 to 40, and
[0040] a halogen and/or a halogen-containing compound containing
halogen atoms in an amount of 0.0001 gram atom or more relative to
one gram atom of the metallic magnesium,
[0041] in a stirring vessel with a stirring axis provided with a
stirring blade having a blade diameter d(m) at a speed of rotation
n (number of revolution per minute) under conditions of
n.sup.3d.sup.2 being from 4.3.times.10.sup.3 to
4.0.times.10.sup.6.
[20] A method for producing a magnesium compound, comprising
reacting
[0042] metallic magnesium having an oxidized coating film with a
thickness of 1 .mu.m or less,
[0043] an alcohol, and
[0044] a halogen and/or a halogen-containing compound containing
halogen atoms in an amount of 0.0001 gram atom or more relative to
one gram atom of the metallic magnesium.
BRIEF DESCRIPTION OF DRAWINGS
[0045] FIG. 1 is a schematic drawing showing the catalyst for
olefin polymerization, and a process for producing an olefin
polymer, provided by the invention.
[0046] FIG. 2 is a schematic drawing showing another catalyst for
olefin polymerization, and a process for producing an olefin
polymer, provided by the invention.
[0047] FIG. 3 is a schematic drawing showing still another catalyst
for olefin polymerization, and a process for producing an olefin
polymer, provided by the invention.
[0048] FIG. 4 is a schematic drawing showing yet another catalyst
for olefin polymerization, and a process for producing an olefin
polymer, provided by the invention.
PREFERRED EMBODIMENTS OF THE INVENTION
[0049] Catalyst components and the like used in the invention will
be explained hereinafter. The embodiments shown hereinafter are
preferred embodiments, and the invention is not limited
thereto.
1. Catalyst Components
[A1] Solid Catalyst Component for Olefin Polymerization
[0050] (a1) Magnesium Compound
[0051] In view of the form of polymer particles and polymerization
activity, the invention uses, as a magnesium compound (a1), a
compound that is obtained by reacting metallic magnesium having a
sphericity (S) of less than 4.00, preferably less than 2.50, an
alcohol, and a halogen and/or a halogen-containing compound
containing halogen atoms in an amount of 0.0001 gram atom or more
relative to one gram atom of the metallic magnesium. The sphericity
(S) is represented by the following formula (I),
S=(L.sub.1/L.sub.2).sup.3 (I)
[0052] wherein L.sub.1 represents the maximum diameter of
projection views of metallic magnesium determined by photographing
with a scanning electron microscope and thereafter an image
processing, and L.sub.2 represents a diameter of a circle having an
area equal to the area of the projection view of metallic
magnesium.
[0053] The form of polymer particles are degraded and
polymerization activity also decrease, if the sphericity (S) of
metallic magnesium is 4.00 or more. We think that this is caused by
that the use of metallic magnesium with a low sphericity leads to
the generation of large particles of solid catalyst component with
a lower polymerization activity.
[0054] The sphericity (S) shows the degree of spherical form of a
substance. The substance with sphericity=1 means a complete sphere.
Metallic magnesium particles each are closer to a complete sphere
as S is closer to 1.
[0055] Such metallic magnesium with a sphericity of less than 4.00
can be produced by the combination of cutting with a lathe, a file
or the like and milling with a ball mill or the like, or an
atomization method (melting/spray method).
[0056] The alcohol is preferably selected from lower alcohols
having 1 to 6 carbon atoms. Ethanol is particularly preferred,
since ethanol serves to give a solid product that remarkably
improves the exhibition of catalytic performances of polymerization
activity and the like. While the purity and water content of the
alcohol are not critical, either. When an alcohol having a large
water content is used, however, a coating film of magnesium
hydroxide is formed on the metal magnesium surface, so that it is
preferred to use an alcohol having a water content of 1% or less,
and it is particularly preferred to use an alcohol having a water
content of 2,000 ppm or less. Further, for obtaining an olefin
polymer having better particle properties (individual particle
shape and particle size distribution, hereinafter referred to as
morphology in some cases), a smaller water content is preferred,
and the water content is generally desirably 200 ppm or less.
[0057] The halogen is selected from chlorine, bromine or iodine,
and iodine is particularly suitably used.
[0058] Further, the halogen atom of the halogen-containing compound
is preferably chlorine, bromine or iodine. The halogen-containing
compound is particularly preferably a halogen-containing metal
compound. Specifically, the halogen-containing compound can be
preferably selected from MgCl.sub.2, MgI.sub.2, Mg(OEt)Cl,
Mg(OEt)I, MgBr.sub.2, CaCl.sub.2, NaCl or KBr etc. Of these,
MgCl.sub.2 is particularly preferred. The state, form and particle
size of these compounds are not limited, and a compound being in
any state and having any form and any particle size can be used.
For example, a solution of such a compound in an alcohol solvent
(e.g., ethanol) can be used.
[0059] It appears that Iodine or MgCl.sub.2 is preferred, since the
effect which improves the solubility of the magnesium compound to
ethanol is high.
[0060] The amount of the alcohol per mole of the metal magnesium is
preferably 2 to 100 mol, particularly preferably 5 to 50 mol. When
the amount of the alcohol is too large, the yield of the magnesium
compound (a1) having excellent morphology may decrease. When it is
too small, stirring in a reaction vessel may not smoothly proceed,
while the molar ratio is not limited thereto.
[0061] When the halogen or the halogen-containing compound is used,
the amount of the halogen atoms in the halogen or the
halogen-containing compound per gram atom of the metal magnesium is
0.0001 gram atom or more, preferably 0.0005 gram atom or more, more
preferably 0.001 gram atom or more. When the amount of the halogen
is less than 0.0001 gram atom, and when the magnesium compound (a1)
is used as a support of a solid catalyst component, the catalyst
may be poor in polymerization activity or an olefin polymer may be
defective in morphology, and the like.
[0062] In the invention, the halogens and the halogen-containing
compounds may be used solely each, and two or more halogens or
halogen-containing compounds of these may be used in combination.
Further, the halogen and the halogen-containing compound may be
used in combination. When the halogen and the halogen-containing
compound are used in combination, the amount of total halogen atoms
in the halogen and the halogen-containing compound per gram atom of
the metal magnesium is 0.0001 gram atom or more, preferably 0.0005
gram atom or more, more preferably 0.001 gram atom or more.
[0063] While the upper limit of the amount(s) of the halogen and/or
the halogen-containing compound is not specially limited, the upper
limit may be set as required so long as the magnesium compound (a1)
for use in the invention can be obtained. Generally, the above
upper limit is preferably less than 0.06 gram atom.
[0064] In the process for the production of the magnesium compound
(a1), provided by the invention, the amount of the halogen and/or
the halogen-containing compound is determined as required, whereby
the particle size of the magnesium compound (a1) can be controlled
as required.
[0065] The magnesium compound (a1) is usually prepared by reacting
the metallic magnesium having the above sphericity (S), the alcohol
and the halogen and/or the halogen-containing compound until the
generation of hydrogen gas is no longer observed (generally, for 1
to 30 hours). Specifically, when iodine is used as a halogen, the
magnesium compound (a1) can be prepared by a method in which iodine
in the form of a solid is charged into the metal magnesium and the
alcohol and then the mixture is allowed to react under heat, a
method in which a solution of iodine in an alcohol is added
dropwise to the metal magnesium and the alcohol and the mixture is
allowed to react under heat, or a method in which, while the metal
magnesium and an alcohol solution are heated, a solution of iodine
in an alcohol is added dropwise to allow the mixture to react.
[0066] Each method is preferably carried out in the atmosphere of
an inert gas (e.g., nitrogen gas or argon gas) and optionally in
the presence of an inert organic solvent (e.g., saturated
hydrocarbon such as n-hexane).
[0067] The metallic magnesium, the alcohol and the halogen and/or
the halogen-containing compound are usually allowed to react at the
temperature of 30 to 90.degree. C., preferably at 30 to 60.degree.
C. The performance improves in the range thereof. It appears that
the uniform magnesium compound can be produced since a balance
between the rate of reaction and the solubility is excellent.
[0068] Further, it is not required to charge the entire amount of
each of the metal magnesium, the alcohol and the halogen and/or the
halogen-containing compound at once from the beginning, and they
may be divided and partially charged. For example, the alcohol is
entirely charged in the beginning, the metal magnesium is divided
into several portions and such portions are charged separately. In
this embodiment, the momentary generation of a large amount of
hydrogen gas can be prevented, which is desirable in view of
safety. Further, the size of a reaction vessel can be decreased.
Further, it is also made possible to prevent the dissipation of
alcohol, halogen and the like caused by the momentary generation of
a large amount of hydrogen gas. While the number of the divisional
portions can be determined by taking account of the size of the
reaction vessel and is not specially limited, suitably, each is
generally divided into five to ten portions in view of
complicatedness of procedures.
[0069] Further, the reaction may be carried out by any one of a
batch method and a continuous method. Furthermore, there may be
employed a variant method in which the entire amount of the alcohol
is charged in the beginning, a small amount of the metal magnesium
is added to the alcohol, a product formed by a reaction is removed
by separating it into other vessel, then, a small amount of the
metal magnesium is charged, and these procedures are repeated.
[0070] When the magnesium compound (a1) thus obtained is used for
the preparation of the solid catalyst component [A1], a dry product
may be used, or a product obtained by filtering and then washing
with an inert solvent such as heptane may be used.
[0071] In any case, the magnesium compound (a1) that is obtained in
the invention can be used as a support of the solid catalyst
component, without any pulverization or any sieving procedure for
attaining a uniform particle size distribution. The magnesium
compound (a1) is nearly spherical and has a sharp particle size
distribution. Furthermore, the variation in sphericity of particles
of the magnesium compound (a1) is small.
[0072] The magnesium compound (a1) generally has a sphericity (S')
of less than 1.30, preferably less than 1.28. The sphericity (S')
is represented by the following formula (III),
S'=(L.sub.3/L.sub.4).sup.3 (III)
[0073] wherein L.sub.3 represents the maximum diameter of
projection views of the magnesium compound determined by
photographing with a scanning electron microscope and thereafter an
image processing, and L.sub.4 represents a diameter of a circle
having an area equal to the area of the projection view of
magnesium compound.
[0074] The magnesium compound (a1) with such a sphericity (S') is
preferred in the view of catalyst activity and form of polymer
particles.
[0075] Particles of magnesium compound (a1) each are closer to a
complete sphere as S' is closer to 1, like the sphericity (S) of
metallic magnesium.
[0076] The magnesium compound (a1) generally has a particle size
distribution index (P') of less than 4.0, preferably less than 3.8.
The index (P') is represented by the following formula (IV),
P'=(D.sub.90/D.sub.10) (IV)
[0077] wherein D.sub.90 represents a particle size of the metallic
magnesium (a1) corresponding to 90% of cumulative weight
percentage, and D.sub.10 represents a particle size of the metallic
magnesium (a1) corresponding to 10% of cumulative weight
percentage.
[0078] The use of the magnesium compound (a1) with such a particle
size distribution index (P') enables to enhance polymerization
activity and improve the form of polymer particles.
[0079] The particle size distribution index (P') shows the width of
particle size distribution of magnesium compound (a1). A smaller
value thereof means that the particle size distribution is narrow
or sharp, or that many particles of magnesium compound (a1) with a
uniform diameter are contained.
[0080] The magnesium compound (a1) with such a sphericity (S') of
less than 1.30 and a particle size distribution index (P') of less
than 4.0 can be produced by using metallic magnesium with the
above-mentioned sphericity (S).
[0081] The magnesium compounds (a1) may be used solely, or two or
more thereof may be used in combination.
[0082] Such magnesium compounds (a1) are solid, and substantially
made of magnesium alkoxides practically.
[0083] Specific examples of the magnesium alkoxides include
dialkoxymagnesium compounds such as dimethoxymagnesium,
diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium,
dihexyloxymagnesium, dioctoxymagnesium, diphenoxymagnesium and
dicyclohexyloxymagnesium, diallyloxymagnesium; alkoxyalkylmagnesium
compounds such as ethoxyethylmagnesium, phenoxymethylmagnesium,
ethoxyphenylmagnesium, cyclohexyloxyphenylmagnesium,
allyloxyalkylmagnesium, alkoxyallylmagnesium,
allyloxyallylmagnesium; alkoxymagnesium halides such as
butoxymagnesium chloride, cyclohexyloxymagnesium chloride,
phenoxymagnesium chloride, ethoxymagnesium chloride,
ethoxymagnesium bromide, butoxymagnesium bromide and
ethoxymagnesium iodide, and allyloxymagnesium halides. Of these
alkoxy-group-containing magnesium compounds, dialkoxymagnesium
compounds are preferred, and diethoxymagnesium is particularly
preferred, in view of polymerization activity and
stereoregularity.
[0084] (b1) Titanium Compound
[0085] In view of polymerization activity and the like, the
titanium compound can be preferably selected from compounds
represented by the following general formula (V),
TiX.sub.n(OR).sub.4-n (V)
[0086] wherein X represents a halogen atom, and R is a hydrocarbon
group having 1 to 10 carbon number. One of these may be the same
as, or different from, the other or every other one. N is an
integer of 0 to 4.
[0087] In the above general formula (V), the halogen atom X is
preferably a chlorine or bromine atom, particularly preferably a
chlorine atom. The hydrocarbon group R is preferably an alkyl
group, an alkenyl group, a cycloalkenyl group, an aryl group or an
aralkyl group and the like, and particularly preferably an linear
or branched alkyl group. Further, R may be a saturated or an
unsaturated group. It may be a linear or branched, or it may be
cyclic, and it may contain a hetero element such as sulfur,
nitrogen, oxygen, silicon or phosphorus. Specific examples of R
include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, allyl,
butenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, tolyl,
benzyl and phenethyl and the like. And, n is preferably 4.
[0088] Specific examples of the titanium compounds (b1) of the
above general formula (V) include tetraalkoxytitanium such as
tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium,
tetraisopropoxytitanium, tetra-n-butoxytitanium,
tetraisobutoxytitanium, tetracyclohexyloxytitanium and
tetraphenoxytitanium; titanium tetrahalides such as titanium
tetrachloride, titanium tetrabromide and titanium tetraiodide;
alkoxytitanium trihalides such as methoxytitanium trichloride,
ethoxytitanium trichloride, propoxytitanium trichloride,
n-butoxytitanium trichloride and ethoxytitanium tribromide;
dialkoxytitanium dihalides such as dimethoxytitanium dichloride,
diethoxytitanium dichloride, diisopropoxytitanium dichloride,
di-n-propoxytitanium dichloride and diethoxytitanium dibromide; and
trialkoxytitanium monohalides such as trimethoxytitanium chloride,
triethoxytitanium chloride, triisopropoxytitanium chloride,
tri-n-propoxytitanium chloride and tri-n-butoxytitanium chloride.
Of these, high-halogenated titanium compounds are preferred, and
titanium tetrachloride is particularly preferred, in view of
polymerization activity. These titanium compounds (b1) may be used
solely, or two or more thereof may be used in combination.
[0089] (c1) Halogenated Compound
[0090] If necessary, a halogenated compound (c1) is employed in a
solid catalyst component for olefin polymerization. The halogenated
compound (c1) is preferably used since it may improve the
particulate form of an olefin polymer and make particle size
distribution narrower. Halogenated compounds (c1) include halogens
such as iodine, bromine, chlorine and fluorine; hydrogen halides
such as hydrogen iodide, hydrogen bromide, hydrogen chloride and
hydrogen fluoride; silicon tetrachloride and silicon tetrabromide;
silicon halides such as trichlorosilane, dichlorosilane and
monochlorosilane; carbon halides such as carbon tetrachloride and
hexacholoroethane; halogen-substituted alcohols such as
2,2,2-trichloroethanol; halogen-substituted phenols such as
p-chlorophenol; boron halides such as boron trichloride; aluminum
halides such as aluminum trichloride; and tin halides such as tin
tetrachloride. Of these, silicon tetrachloride is preferred in view
of controlling the particle size of a polymer. These halogenated
compounds (c1) may be used solely, or two or more thereof may be
used in combination.
[0091] (d1) Electron-Donating Compound
[0092] If necessary, an electron-donating compound (d1) is employed
in a solid catalyst component for olefin polymerization. The
electron-donating compound (d1) is preferably used since it may
improve the stereoregularity of an olefin polymer. The
electron-donating compounds (d1) include oxygen-containing
compounds such as alcohols, phenols, ketones, aldehydes, carboxylic
acids, malonic acid, esters of organic acids or inorganic acids and
ethers such as monoether, diether and polyether, and
nitrogen-containing compounds such as ammonia, amine, nitrile and
isocyanate. Of these, esters of polyhydric carboxylic acids are
preferred, and esters of aromatic polyhydric carboxylic acids are
more preferred. Of these, a monoester and/or a diester of aromatic
dicarboxylic acid are/is particularly preferred in view of
polymerization activity. Further, the organic groups of the ester
portions are preferably a linear, branched or cyclic aliphatic
hydrocarbon group.
[0093] Specific examples of the electron-donating compounds include
dialkyl esters such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl,
3-methylbutyl, 1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,
3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl,
n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, 2-methylhexyl,
3-methylhexyl, 4-methylhexyl, 2-ethylhexyl, 3-ethylhexyl,
4-ethylhexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylpentyl or
3-ethylpentyl dicarboxylates such as phthalate,
naphthalene-1,2-dicarboxylate, naphthalene-2,3-dicarboxylate,
5,6,7,8-tetrahydronaphthalene-1,2-dicarboxylate,
5,6,7,8-tetrahydronaphthalene-2,3-dicarboxylate,
indan-4,5-dicarboxylate and indan-5,6-dicarboxylate. Of these,
phthalic acid diesters are preferred, and phthalic acid diesters in
which the organic group of an ester portion is a linear or branched
aliphatic hydrocarbon group having 4 or more carbon atoms are
particularly preferred. Preferable specific examples thereof
include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl
phthalate and diethyl phthalate and the like. These
electron-donating compounds (d1) may be used solely, or two or more
thereof may be used in combination.
[A2] Solid Catalyst Component for Olefin Polymerization
[0094] (a2) Magnesium Compound
[0095] In view of improving the form or morphology of polymer
powder and polymerization activity, the invention uses, as a
magnesium compound (a2), a compound that is obtained by reacting
metallic magnesium having a particle size distribution index (P) of
less than 4.0, preferably less than 3.0, an alcohol, and a halogen
and/or a halogen-containing compound containing halogen atoms in an
amount of 0.0001 gram atom or more relative to one gram atom of the
metallic magnesium. The index (P) is represented by the following
formula (II),
P=(D.sub.90/D.sub.10) (II)
[0096] wherein D.sub.90 represents a particle size of the metallic
magnesium corresponding to 90% of cumulative weight percentage, and
D.sub.10 represents a particle size of the metallic magnesium
corresponding to 10% of cumulative weight percentage.
[0097] The metallic magnesium with an index (P) of 4.0 or more is
not preferred since a solid catalyst component with a high catalyst
activity cannot be obtained from a magnesium compound prepared by
reacting it.
[0098] Such metallic magnesium (a2) with a particle size
distribution index of less than 4.0 can be produced by preparing
particles by cutting, mechanically milling or melting/spray, and
then sieving them with meshes and so on.
[0099] The metallic magnesium is not critical with regard to its
form and the like so far as it has the above particle size
distribution index. Therefore metallic magnesium having any
particle form, for example, metallic magnesium having a granular,
ribbon-shaped or powdery form, may be used.
[0100] The average particle size D.sub.50 corresponding to 50% of
cumulative weight percentage of the metallic magnesium is
preferably 10 to 10,000 .mu.m, more preferably 50 to 2,000 .mu.m.
If the average particle size is smaller, its reaction may proceed
with violence and difficult to be controlled. If the particle size
is too large, its reaction time may be long with a low
producibility. If it is out of the range, the morphology such as
particle size distribution and sphericity of a magnesium compound
obtained may be degraded.
[0101] An alcohol, a halogen and a halogen-containing compound are
the same as those explained in the magnesium compound (a1) and
their explanation is thus omitted.
[0102] In order to produce the magnesium compound (a2), metallic
magnesium with the above particle size distribution index (P),
alcohol, and halogen and/or halogen-containing compound are
generally reacted in the same manner as in the magnesium compound
(a1).
[0103] The magnesium compound (a2) of the invention can be used as
a support for a solid catalyst component without operations such as
milling or classification for a narrow particle size distribution
like the magnesium compound (a1). The magnesium compound (a2) is
nearly spherical and has a sharp particle size distribution. The
particles thereof have a small variability of sphericity.
[0104] The magnesium compound (a2) generally has a particle size
distribution index (P') represented by the above formula (IV) of
less than 3.4, preferably less than 3.2.
[0105] By using a magnesium compound (a2) with such a particle size
distribution index (P'), the polymerization activity is enhanced
and a polymer with more excellent particle morphology can be
obtained.
[0106] The magnesium compound (a2) generally has a sphericity (S')
represented by the above formula (III) of less than 2.00,
preferably less than 1.50.
[0107] The magnesium compound (a2) with such a sphericity (S') is
preferred in view of catalyst activity and morphology of polymer
particles.
[0108] Such a magnesium compound (a2) with a particle size
distribution index (P') of less than 3.4 and a sphericity (S') of
less than 2.00 can be produced by using metallic magnesium with the
above particle size distribution index (P).
[0109] The magnesium compound (a2) may be used solely or two or
more thereof prepared by different methods may be used in
combination.
[0110] Such a magnesium compound (a2) is solid and substantially
made of a magnesium alkoxide. Examples of the magnesium alkoxide
are the same as those of the magnesium compound (a1).
[0111] (b2) Titanium Compound
[0112] The titanium compound (b2) is as explained with regard to
the titanium compound (b1) for use in the solid catalyst component
[A1], so that its explanation is omitted.
[0113] (c2) Halogenated Compound
[0114] The halogenated compound (c2) is as explained with regard to
the titanium compound (c1) for use in the solid catalyst component
[A1], so that its explanation is omitted.
[0115] (d2) Electron-Donating Compound
[0116] The electron-donating compound (d2) is as explained with
regard to the electron-donating compound (d1) for use in the solid
catalyst component [A1], so that its explanation is omitted.
[A3] Solid Catalyst Component for Olefin Polymerization
[0117] (a3) Magnesium Compound
[0118] The invention uses, as a magnesium compound (a3), a compound
that is obtained by reacting with stirring metallic magnesium, an
average particle size (D.sub.50) corresponding to 50% of cumulative
weight percentage of the metallic magnesium being from 50 to 2,000
.mu.m, an alcohol at a molar ratio relative to one mol of the
metallic magnesium (ROH/Mg) of from 4 to 40, and a halogen and/or a
halogen-containing compound containing halogen atoms in an amount
of 0.0001 gram atom or more relative to one gram atom of the
metallic magnesium, in a stirring vessel with a stirring axis
provided with a stirring blade having a blade diameter d(m) at a
speed of rotation n (number of revolution per minute) under
conditions of n.sup.3d.sup.2 being from 4.3.times.10.sup.3 to
4.0.times.10.sup.6.
[0119] If D.sub.50, ROH/Mg and n.sup.3d.sup.2 are out of the above
range, the particle size distribution of polymer powder obtained
may be wider, its sphericity may decrease or it may
agglomerate.
[0120] We presume as to D.sub.50 that the reason therefor is as
follows. Particles of magnesium compound consist of plate-like
crystals. The particle size and form of a magnesium compound depend
on the balance of a reaction speed (promoting agglomeration of
plate-like crystals), collision between particles, collision
between particles and a wall of instrument or a shear from a fluid
(suppressing agglomeration of crystals). From this point of view,
if the reaction occurs at the same time, more uniform particles can
be obtained. In the case of using particles with a smaller
diameter, the reaction speed becomes higher due to the large
specific surface area but the amount of a coating film becomes
larger. This may influence the uniformity of reaction. We presume
as to ROH/Mg that if the Mg concentration is too high, stirring may
disadvantageously become ununiform, and if the Mg concentration is
too low, particles may disadvantageously insufficiently collide
with each other. We presume as to n.sup.3d.sup.2 that if the
mixture is weakly stirred, its flow may become uniform with an
ununiform reaction, and if it is strongly stirred, it may become
difficult for the plate-like crystals of magnesium compound to
agglomerate as larger particles.
[0121] D.sub.50 is preferably 75 to 1,800 .mu.m, ROH/Mg is
preferably 5 to 20, and n3d2 is preferably 1.3.times.10.sup.4 to
8.4.times.10.sup.5.
[0122] Such metallic magnesium with an average particle size
(D.sub.50) of 50 to 2,000 .mu.m can be produced by a mechanically
milling, cutting, melting/spray and so on.
[0123] A blade diameter d and rotary speed n are not limited and
they can be properly adjusted so far as n.sup.3d.sup.2 meets the
above requirement.
[0124] Any blades used for slurry mixing stirring such as a max
blend blade, full-zone blade, paddle (flat) blade, inclined blade,
turbine blade and anchor blade may be used as the stirring blade.
They may be used in ordinary form or multistage form. A plurality
of baffles may be provided on the sidewall of a stirring vessel
along the axial direction.
[0125] Of these blades, a max blend blade with baffles is
preferred.
[0126] The metallic magnesium is not critical with regard to its
form and the like so far as it has the above average particle size
(D.sub.50). Therefore metallic magnesium having any particle form,
for example, metallic magnesium having a granular, ribbon-shaped or
powdery form, may be used.
[0127] An alcohol, a halogen and a halogen-containing compound are
the same as those explained in the magnesium compound (a1) except
for the above-explanation and their explanation is thus
omitted.
[0128] In order to produce the magnesium compound (a3), metallic
magnesium with the above average particle size (D.sub.50), alcohol
with the above molar ratio (ROH/Mg), and halogen and/or
halogen-containing compound with the above gram atomic ratio are
reacted under the above stirring conditions like the magnesium
compound (a1).
[0129] The magnesium compound (a3) of the invention can be used as
a support for a solid catalyst component without operations such as
milling or classification for a narrow particle distribution like
the magnesium compound (a1). The magnesium compound (a3) is nearly
spherical and has a sharp particle size distribution. The particles
thereof have a small variability of sphericity.
[0130] The magnesium compound (a3) generally has a particle size
distribution index (P') represented by the above formula (IV) of
less than 3.4, preferably less than 3.2.
[0131] By using a magnesium compound (a3) with such a particle size
distribution index (P'), the polymerization activity is enhanced
and a polymer with more excellent particle morphology can be
obtained.
[0132] The magnesium compound (a3) generally has a sphericity (S')
represented by the above formula (III) of less than 1.30,
preferably less than 1.28.
[0133] The magnesium compound (a3) with such a sphericity (S') is
preferred in view of catalyst activity and morphology of polymer
particles.
[0134] Such a magnesium compound (a3) with a particle size
distribution index (P') of less than 3.4 and a sphericity (S') of
less than 1.30 can be produced by reacting the above metallic
magnesium, alcohol and halogen and/or halogen-containing compound
under the above stirring conditions.
[0135] The magnesium compound (a3) may be used solely or two or
more thereof prepared by different methods may be used in
combination.
[0136] Such a magnesium compound (a3) is solid and substantially
made of a magnesium alkoxide. Examples of the magnesium alkoxide
are the same as those of the magnesium compound (a1).
[0137] (b3) Titanium Compound
[0138] The titanium compound (b3) is as explained with regard to
the titanium compound (b1) for use in the solid catalyst component
[A1], so that its explanation is omitted.
[0139] (c3) Halogenated Compound
[0140] The halogenated compound (c3) is as explained with regard to
the titanium compound (c1) for use in the solid catalyst component
[A1], so that its explanation is omitted.
[0141] (d3) Electron-Donating Compound
[0142] The electron-donating compound (d3) is as explained with
regard to the electron-donating compound (d1) for use in the solid
catalyst component [A1], so that its explanation is omitted.
[A4] Solid Catalyst Component for Olefin Polymerization
[0143] (a4) Magnesium Compound
[0144] In view of the form of polymer particles and polymerization
activity, the invention uses, as a magnesium compound (a4), a
compound that is obtained by reacting metallic magnesium having an
oxidized coating film with a thickness of 1 .mu.m or less,
preferably 0.5 .mu.m or less, more preferably 0.1 .mu.m or less, an
alcohol, and a halogen and/or a halogen-containing compound
containing halogen atoms in an amount of 0.0001 gram atom or more
relative to one gram atom of the metallic magnesium.
[0145] If metallic magnesium having an oxidized coating film with a
thickness more than 1 .mu.m is used, the particulate morphology of
a magnesium compound (a4) or polyolefin obtained therefrom, or
polymerization activity may be degraded.
[0146] Compounds constituting the oxidized coating film include
Mg(OH).sub.2, MgO, MgCO.sub.3, MgSO.sub.4, double salts thereof and
those containing crystal water. Examples of
crystal-water-containing compounds include MgSO.sub.4 7H.sub.2O.
Examples of the double salts include (MgCO.sub.3).sub.4
Mg(OH).sub.2 5H.sub.2O. The content thereof is generally 1 wt. % or
less.
[0147] Such metallic magnesium having an oxidized coating film with
a thickness of 1 .mu.m or less can be produced by being formed into
particles, for example, cutting, milling, sieving or melting/spray,
in an atmosphere of an inert gas such as nitrogen.
[0148] The metallic magnesium is not critical with regard to its
form and the like, so far as an oxidized coating film has a
thickness of 1 .mu.m or less. Therefore metallic magnesium having
any particle form, for example, metallic magnesium having a
granular, ribbon-shaped or powdery form, may be used. However, in
order to ensure homogeneous reaction, particles with an average
diameter of 1 cm or less are preferably used. When producing the
particles with an average diameter of 1 cm or less, metallic
magnesium may be subjected to processing such as cutting, milling,
sieving and melting/spray preferably in an atmosphere of an inert
gas such as nitrogen.
[0149] An alcohol, a halogen and a halogen-containing compound are
the same as those explained in the magnesium compound (a1) and
their explanation is thus omitted.
[0150] In order to produce the magnesium compound (a4), metallic
magnesium satisfying the above requirements, an alcohol, a halogen
and/or halogen-containing compound are reacted in the same manner
as in the magnesium compound (a1).
[0151] The magnesium compound (a4) of the invention can be used as
a support for a solid catalyst component without operations such as
milling or classification for a narrow particle distribution like
the magnesium compound (a1). The magnesium compound (a4) is nearly
spherical and has a sharp particle size distribution. The particle
thereof has a small variability of sphericity.
[0152] The magnesium compound (a4) generally has a particle size
distribution index (P') represented by the above formula (IV) of
less than 3.4, preferably less than 3.2.
[0153] The magnesium compound (a4) generally has a sphericity (S')
represented by the above formula (III) of less than 2.00,
preferably 1.50.
[0154] Such a magnesium compound (a4) with a particle size
distribution index (P') of less than 3.4 and a sphericity (S') of
less than 2.00 is preferred in view of catalyst activity and
morphology of polymer particles. Using the above metallic magnesium
can produce such a magnesium compound (a4).
[0155] The magnesium compound (a4) may be used solely or two or
more thereof prepared by different methods may be used in
combination.
[0156] Such a magnesium compound (a4) is solid and substantially
made of a magnesium alkoxide. Examples of the magnesium alkoxide
are the same as those of the magnesium compound (a1).
[0157] (b4) Titanium Compound
[0158] The titanium compound (b4) is as explained with regard to
the titanium compound (b1) for use in the solid catalyst component
[A1], so that its explanation is omitted.
[0159] (c4) Halogenated Compound
[0160] The halogenated compound (c4) is as explained with regard to
the titanium compound (c1) for use in the solid catalyst component
[A1], so that its explanation is omitted.
[0161] (d4) Electron-Donating Compound
[0162] The electron-donating compound (d4) is as explained with
regard to the electron-donating compound (d1) for use in the solid
catalyst component [A1], so that its explanation is omitted.
[B] Organic Aluminum Compound
[0163] Although not specially limited, the organic aluminum
compound [B] can be preferably selected from an organic aluminum
compound having an alkyl group, a halogen atom, a hydrogen atom and
an alkoxy group, aluminoxane, or a mixture of these. Specific
examples thereof include trialkylaluminum compounds such as
trimethylaluminum, triethylaluminum, triisopropylaluminum,
triisobutylaluminum and trioctylaluminum; dialkylaluminum
monochlorides such as diethylaluminum monochloride,
diisopropylaluminum monochloride, diisobutylaluminum monochloride
and dioctylaluminum monochloride; alkylaluminum sesquihalides such
as ethylaluminum sesquichloride; and linear aluminoxanes such as
methylaluminoxane. Of these organic aluminum compounds,
trialkylaluminum having a lower alkyl group having 1 to 5 carbon
atoms is preferred, and trimethylaluminum, triethylaluminum,
tripropylaluminum and triisobutylaluminum are particularly
preferred. These organic aluminum compounds [B] may be used solely,
or two or more thereof may be used in combination.
[C] Electron-Donating Compound
[0164] If necessary, an electron-donating compound [C] is used for
a catalyst for olefin polymerization. The electron-donating
compound [C] is preferably used since it may improve the
stereoregularity of olefin polymer. The electron-donating compound
[C] can be selected from an organosilicon compound having an alkoxy
group, a nitrogen-containing compound, a phosphorus-containing
compound or an oxygen-containing compound. Of these, it is
particularly preferred to use an organosilicon compound having an
alkoxy group.
[0165] Specific examples of the organosilicon compound having an
alkoxy group include trimethylmethoxysilane, trimethylethoxysilane,
triethylmethoxysilane, triethylethoxysilane,
dimethyldimethoxysilane, dimethyldiethoxysilane,
ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane,
diisopropyldimethoxysilane, diisobutyldimethoxysilane,
isopropylisobutyldimethoxysilane, di-t-butyldimethoxysilane,
t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane,
t-butylpropyldimethoxysilane, t-butylisopropyldimethoxysilane,
t-butylbutyldimethoxysilane, t-butylisobutyldimethoxysilane,
t-butyl(s-butyl)dimethoxysilane, t-butylamyldimethoxysilane,
t-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane,
t-butyloctyldimethoxysilane, t-butylnonyldimethoxysilane,
t-butyldecyldimethoxysilane,
t-butyl(3,3,3-trifluoromethylpropyl)dimethoxysilane,
cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane,
cyclohexylpropyldimethoxysilane, cyclohexylisobutyldimethoxysilane,
dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane,
cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane,
cyclopentylpropyldimethoxysilane,
cyclopentyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane,
cyclopentylcyclohexyldimethoxysilane,
bis(2-methylcyclopentyl)dimethoxysilane,
bis(2,3-dimethylcyclopentyl)dimethoxysilane,
.alpha.-naphthyl-1,1,2-trimethylpropyldimethoxysilane,
n-tetradecanyl-1,1,2-trimethylpropyldimethoxysilane,
1,1,2-trimethylpropylmethyldimethoxysilane,
1,1,2-trimethylpropylethyldimethoxysilane,
1,1,2-trimethylpropylisopropyldimethoxysilane,
1,1,2-trimethylpropylcyclopentyldimethoxysilane,
1,1,2-trimethylpropylcyclohexyldimethoxysilane,
1,1,2-trimethylpropylmyristyldimethoxysilane,
diphenyldimethoxysilane, diphenyldiethoxysilane,
phenyltriethoxysilane, methyltrimethoxysilane,
methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,
propyltrimethoxysilane, isopropyltrimethoxysilane,
butyltrimethoxysilane, butyltriethoxysilane,
isobutyltrimethoxysilane, t-butyltrimethoxysilane,
s-butyltrimethoxysilane, amyltrimethoxysilane,
isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyl
trimethoxysilane, norbornenetrimethoxysilane, indenyl
trimethoxysilane, 2-methylcyclopentyl trimethoxysilane,
ethyltriisopropoxysilane,
methylcyclopentyl(t-butoxy)dimethoxysilane,
isopropyl(t-butoxy)dimethoxysilane,
t-butyl(t-butoxy)dimethoxysilane, (isobutoxy)dimethoxysilane,
vinyltriethoxysilane, vinyltributoxysilane, chlorotriethoxysilane,
.gamma.-chloropropyltrimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
1,1,2-trimethylpropyltrimethoxysilane,
1,1,2-trimethylpropylisopropoxydimethoxysilane,
1,1,2-trimethylpropyl(t-butoxy)dimethoxysilane, tetramethoxysilane,
tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, ethyl
silicate, butyl silicate, trimethylphenoxysilane,
methyltriallyloxysilane, vinyltris(.beta.-methoxyethoxy)silane,
vinyltrisacetoxysilane and dimethyltetraethoxydisiloxane and the
like. Of these, dicyclopentyldimethoxysilane,
cyclohexylisobutyldimethoxysilane and
cyclohexylmethyldimethoxysilane are preferred.
[0166] Further, the above organosilicon compound also includes a
compound obtained by reacting a silicon compound having no Si--O--C
bond with an organic compound having an O--C bond in advance or by
reacting these compounds during the polymerization of an
.alpha.-olefin. Specifically, a compound obtained by reacting
silicon tetrachloride and an alcohol is included.
[0167] Specific examples of the nitrogen-containing compound
include 2,6-substituted piperidines such as
2,6-diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine and
N-methyl-2,2,6,6-tetramethylpiperidine; 2,5-substituted azolidines
such as 2,5-diisopropylazolidine and
N-methyl-2,2,5,5-tetramethylazolidine; substituted
methylenediamines such as N,N,N',N'-tetramethylmethylenediamine and
N,N,N',N'-tetraethylmethylenediamine; and substituted
imidazolidines such as 1,3-dibenzylimidazolidine and
1,3-dibenzyl-2-phenylimidazolidine.
[0168] Specific examples of the phosphorus-containing compound
include phosphorous acid esters such as triethyl phosphite,
tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl
phosphite, triisobutyl phosphite, diethyl-n-butyl phosphite and
diethylphenyl phosphite.
[0169] Specific examples of the oxygen-containing compound include
2,5-substituted tetrahydrofurans such as
2,2,5,5-tetramethyltetrahydrofuran and
2,2,5,5-tetraethyltetrahydrofuran; and dimethoxymethane derivatives
such as 1,1-dimethoxy-2,3,4,5-tetrachlorocyclopentadiene,
9,9-dimethoxyfluorene and diphenyldimethoxymethane.
[0170] These electron-donating compounds [C] may be used solely, or
two or more thereof may be used in combination.
2. Method of Preparation of Solid Catalyst Component
[0171] As a method of preparing the solid catalyst component [A1]
to [A4], there is exemplified a method in which the above magnesium
compound (a1) to (a4) and the titanium compound (b1) to (b4), if
necessary, and the halogenated compound (c1) to (c4) and/or the
electron-donating compound (d1) to (d4) are brought into contact
and react with each other, and preferably the reaction mixture is
thereafter brought into contact and reacts with the titanium
compound (b1) to (b4) again (at least once). When the titanium
compound (b1) to (b4) is brought into contact twice or more, the
titanium compound (b1) to (b4) can be sufficiently supported on the
magnesium compound (a1) to (a4) as a support of catalyst. The order
of other contacts is not critical.
[0172] Further, these components may be brought into contact in the
presence of an inert solvent such as a hydrocarbon, or each
component may be diluted with an inert solvent such as a
hydrocarbon before they are brought into contact. Examples of the
above inert solvent include aliphatic hydrocarbons such as
n-pentane, isopentane, n-hexane, n-heptane, n-octane and isooctane,
aromatic hydrocarbons such as benzene, toluene, and xylene, or
mixtures thereof. Of these, an aliphatic hydrocarbon is
preferred.
[0173] The amount of the titanium compound (b1) to (b4) per mole of
magnesium of the magnesium compound (a1) to (a4) is generally 0.5
to 100 moles, preferably 1 to 50 moles. If the amount is less than
0.5 mole, the polymerization activity per titanium may decrease. On
the other hand, if it exceeds 100 moles, the polymerization
activity per solid catalyst component may decrease.
[0174] When the halogenated compound (c1) to (c4) is used, the
amount thereof per mole of magnesium of the magnesium compound (a1)
to (a4) is generally 0.005 to 100 moles. If the amount is less than
0.005 mole, the polymerization activity per titanium or the
stereoregularity of polymer may decrease. On the other hand, if it
exceeds 100 moles, the polymerization activity per solid catalyst
component may decrease.
[0175] Further, when the electron-donating compound (d1) to (d4) is
used, the amount thereof per mole of magnesium of the magnesium
compound (a1) to (a4) is generally 0.01 to 10 mol, preferably 0.05
to 0.15 mol. If the amount is less than 0.01 mole, the
stereoregularity of polymer may decrease. On the other hand, if it
exceeds 10 moles, the polymerization activity per titanium may
decrease.
[0176] These compounds are brought into contact generally in a
temperature range of -20 to 200.degree. C., preferably 20 to
150.degree. C. Further, the contact time is generally 1 minute to
24 hours, preferably 10 minutes to 6 hours. When the contact
reaction is carried out at the above temperature and/or for the
above time, the polymerization activity can be high and an olefin
polymer can be obtained in an excellent form. Differing depending
upon a type of a solvent when it is used and a contact temperature,
etc., the pressure for the contact is generally in the range of 0
to 5 MPa, preferably 0 to 1 MPa. During the contacting procedures,
preferably, they are stirred in view of the uniformity and
efficiency of the contact. These contact conditions are also
applicable to the contact reaction that is carried out for the
second time or more with regard to the titanium compound (b1) to
(b4).
[0177] When a solvent is used in the contact procedure of the
titanium compound (b1) to (b4), the amount of the solvent per mole
of the titanium compound (b1) to (b4) is generally 5,000
milliliters or less, preferably 10 to 1,000 milliliters. When the
ratio is outside the above range, the uniformity or efficiency of
the contact may be degraded.
[0178] Further, a reaction product, which is from the first contact
reaction of the compounds, is washed with an inert solvent,
generally at a temperature of 90 to 150.degree. C., preferably 120
to 140.degree. C. When the washing temperature is outside the above
range, the catalyst activity or the stereoregularity may not be
improved. The inert solvent can be selected from the already
explained aliphatic hydrocarbons and aromatic hydrocarbons.
[0179] Although not especially limited with regard to the washing
temperature after the contact reaction which is carried out for the
second time or more with the titanium compound (b1) to (b4), the
washing is carried out with an inert solvent, generally at a
temperature of 90 to 150.degree. C., preferably 120 to 140.degree.
C., in view of stereoregularity.
[0180] Although not especially limited, the washing method is
preferably selected from a decantation or filtering method.
Although the amount of the inert solvent, the washing time period
and the number of times of the washing are not critical, the
washing is carried out generally with a solvent in an amount, per
mole of the magnesium compound (a1) to (a4), of 100 to 100,000
milliliters, preferably 1,000 to 50,000 milliliters, generally for
1 minute to 24 hours, preferably 10 minutes to 6 hours. When the
above ratio is outside the above range, the washing may be
incomplete.
[0181] While the pressure in the above case differs depending upon
the type of the solvent, the washing temperature, and the like, the
pressure is generally in the range of 0 to 5 MPa, preferably 0 to 1
MPa. For the uniformity of the washing and the washing efficiency,
it is preferred to stir the reaction mixture during the washing.
The thus-obtained solid catalyst component [A1] to [A4] can be
stored in a dry state or in an inert solvent such as a
hydrocarbon.
3. Process for Producing Olefin Polymer
[0182] Although the amount of each component of the catalyst for
olefin polymerization is not especially limited, provided by the
invention, each of the solid catalyst components [A1] to [A4] is
used in such an amount that the titanium atom amount per liter of a
reaction volume is generally in the range of 0.00005 to 1 mmol.
[0183] The organic aluminum compound [B] is used in such an amount
that the aluminum/titanium (atomic ratio) is generally in the range
of 1 to 1,000, preferably 10 to 1,000. When the above atomic ratio
is outside the above range, the catalyst activity is sometimes
insufficient.
[0184] Further, the electron-donating compound [C] is used in such
an amount that the [C]/[B] (molar ratio) is generally in the range
of 0.001 to 5.0, preferably 0.01 to 2.0, more preferably 0.05 to
1.0. When the above molar ratio is outside the above range, the
sufficient catalyst activity and the stereoregularity sometimes
cannot be obtained. When a preliminary polymerization is carried
out, however, the amount of the electron-donating compound [C] can
be further decreased.
[0185] The olefin for use in the invention is preferably an -olefin
of the following general formula (VI).
R.sup.1--CH.dbd.CH.sub.2 VI
[0186] In the above general formula (VI), R.sup.1 is a hydrogen
atom or a hydrocarbon group, and the hydrocarbon group may be
saturated or unsaturated, may be linear or branched, or may be
cyclic. Specific examples of the olefin include ethylene,
propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,
1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcyclohexane,
butadiene, isoprene, piperylene, and the like. These olefins may be
used solely, or two or more olefins thereof may be used in
combination. Of the above olefins, ethylene and propylene are
particularly preferred.
[0187] In the polymerization of an olefin in the invention, the
preliminary polymerization of an olefin may be carried out as
required before the regular polymerization thereof in view of the
polymerization activity and the stereoregularity and power form of
an olefin polymer. In this case, the preliminary polymerization of
an olefin is carried out in the presence of a catalyst that is a
mixture of predetermined amounts of the solid catalyst component
[A1] to [A4], the organic aluminum compound [B] and optionally the
electron-donating compound [C] generally in the temperature range
of 0 to 100.degree. C. under a pressure of atmospheric pressure to
approximately 5 MPa, and then the regular polymerization of the
olefin is carried out in the presence of the catalyst and the
preliminary polymerization product. The polymerization activity and
the particle properties of a polymer can be improved by carrying
out the preliminary polymerization.
[0188] Although the polymerization type of the regular
polymerization is not especially limited, any one of solution
polymerization, slurry polymerization, gaseous phase
polymerization, bulk polymerization, etc., can be employed.
Further, any one of a batch polymerization and a continuous
polymerization can be employed, and there can be employed two-step
polymerization or multi-step polymerization that is carried out
under different conditions.
[0189] Although the reaction condition is not especially limited,
the polymerization pressure therefor is generally selected from the
range of atmospheric pressure to 8 MPa, preferably 0.2 to 5 MPa,
and the polymerization temperature is generally selected from the
range of 0 to 200.degree. C., preferably 30 to 100.degree. C., as
required in view of polymerization activity. Although differing
depending upon olefins and the polymerization temperature, the
polymerization time period is generally 5 minutes to 20 hours,
preferably approximately 10 minutes to 10 hours.
[0190] The molecular weight of an olefin polymer can be adjusted by
adding a chain transfer agent, preferably, hydrogen. Further, an
inert gas such as nitrogen may be present. For the catalyst
components of the invention, the solid catalyst component [A1] to
[A4], the organic aluminum compound [B] and the electron-donating
compound [C] may be mixed in predetermined amounts, and immediately
thereafter, followed by the introduction of an olefin for
polymerization. Alternatively, the above mixture may be aged for
approximately 0.2 to 3 hours after the contact, and then followed
by the introduction of an olefin for polymerization. Further, the
above catalyst component may be suspended in an inert solvent, an
olefin, or the like and fed. In the invention, the post treatment
after the polymerization can be carried out according to a
conventional method. That is, in a gaseous phase polymerization
method, a nitrogen current may be allowed to pass through particles
of a polymer powder introduced out of a polymerizer after the
polymerization, for removing an olefin contained therein. Further,
a polymer may be pelletized with an extruder as required, and in
this case, a small amount of water, an alcohol or the like may be
added for deactivating the catalyst completely. In a bulk
polymerization method, a polymer that is withdrawn from a
polymerizer after the polymerization can be pelletized after a
monomer is completely separated from the polymer.
EXAMPLES
[0191] The invention will be explained with reference to Example
hereinafter, while the invention shall not be limited to the
following Examples. The sphericity (S), particle size distribution
index (P), average particle size (D.sub.50) and thickness of
oxidized coating film of metallic magnesium; the sphericity (S')
and particle size distribution index (P') of magnesium compounds;
the sphericity (S'') and particle size distribution index (P'') of
polymer powders; and the stereoregularity [mmmm] of polymers were
determined as follows.
(1) Sphericity (S) of metallic magnesium: Metallic magnesium was
photographed 40 times with an optical microscope (OLYMPUS Co.,
Ltd., BHS-751P). The photograph was subjected to image processing
with an image analyzer (Nexsus Co., Ltd.). In the processing,
particles less than 20 pixels (1 pixel: 0.4 .mu.m.times.10.4 .mu.m)
were removed and the about 300 remaining particles were analyzed.
The maximum diameter L.sub.1 of projection views of the particles,
and the diameter L.sub.2 of the circle having the same area as that
of projection view with the diameter L.sub.1 were determined. Then
a sphericity was calculated using the above formula (I). (2)
Particle size distribution index (P) of metallic magnesium: A
particle size distribution measured with sieves was plotted on a
logarithmic-normal probability paper, and a 50% particle size was
used as an average particle size (D.sub.50). Further, a 90%
particle size (D.sub.90) and a 10% particle size (D.sub.10) were
determined and then a particle size distribution index was
calculated using the above formula (II). (3) Average particle size
(D.sub.50) of metallic magnesium: A particle size distribution
measured with sieves was plotted on a logarithmic-normal
probability paper, and a 50% particle size was used as an average
particle size (D.sub.50). (4) Thickness of oxidized coating film of
metallic magnesium: Analysis was carried out with an ESCA (Electron
Spectroscopy for Chemical Analysis). Specifically metallic
magnesium was subjected to Ar ion etching and a layer from the
uppermost surface to the depth of 3 .mu.m was analyzed. The
existence of an oxidized coating film was confirmed by using
standard reagents (MgCO.sub.3, Mg(OH).sub.2, MgSO.sub.4, MgO,
MgSO.sub.4 7H.sub.2O and (MgCO.sub.3).sub.4 Mg(OH).sub.2 5H.sub.2O)
(5) Sphericity (S') of magnesium compound: A magnesium compound was
dried and then photographed 300 times (150 times in Examples 15 to
18) with a scanning electron microscope (JEOL Ltd., JSM-25SIII) at
an accelerating voltage of 5 KV to obtain a negative. Next the
negative was image-processed by a transmission method. In the image
processing, particles less than 20 pixels (1 pixel: 0.695
.mu.m.times.0.695 .mu.m (1.389 .mu.m.times.1.389 .mu.m in Examples
15 to 18)) were removed and the about 2,000 remaining particles
were analyzed with an image analyzer (Nexsus Co., Ltd.). The
maximum diameter L.sub.3 of projection views of the particles, and
the diameter L.sub.4 of the circle having the same area as that of
projection view with the diameter L.sub.3 were determined. Then a
sphericity was calculated using the above formula (III). (6)
Particle size distribution index (P') of magnesium compound: The
particle size of a magnesium compound was measured by a light
transmission method while the magnesium compound was suspended in a
hydrocarbon. The particle size distribution measured was plotted on
a logarithmic-normal probability paper, and a 50% particle size was
used as an average particle size (D.sub.50). Further, a 90%
particle size (D.sub.90) and a 10% particle size (D.sub.10) were
determined and then the particle size distribution index was
calculated using the above formula (IV). (7) Sphericity (S'') of
polymer powder: In Examples 1 to 4 and Comparative Examples 1 to 3,
the sphericity (S'') was measured in the same manner as the
sphericity (S') of a magnesium compound.
[0192] In Examples 5 to 14 and Comparative Examples 4 to 12, the
sphericity (S'') was measured in the same manner as the sphericity
(S') of a magnesium compound except that the following. The
polyolefin powder was photographed 40 times with a optical
microscope (OLYMPUS Co., Ltd., BHS-751P), and the photograph was
subjected to image processing. In the processing, one pixel was
10.4 .mu.m.times.10.4 .mu.m and about 300 particles were
analyzed.
[0193] In Examples 15 to 18 and Comparative Examples 13 to 15, the
sphericity (S'') was measured in the same manner as the sphericity
(S') of a magnesium compound except that polyolefin powder was
image-analyzed by a direct reflection method and one pixel was
0.0813 mm.times.0.0813 mm in the image analysis processing.
(8) Particle size distribution index (P'') of polymer powder: The
particle size distribution index (P'') was measured in the same
manner as the particle size distribution index (P) of metallic
magnesium. (9) Stereoregularity of polymer [mmmm]: A polymer was
dissolved in 1,2,4-trichlorobenzene, and the stereoregularity of
the polymer was quantitatively determined on the basis of signals
of methyl group measured with a .sup.13C-NMR (JEOL Ltd., EX-400) at
130.degree. C. by a proton complete decoupling method.
[0194] The isotactic pentad fraction [mmmm] means the isotactic
fraction in pentad units of a polypropylene molecule chain
determined on the basis of .sup.13C-NMR spectrum, proposed by A.
Zambelli, et al., in Macromolecules, vol. 6, page 925 (1973).
[0195] Further, a method of determining assignment of peaks of
.sup.13C-NMR spectrum was according to the assignment proposed by
A. Zambelli, et al., in Macromolecules, vol. 8, page 687
(1975).
Example 1
(1) Preparation of Magnesium Compound
[0196] A three-necked flask with a stirrer, having an internal
volume of 0.5 L, was subjected to replacement of an atmosphere
therein with nitrogen gas. The flask was charged with 122 g of
ethanol (2.64 gram atoms), 0.8 g of iodine (6.3 mg atoms) and 8 g
of metallic magnesium (0.33 gram atoms) with a sphericity of 1.85,
which had been produced by an atomization method. The mixture was
reacted with stirring (350 rpm) at 78.degree. C. until hydrogen was
not generated from the system to give a magnesium compound
(diethoxymagnesium). Table 1 shows the results.
[0197] (2) Preparation of Solid Catalyst Component
[0198] A three-necked flask with a stirrer, having an internal
volume of 0.5 L, was subjected to replacement of an atmosphere
therein with nitrogen gas, and then the flask was charged with 80
mL of dehydrated octane and 16 g of the magnesium compound
(support) prepared in the above (1). The mixture was heated to
40.degree. C. Thereto was added 2.4 mL (23 mmol) of silicon
tetrachloride and stirred for 20 minutes, followed by adding 3.4 mL
(13 mmol) of di-n-butyl phthalate. The resultant solution was
heated to 80.degree. C. and 77 mL (0.70 mol) of titanium
tetrachloride was dropwise added using a dropping funnel. Then, the
mixture was stirred at an internal temperature of 125.degree. C.
for 1 hour to carry out a titanation procedure. After sufficiently
washing with dehydrated octane, 122 mL (1.11 mol) of titanium
tetrachloride was added and the mixture was stirred at an internal
temperature of 125.degree. C. for 2 hours to carry out a second
titanation procedure. Sufficient washing with dehydrated octane
gave a solid catalyst component.
[0199] (3) Propylene Slurry Polymerization
[0200] An autoclave made of stainless steel with a stirrer, having
an internal volume of 1 L, was fully dried and then subjected to
replacement of an atmosphere therein with nitrogen. The autoclave
was charged with 500 mL of dehydrated heptane. The autoclave was
further charged with 2.0 mmol of triethylaluminum, 0.25 mmol of
dicyclopentyldimethoxysilane and 0.0025 mmol, as Ti atom, of the
solid catalyst component prepared in the above (2), and hydrogen
was introduced up to 0.1 MPa. Then, while propylene was introduced,
the autoclave was temperature-increased to 80.degree. C. and
pressure-increased to a total pressure of 0.8 MPa, followed by
polymerization for 1 hour.
[0201] Then, the temperature and the pressure in the autoclave were
decreased, and the reaction product was taken out and poured into 2
L of methanol to deactivate the catalyst. The product was separated
by filtration and vacuum-dried to give a polypropylene. Table 1
shows the results.
Example 2
(1) Preparation of Magnesium Compound
[0202] A magnesium compound was obtained in the same manner as in
Example 1(1) except that the amount of iodine was changed to 0.24 g
(1.9 mg atoms), the reaction temperature was changed to 50.degree.
C. and the stirring speed was changed to 525 rpm. Table 1 shows the
results.
[0203] (2) Preparation of Solid Catalyst Component
[0204] A solid catalyst component was obtained in the same manner
as in Example 1(2) except that the magnesium compound prepared in
the above (1) was used.
[0205] (3) Propylene Slurry Polymerization
[0206] Propylene was polymerized in the same manner as in Example
1(3) except that the solid catalyst component prepared in the above
(2) was used. Table 1 shows the results.
Example 3
(1) Preparation of Magnesium Compound
[0207] A magnesium compound was obtained in the same manner as in
Example 1(1) except that the iodine was replaced with 0.30 g of
anhydrous magnesium chloride (6.3 mg atoms) in Example 1(1). Table
1 shows the results.
[0208] (2) Preparation of Solid Catalyst Component
[0209] A solid catalyst component was obtained in the same manner
as in Example 1(2) except that the magnesium compound prepared in
the above (1) was used.
[0210] (3) Propylene Slurry Polymerization
[0211] Propylene was polymerized in the same manner as in Example
1(3) except that the solid catalyst component prepared in the above
(2) was used. Table 1 shows the results.
Example 4
(1) Preparation of Magnesium Compound
[0212] A magnesium compound was obtained in the same manner as in
Example 1(1) except that metallic magnesium with a sphericity of
2.93 (prepared by a cutting and ball mill method) was used. Table 1
shows the results.
[0213] (2) Preparation of Solid Catalyst Component
[0214] A solid catalyst component was obtained in the same manner
as in Example 1(2) except that the magnesium compound prepared in
the above (1) was used.
[0215] (3) Propylene Slurry Polymerization
[0216] Propylene was polymerized in the same manner as in Example
1(3) except that the solid catalyst component prepared in the above
(2) was used. Table 1 shows the results.
Comparative Example 1
[0217] (1) Preparation of Magnesium Compound
[0218] A magnesium compound was obtained in the same manner as in
Example 1(1) except that metallic magnesium with a sphericity of
5.20 (prepared by a cutting method) was used. Table 1 shows the
results.
[0219] (2) Preparation of Solid Catalyst Component
[0220] A solid catalyst component was obtained in the same manner
as in Example 1(2) except that the magnesium compound prepared in
the above (1) was used.
[0221] (3) Propylene Slurry Polymerization
[0222] Propylene was polymerized in the same manner as in Example
1(3) except that the solid catalyst component prepared in the above
(2) was used. Table 1 shows the results.
Comparative Example 2
[0223] (1) Preparation of Magnesium Compound
[0224] A magnesium compound was obtained in the same manner as in
Example 1(1) except that metallic magnesium with a sphericity of
5.80 (prepared by a cutting method) was used and the reaction
temperature was changed to 60.degree. C. Table 1 shows the
results.
[0225] (2) Preparation of Solid Catalyst Component
[0226] A solid catalyst component was obtained in the same manner
as in Example 1(2) except that the magnesium compound prepared in
the above (1) was used.
[0227] (3) Propylene Slurry Polymerization
[0228] Propylene was polymerized in the same manner as in Example
1(3) except that the solid catalyst component prepared in the above
(2) was used. Table 1 shows the results.
Comparative Example 3
[0229] (1) Preparation of Magnesium Compound
[0230] A magnesium compound was obtained in the same manner as in
Example 3(1) except that metallic magnesium with a sphericity of
6.95 (prepared by a cutting method) was used. Table 1 shows the
results.
[0231] (2) Preparation of Solid Catalyst Component
[0232] A solid catalyst component was obtained in the same manner
as in Example 1(2) except that the magnesium compound prepared in
the above (1) was used.
[0233] (3) Propylene Slurry Polymerization
[0234] Propylene was polymerized in the same manner as in Example
1(3) except that the solid catalyst component prepared in the above
(2) was used. Table 1 shows the results.
TABLE-US-00001 TABLE 1 Com. Com. Com. Item Unit Ex. 1 Ex. 2 Ex. 3
Ex. 4 Ex. 1 Ex. 2 Ex. 3 Support Sphericity of Metallic Mg (S) 1.85
1.85 1.85 2.93 5.20 5.80 6.95 Initiator I.sub.2 I.sub.2 MgCl.sub.2
I.sub.2 I.sub.2 I.sub.2 MgCl.sub.2 Halogen Comp./Mg (gram atom
0.019 0.0057 0.019 0.019 0.019 0.019 0.019 molar) Reaction
Temperature (.degree. C.) 78 50 78 78 78 60 78 Number of Rotation
(rpm) 350 525 350 350 350 350 350 Average Particle Size (D.sub.50)
(.mu.m) 68 34 69 67 76 62 80 Sphericity (S') 1.23 1.21 1.25 1.28
1.34 1.38 1.85 PDDI (P') 3.4 3.3 3.7 3.8 4.9 3.8 6.9 Polymer
Polymerization Activity (kg/g-Cat) 16.8 24.9 16.3 15.8 13.1 15.0
12.7 Stereoregularity ([mmmm]) (mol %) 98.3 98.4 98.2 98.3 98.2
98.3 98.3 Average Particle Size (D.sub.50) (.mu.m) 1230 660 1210
1250 1320 1040 1380 Sphericity (S'') 1.23 1.20 1.24 1.29 1.36 1.40
1.90 PDDI (P'') 3.5 3.4 3.8 3.8 5.2 3.9 7.2 Ex.: Example Com. Ex.:
Comparative Example Halogen Comp.: Halogen and/or
Halogen-containing Compound PDDI: Particle size Distribution
Index
Example 5
(1) Preparation of Magnesium Compound
[0235] A three-necked flask with a stirrer, having an internal
volume of 0.5 L, was replaced with nitrogen gas, and then 122 g
(2.64 gram atoms) of dehydrated ethanol, 0.8 g (6.3 mg atoms) of
iodine and 8 g (0.33 gram atoms) of metallic magnesium with a
particle size distribution index of 1.4 (sieved after cutting and
milling) were added therein. The mixture was reacted at 78.degree.
C. while stirring (350 rpm) until hydrogen was no longer generated
from the system to obtain a magnesium compound (diethoxymagnesium).
Table 2 shows the results.
[0236] (2) Preparation of Solid Catalyst Component
[0237] A three-necked flask with a stirrer, having an internal
volume of 0.5 L, was subjected to replacement of an atmosphere
therein with nitrogen gas, and then the flask was charged with 80
mL of dehydrated octane and 16 g of the magnesium compound
(support) prepared in the above (1). The mixture was heated to
40.degree. C. Thereto was added 2.4 mL (23 mmol) of silicon
tetrachloride and stirred for 20 minutes, followed by adding 3.4 mL
(13 mmol) of di-n-butyl phthalate. The resultant solution was
heated to 80.degree. C. and 77 mL (0.70 mol) of titanium
tetrachloride was dropwise added using a dropping funnel. Then, the
mixture was stirred at an internal temperature of 125.degree. C.
for 1 hour to carry out a titanation procedure. After sufficiently
washing with dehydrated octane, 122 mL (1.11 mol) of titanium
tetrachloride was added and the mixture was stirred at an internal
temperature of 125.degree. C. for 2 hours to carry out a second
titanation procedure. Sufficient washing with dehydrated octane
gave a solid catalyst component.
[0238] (3) Propylene Slurry Polymerization
[0239] An autoclave made of stainless steel with a stirrer, having
an internal volume of 1 L, was fully dried and then subjected to
replacement of an atmosphere therein with nitrogen. The autoclave
was charged with 500 mL of dehydrated heptane. The autoclave was
further charged with 2.0 mmol of triethylaluminum, 0.25 mmol of
dicyclopentyldimethoxysilane and 0.0025 mmol, as Ti atom, of the
solid catalyst component prepared in the above (2), and hydrogen
was introduced up to 0.1 MPa. Then, while propylene was introduced,
the autoclave was temperature-increased to 80.degree. C. and
pressure-increased to a total pressure of 0.8 MPa, followed by
polymerization for 1 hour.
[0240] Then, the temperature and the pressure in the autoclave were
decreased, and the reaction product was taken out and poured into 2
L of methanol to deactivate the catalyst. The product was separated
by filtration and vacuum-dried to give a polypropylene. Table 2
shows the results.
Example 6
(1) Preparation of Magnesium Compound
[0241] A magnesium compound was obtained in the same manner as in
Example 5(1) except that the amount of iodine was changed to 0.24 g
(1.9 mg atoms), the reaction temperature was changed to 50.degree.
C. and the number of stirring was changed to 525 rpm. Table 2 shows
the results.
[0242] (2) Preparation of Solid Catalyst Component
[0243] A solid catalyst component was obtained in the same manner
as in Example 5(2) except that the magnesium compound prepared in
the above (1) was used.
[0244] (3) Propylene Slurry Polymerization
[0245] Propylene was polymerized in the same manner as in Example
5(3) except that the solid catalyst component prepared in the above
(2) was used. Table 2 shows the results.
Example 7
(1) Preparation of Magnesium Compound
[0246] A magnesium compound was obtained in the same manner as in
Example 5(1) except that the iodine was replaced with 0.30 g of
anhydrous magnesium chloride (6.3 mg atoms) in Example 5(1). Table
1 shows the results.
[0247] (2) Preparation of Solid Catalyst Component
[0248] A solid catalyst component was obtained in the same manner
as in Example 5(2) except that the magnesium compound prepared in
the above (1) was used.
[0249] (3) Propylene Slurry Polymerization
[0250] Propylene was polymerized in the same manner as in Example
5(3) except that the solid catalyst component prepared in the above
(2) was used. Table 2 shows the results.
Example 8
(1) Preparation of Magnesium Compound
[0251] A magnesium compound was obtained in the same manner as in
Example 5(1) except that metallic magnesium with a particle size
distribution index of 3.0 (sieved after cutting and milling) was
used. Table 2 shows the results.
[0252] (2) Preparation of Solid Catalyst Component
[0253] A solid catalyst component was obtained in the same manner
as in Example 5(2) except that the magnesium compound prepared in
the above (1) was used.
[0254] (3) Propylene Slurry Polymerization
[0255] Propylene was polymerized in the same manner as in Example
5(3) except that the solid catalyst component prepared in the above
(2) was used. Table 2 shows the results.
Example 9
(1) Preparation of Magnesium Compound
[0256] A magnesium compound was obtained in the same manner as in
Example 5(1) except that metallic magnesium with a particle size
distribution index of 1.8 (sieved after cutting and milling) was
used. Table 2 shows the results.
[0257] (2) Preparation of Solid Catalyst Component
[0258] A solid catalyst component was obtained in the same manner
as in Example 5(2) except that the magnesium compound prepared in
the above (1) was used.
[0259] (3) Propylene Slurry Polymerization
[0260] Propylene was polymerized in the same manner as in Example
5(3) except that the solid catalyst component prepared in the above
(2) was used. Table 2 shows the results.
Comparative Example 4
[0261] (1) Preparation of Magnesium Compound
[0262] A magnesium compound was obtained in the same manner as in
Example 5(1) except that metallic magnesium with a particle size
distribution index of 4.9 (sieved after cutting and milling, and
collected particles of widely varied diameters when sieved) was
used. Table 2 shows the results.
[0263] (2) Preparation of Solid Catalyst Component
[0264] A solid catalyst component was obtained in the same manner
as in Example 5(2) except that the magnesium compound prepared in
the above (1) was used.
[0265] (3) Propylene Slurry Polymerization
[0266] Propylene was polymerized in the same manner as in Example
5(3) except that the solid catalyst component prepared in the above
(2) was used. Table 2 shows the results.
Comparative Example 5
[0267] (1) Preparation of Magnesium Compound
[0268] A magnesium compound was obtained in the same manner as in
Example 5(1) except that metallic magnesium with a particle size
distribution index of 5.4 (sieved after cutting and milling, and
collected particles of widely varied diameters when sieved) was
used and the reaction temperature was changed to 60.degree. C.
Table 2 shows the results.
[0269] (2) Preparation of Solid Catalyst Component
[0270] A solid catalyst component was obtained in the same manner
as in Example 5(2) except that the magnesium compound prepared in
the above (1) was used
[0271] (3) Propylene Slurry Polymerization
[0272] Propylene was polymerized in the same manner as in Example
5(3) except that the solid catalyst component prepared in the above
(2) was used. Table 2 shows the results.
Comparative Example 6
[0273] (1) Preparation of Magnesium Compound
[0274] A magnesium compound was obtained in the same manner as in
Example 7(1) except that metallic magnesium with a particle size
distribution index of 7.0 (only cut and milled) was used. Table 2
shows the results.
[0275] (2) Preparation of Solid Catalyst Component
[0276] A solid catalyst component was obtained in the same manner
as in Example 5(2) except that the magnesium compound prepared in
the above (1) was used.
[0277] (3) Propylene Slurry Polymerization
[0278] Propylene was polymerized in the same manner as in Example
5(3) except that the solid catalyst component prepared in the above
(2) was used. Table 2 shows the results.
TABLE-US-00002 TABLE 2 Item Unit Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Com.
Ex. 4 Com. Ex. 5 Com. Ex. 6 Support PDDI of Metallic 1.4 1.4 1.4
3.0 1.8 4.9 5.4 7.0 Mg (P) Initiator I.sub.2 I.sub.2 MgCl.sub.2
I.sub.2 I.sub.2 I.sub.2 I.sub.2 MgCl.sub.2 Halogen Comp./Mg (gram
atom 0.019 0.0057 0.019 0.019 0.019 0.019 0.019 0.019 molar)
Reaction Temperature (.degree. C.) 78 50 78 78 78 78 60 78 Number
of Rotation (rpm) 350 525 350 350 350 350 350 350 Average Particle
(.mu.m) 69 34 70 68 69 74 61 77 Size (D.sub.50) PDDI (P') 2.8 2.6
2.9 3.1 3.2 4.8 3.8 6.2 Sphericity (S') 1.30 1.28 1.31 1.32 1.30
1.36 1.35 1.63 Polymer Polymerization (kg/g-Cat) 16.4 23.9 15.5
15.7 16.4 13.8 15.4 13.2 Activity Stereoregularity (mol %) 98.3
98.4 98.2 98.3 98.3 98.2 98.3 98.3 ([mmmm]) Average Particle
(.mu.m) 1,240 650 1,190 1,220 1,240 1,300 1,030 1,340 Size
(D.sub.50) PDDI (P'') 2.9 2.7 3.0 3.2 3.4 5.0 3.9 6.4 Sphericity
(S'') 1.30 1.28 1.30 1.33 1.30 1.38 1.36 1.65 Ex.: Example Com.
Ex.: Comparative Example Halogen Comp.: Halogen and/or
Halogen-containing Compound PDDI: Particle size Distribution
Index
Example 10
(1) Preparation of Magnesium Compound
[0279] A three-necked flask, which has a stirrer with four baffles
(maxblend blade, blade diameter (d)=0.09 m) and has an internal
volume of 5 L, was replaced with nitrogen gas. The flask was
charged with 2,274 g (49 gram atoms) of dehydrated ethanol, 12 g
(95 mg atoms) of iodine and 120 g (4.9 gram atoms) of metallic
magnesium with an average particle size of 400 .mu.m (cut and
milled product) (ethanol/metallic magnesium (ROH/Mg) (molar
ratio)=10). The mixture was reacted at 78.degree. C. while stirring
(number of stirring (n)=250 (number of revolution per minute)
(hereinafter referred to as "rpm"),
n.sup.3d.sup.2=1.27.times.10.sup.5) until hydrogen was no longer
generated from the system to obtain a magnesium compound
(diethoxymagnesium). Table 3 shows the results.
[0280] (2) Preparation of Solid Catalyst Component
[0281] A three-necked flask with a stirrer, having an internal
volume of 0.5 L, was subjected to replacement of an atmosphere
therein with nitrogen gas, and then the flask was charged with 80
mL of dehydrated octane and 16 g of the magnesium compound
(support) prepared in the above (1). The mixture was heated to
40.degree. C. Thereto was added 2.4 mL (23 mmol) of silicon
tetrachloride and stirred for 20 minutes, followed by adding 3.4 mL
(13 mmol) of di-n-butyl phthalate. The resultant solution was
heated to 80.degree. C. and 77 mL (0.70 mol) of titanium
tetrachloride was dropwise added using a dropping funnel. Then, the
mixture was stirred at an internal temperature of 125.degree. C.
for 1 hour to carry out a titanation procedure. After sufficiently
washing with dehydrated octane, 122 mL (1.11 mol) of titanium
tetrachloride was added and the mixture was stirred at an internal
temperature of 125.degree. C. for 2 hours to carry out a second
titanation procedure. Sufficient washing with dehydrated octane
gave a solid catalyst component.
[0282] (3) Propylene Slurry Polymerization
[0283] An autoclave made of stainless steel with a stirrer, having
an internal volume of 1 L, was fully dried and then subjected to
replacement of an atmosphere therein with nitrogen. The autoclave
was charged with 500 mL of dehydrated heptane. The autoclave was
further charged with 2.0 mmol of triethylaluminum, 0.25 mmol of
dicyclopentyldimethoxysilane and 0.0025 mmol, as Ti atom, of the
solid catalyst component prepared in the above (2), and hydrogen
was introduced up to 0.1 MPa. Then, while propylene was introduced,
the autoclave was temperature-increased to 80.degree. C. and
pressure-increased to a total pressure of 0.8 MPa, followed by
polymerization for 1 hour.
[0284] Then, the temperature and the pressure in the autoclave were
decreased, and the reaction product was taken out and poured into 2
L of methanol to deactivate the catalyst. The product was separated
by filtration and vacuum-dried to give a polypropylene. Table 3
shows the results.
Example 11
(1) Preparation of Magnesium Compound
[0285] A magnesium compound was obtained in the same manner as in
Example 10(1) except that the amount of iodine was changed to 3.6 g
(28 mg atoms), the reaction temperature was changed to 50.degree.
C. and the number of stirring (n) was changed to 375 rpm
(n.sup.3d.sup.2=4.27.times.10.sup.5). Table 3 shows the
results.
[0286] (2) Preparation of Solid Catalyst Component
[0287] A solid catalyst component was obtained in the same manner
as in Example 10(2) except that the magnesium compound prepared in
the above (1) was used.
[0288] (3) Propylene Slurry Polymerization
[0289] Propylene was polymerized in the same manner as in Example
10(3) except that the solid catalyst component prepared in the
above (2) was used. Table 3 shows the results.
Example 12
(1) Preparation of Magnesium Compound
[0290] A magnesium compound was obtained in the same manner as in
Example 10(1) except that the iodine was replaced with 1.5 g (31 mg
atoms) of anhydrous magnesium chloride and 40 g (1.6 g atoms) of
metallic magnesium (ROH/Mg=30) was used. Table 3 shows the
results.
[0291] (2) Preparation of Solid Catalyst Component
[0292] A solid catalyst component was obtained in the same manner
as in Example 10(2) except that the magnesium compound prepared in
the above (1) was used.
[0293] (3) Propylene Slurry Polymerization
[0294] Propylene was polymerized in the same manner as in Example
10(3) except that the solid catalyst component prepared in the
above (2) was used. Table 3 shows the results.
Example 13
(1) Preparation of Magnesium Compound
[0295] A magnesium compound was obtained in the same manner as in
Example 10(1) except that metallic magnesium with an average
particle size (D.sub.50) of 75 .mu.m (cut and milled product) was
used, ethanol/metallic magnesium (molar ratio) was changed to 8 and
the number of stirring (n) was changed to 150 rpm
(n.sup.3d.sup.2=2.73.times.10.sup.4). Table 3 shows the
results.
[0296] (2) Preparation of Solid Catalyst Component
[0297] A solid catalyst component was obtained in the same manner
as in Example 10(2) except that the magnesium compound prepared in
the above (1) was used.
[0298] (3) Propylene Slurry Polymerization
[0299] Propylene was polymerized in the same manner as in Example
10(3) except that the solid catalyst component prepared in the
above (2) was used. Table 3 shows the results.
Example 14
(1) Preparation of Magnesium Compound
[0300] A magnesium compound was obtained in the same manner as in
Example 13(1) except that metallic magnesium with an average
particle size (D.sub.50) of 1,800 .mu.m (cut and milled product)
was used and the number of stirring (n) was 400 rpm
(n.sup.3d.sup.2=5.18.times.10.sup.5). Table 3 shows the
results.
[0301] (2) Preparation of Solid Catalyst Component
[0302] A solid catalyst component was obtained in the same manner
as in Example 10(2) except that the magnesium compound prepared in
the above (1) was used.
[0303] (3) Propylene Slurry Polymerization
[0304] Propylene was polymerized in the same manner as in Example
10(3) except that the solid catalyst component prepared in the
above (2) was used. Table 3 shows the results.
Comparative Example 7
[0305] (1) Preparation of Magnesium Compound
[0306] A magnesium compound was obtained in the same manner as in
Example 13(1) except that metallic magnesium with an average
particle size (D.sub.50) of 2,400 .mu.m (cutting and milling
product) was used and the number of stirring (n) was changed to 250
rpm (n.sup.3d.sup.2=1.27.times.10.sup.5) Table 3 shows the
results.
[0307] (2) Preparation of Solid Catalyst Component
[0308] A solid catalyst component was obtained in the same manner
as in Example 10(2) except that the magnesium compound prepared in
the above (1) was used.
[0309] (3) Propylene Slurry Polymerization
[0310] Propylene was polymerized in the same manner as in Example
10(3) except that the solid catalyst component prepared in the
above (2) was used. Table 3 shows the results.
Comparative Example 8
[0311] (1) Preparation of Magnesium Compound
[0312] A magnesium compound was obtained in the same manner as in
Example 11(1) except that metallic magnesium with an average
particle size (D.sub.50) of 40 .mu.m (cut and milled product) and
the amount of iodine was changed to 3.6 g (28 mg atoms) and the
number of stirring (n) was changed to 200 rpm (n.sup.3d.sup.2
6.48.times.10.sup.4). Table 3 shows the results.
[0313] (2) Preparation of Solid Catalyst Component
[0314] A solid catalyst component was obtained in the same manner
as in Example 10(2) except that the magnesium compound prepared in
the above (1) was used.
[0315] (3) Propylene Slurry Polymerization
[0316] Propylene was polymerized in the same manner as in Example
10(3) except that the solid catalyst component prepared in the
above (2) was used. Table 3 shows the results.
Comparative Example 9
[0317] (1) Preparation of Magnesium Compound
[0318] A magnesium compound was obtained in the same manner as in
Example 10(1) except that ethanol/metallic magnesium (molar ratio)
was changed to 50. Table 3 shows the results.
[0319] (2) Preparation of Solid Catalyst Component
[0320] A solid catalyst component was obtained in the same manner
as in Example 10(2) except that the magnesium compound prepared in
the above (1) was used.
[0321] (3) Propylene Slurry Polymerization
[0322] Propylene was polymerized in the same manner as in Example
10(3) except that the solid catalyst component prepared in the
above (2) was used. Table 3 shows the results.
Comparative Example 10
[0323] (1) Preparation of Magnesium Compound
[0324] A magnesium compound was obtained in the same manner as in
Example 10(1) except that ethanol/metallic magnesium (molar ratio)
was changed to 3. Table 3 shows the results.
[0325] (2) Preparation of Solid Catalyst Component
[0326] A solid catalyst component was obtained in the same manner
as in Example 10(2) except that the magnesium compound prepared in
the above (1) was used.
[0327] (3) Propylene Slurry Polymerization
[0328] Propylene was polymerized in the same manner as in Example
10(3) except that the solid catalyst component prepared in the
above (2) was used. Table 3 shows the results.
Comparative Example 11
[0329] (1) Preparation of Magnesium Compound
[0330] A magnesium compound was obtained in the same manner as in
Example 13(1) except that metallic magnesium with an average
particle size (D.sub.50) of 600 .mu.m (cut and milled product) was
used and the number of stirring (n) was changed to 60 rpm
(n.sup.3d.sup.2=1.75.times.10.sup.3). Table 3 shows the
results.
[0331] (2) Preparation of Solid Catalyst Component
[0332] A solid catalyst component was obtained in the same manner
as in Example 10(2) except that the magnesium compound prepared in
the above (1) was used.
[0333] (3) Propylene slurry polymerization
[0334] Propylene was polymerized in the same manner as in Example
10(3) except that the solid catalyst component prepared in the
above (2) was used. Table 3 shows the results.
Comparative Example 12
[0335] (1) Preparation of Magnesium Compound
[0336] A magnesium compound was obtained in the same manner as in
Example 13(1) except that metallic magnesium with an average
particle size (D.sub.50) of 200 .mu.m (cut and milled product) was
used and the number of stirring (n) was changed to 800 rpm
(n.sup.3d.sup.2=4.15.times.10.sup.6). Table 3 shows the
results.
[0337] (2) Preparation of Solid Catalyst Component
[0338] A solid catalyst component was obtained in the same manner
as in Example 10(2) except that the magnesium compound prepared in
the above (1) was used.
[0339] (3) Propylene Slurry Polymerization
[0340] Propylene was polymerized in the same manner as in Example
10(3) except that the solid catalyst component prepared in the
above (2) was used. Table 3 shows the results.
TABLE-US-00003 TABLE 3 Com. Item Unit Ex. 10 Ex. 11 Ex. 12 Ex. 13
Ex. 14 Ex. 7 M-Mg Average Particle (.mu.m) 400 400 400 75 1,800
2,400 Size (D.sub.50) Support Initiator I.sub.2 I.sub.2 MgCl.sub.2
I.sub.2 I.sub.2 I.sub.2 Halogen Comp./Mg (gram atom 0.019 0.0057
0.019 0.019 0.019 0.019 molar) ROH/Mg (molar 10 10 30 8 8 8 ratio)
Reaction (.degree. C.) 78 50 78 78 78 78 temperature Number of
Rotation (rpm) 250 375 250 150 400 250 (n) Diameter of (m) 0.09
0.09 0.09 0.09 0.09 0.09 Stirring Blade (d) Stirring Condition
1.27E+05 4.27E+05 1.27E+05 2.73E+04 5.18E+05 1.27E+05
(n.sup.3d.sup.2) Average Particle (.mu.m) 72 35 77 34 54 103 Size
(D.sub.50) PDDI (P) 3.0 2.9 3.2 3.1 3.2 4.3 Sphericity (S) 1.24
1.23 1.26 1.27 1.26 1.48 Polymer Polymerization (kg/g-Cat) 15.7
23.8 14.6 16.4 16.1 13.2 Activity Stereoregularity (mol %) 98.4
98.4 98.3 98.3 98.4 98.1 ([mmmm]) Average Particle (.mu.m) 1,310
650 1,330 580 1,040 1,800 Size (D.sub.50) PDDI (P') 3.1 3.0 3.3 3.2
3.3 4.5 Sphericity (S') 1.24 1.23 1.26 1.28 1.27 1.48 Com. Com.
Com. Com. Com. Item Unit Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 M-Mg
Average Particle (.mu.m) 40 400 400 600 200 Size (D.sub.50) Support
Initiator I.sub.2 I.sub.2 I.sub.2 I.sub.2 I.sub.2 Halogen Comp./Mg
(gram atom 0.0057 0.019 0.019 0.019 0.019 molar) ROH/Mg (molar 10
50 3 8 8 ratio) Reaction (.degree. C.) 78 78 78 78 78 temperature
Number of Rotation (rpm) 200 250 250 60 800 (n) Diameter of (m)
0.09 0.09 0.09 0.09 0.09 Stirring Blade (d) Stirring Condition
6.48E+04 1.27E+05 1.27E+05 1.75E+03 4.15E+06 (n.sup.3d.sup.2)
Average Particle (.mu.m) 15 88 64 77 17 Size (D.sub.50) PDDI (P)
4.4 4.7 4.8 4.7 4.8 Sphericity (S) 1.73 1.63 1.65 1.98 1.78 Polymer
Polymerization (kg/g-Cat) 12.9 12.7 11.9 12.5 12.2 Activity
Stereoregularity (mol %) 98.2 98.3 98.2 98.2 98.3 ([mmmm]) Average
Particle (.mu.m) 330 1,690 1,220 1,340 360 Size (D.sub.50) PDDI
(P') 4.8 4.9 5.0 4.9 5.1 Sphericity (S') 1.75 1.65 1.68 2.04 1.48
Ex.: Example Com. Ex.: Comparative Example M-Mg: Metallic Mg
Halogen Comp.: Halogen and/or Halogen-containing Compound PDDI:
Particle size Distribution Index
Example 15
(1) Preparation of Magnesium Compound
[0341] A three-necked flask with a stirrer, having an internal
volume of 0.5 L, was replaced with nitrogen gas. The flask was
charged with 122 g (2.64 gram atoms) of dehydrated ethanol, 0.8 g
(6.3 mg atoms) of iodine and 8 g (0.33 gram atoms) of metallic
magnesium with an oxidized coating film having a thickness of 0.05
.mu.m (an average particle size of 400 .mu.m, obtained by cut,
milled and sieved under an atmosphere of nitrogen gas). The mixture
was reacted at 78.degree. C. while stirring (number of stirring
(n)=350 rpm) until hydrogen was no longer generated from the system
to obtain a magnesium compound (diethoxymagnesium). Table 4 shows
the results.
[0342] (2) Preparation of Solid Catalyst Component
[0343] A three-necked flask with a stirrer, having an internal
volume of 0.5 L, was subjected to replacement of an atmosphere
therein with nitrogen gas, and then the flask was charged with 80
mL of dehydrated octane and 16 g of the magnesium compound
(support) prepared in the above (1). The mixture was heated to
40.degree. C. Thereto was added 2.4 mL (23 mmol) of silicon
tetrachloride and stirred for 20 minutes, followed by adding 3.4 mL
(13 mmol) of di-n-butyl phthalate. The resultant solution was
heated to 80.degree. C. and 77 mL (0.70 mol) of titanium
tetrachloride was dropwise added using a dropping funnel. Then, the
mixture was stirred at an internal temperature of 125.degree. C.
for 1 hour to carry out a titanation procedure. After sufficiently
washing with dehydrated octane, 122 mL (1.11 mol) of titanium
tetrachloride was added and the mixture was stirred at an internal
temperature of 125.degree. C. for 2 hours to carry out a second
titanation procedure. Sufficient washing with dehydrated octane
gave a solid catalyst component.
[0344] (3) Propylene Slurry Polymerization
[0345] An autoclave made of stainless steel with a stirrer, having
an internal volume of 1 L, was fully dried and then subjected to
replacement of an atmosphere therein with nitrogen. The autoclave
was charged with 500 mL of dehydrated heptane. The autoclave was
further charged with 2.0 mmol of triethylaluminum, 0.25 mmol of
dicyclopentyldimethoxysilane and 0.0025 mmol, as Ti atom, of the
solid catalyst component prepared in the above (2), and hydrogen
was introduced up to 0.1 MPa. Then, while propylene was introduced,
the autoclave was temperature-increased to 80.degree. C. and
pressure-increased to a total pressure of 0.8 MPa, followed by
polymerization for 1 hour.
[0346] Then, the temperature and the pressure in the autoclave were
decreased, and the reaction product was taken out and poured into 2
L of methanol to deactivate the catalyst. The product was separated
by filtration and vacuum-dried to give a polypropylene. Table 4
shows the results.
Example 16
(1) Preparation of Magnesium Compound
[0347] A magnesium compound was obtained in the same manner as in
Example 15(1) except that the amount of iodine was changed to 0.24
g (1.9 mg atoms), the reaction temperature was changed to
50.degree. C. and the number of stirring was changed to 525 rpm.
Table 4 shows the results.
[0348] (2) Preparation of Solid Catalyst Component
[0349] A solid catalyst component was obtained in the same manner
as in Example 15(2) except that the magnesium compound prepared in
the above (1) was used.
[0350] (3) Propylene Slurry Polymerization
[0351] Propylene was polymerized in the same manner as in Example
15(3) except that the solid catalyst component prepared in the
above (2) was used. Table 4 shows the results.
Example 17
(1) Preparation of Magnesium Compound
[0352] A magnesium compound was obtained in the same manner as in
Example 15(1) except that the iodine was replaced with 0.30 g (6.3
mg atoms) of anhydrous magnesium chloride in Example 15(1). Table 4
shows the results.
[0353] (2) Preparation of Solid Catalyst Component
[0354] A solid catalyst component was obtained in the same manner
as in Example 15(2) except that the magnesium compound prepared in
the above (1) was used.
[0355] (3) Propylene Slurry Polymerization
[0356] Propylene was polymerized in the same manner as in Example
15(3) except that the solid catalyst component prepared in the
above (2) was used. Table 3 shows the results.
Example 18
(1) Preparation of Magnesium Compound
[0357] A magnesium compound was obtained in the same manner as in
Example 15(1) except that metallic magnesium having an oxidized
coating film with a thickness of 0.5 .mu.m (an average particle
size of 400 .mu.m, obtained by cut, milled and sieved under an
atmosphere of nitrogen gas) was used. Table 4 shows the
results.
[0358] (2) Preparation of Solid Catalyst Component
[0359] A solid catalyst component was obtained in the same manner
as in Example 15(2) except that the magnesium compound prepared in
the above (1) was used.
[0360] (3) Propylene Slurry Polymerization
[0361] Propylene was polymerized in the same manner as in Example
15(3) except that the solid catalyst component prepared in the
above (2) was used. Table 4 shows the results.
Comparative Example 13
[0362] (1) Preparation of Magnesium Compound
[0363] A magnesium compound was obtained in the same manner as in
Example 15(1) except that metallic magnesium having an oxidized
coating film with a thickness of 2 .mu.m (an average particle size
of 300 .mu.m, obtained by cut, milled and sieved in air) was used.
Table 4 shows the results.
[0364] (2) Preparation of Solid Catalyst Component
[0365] A solid catalyst component was obtained in the same manner
as in Example 15(2) except that the magnesium compound prepared in
the above (1) was used.
[0366] (3) Propylene Slurry Polymerization
[0367] Propylene was polymerized in the same manner as in Example
15(3) except that the solid catalyst component prepared in the
above (2) was used. Table 4 shows the results.
Comparative Example 14
[0368] (1) Preparation of Magnesium Compound
[0369] A magnesium compound was obtained in the same manner as in
Example 17(1) except that the same metallic magnesium as that in
Comparative Example 1 was used. Table 4 shows the results.
[0370] (2) Preparation of Solid Catalyst Component
[0371] A solid catalyst component was obtained in the same manner
as in Example 15(2) except that the magnesium compound prepared in
the above (1) was used.
[0372] (3) Propylene Slurry Polymerization
[0373] Propylene was polymerized in the same manner as in Example
15(3) except that the solid catalyst component prepared in the
above (2) was used. Table 4 shows the results.
Comparative Example 15
[0374] (1) Preparation of Magnesium Compound
[0375] A magnesium compound was obtained in the same manner as in
Example 15(1) except that the same metallic magnesium as that in
Comparative Example 13 was used and the reaction temperature was
changed to 60.degree. C. Table 4 shows the results.
[0376] (2) Preparation of Solid Catalyst Component
[0377] A solid catalyst component was obtained in the same manner
as in Example 15(2) except that the magnesium compound prepared in
the above (1) was used.
[0378] (3) Propylene Slurry Polymerization
[0379] Propylene was polymerized in the same manner as in Example
15(3) except that the solid catalyst component prepared in the
above (2) was used. Table 4 shows the results.
TABLE-US-00004 TABLE 4 Com. Com. Com. Item Unit Ex. 15 Ex. 16 Ex.
17 Ex. 18 Ex. 13 Ex. 14 Ex. 15 Support Thickness of Oxidized
(.mu.m) 0.05 0.05 0.05 0.5 2 2 2 Film of Metallic Mg Initiator
I.sub.2 I.sub.2 MgCl.sub.2 I.sub.2 I.sub.2 MgCl.sub.2 I.sub.2
Halogen Comp./Mg (gram atom 0.019 0.0057 0.019 0.019 0.019 0.019
0.019 molar) Reaction Temperature (.degree. C.) 78 50 78 78 78 78
60 Number of Rotation (rpm) 350 525 350 350 350 350 350 Average
Particle (.mu.m) 68 35 69 70 72 73 49 Size(D.sub.50) PDDI(P) 3.0
2.9 3.0 3.2 4.7 4.9 3.8 Sphericity(S) 1.30 1.28 1.32 1.31 1.50 1.53
1.40 Polymer Polymerization Activity (kg/g-Cat) 16.2 24.2 15.9 15.0
13.3 13.2 14.9 Stereoregularity (mol %) 98.4 98.4 98.3 98.3 98.2
98.2 98.3 ([mmmm]) Average Particle (.mu.m) 1,250 650 1,200 1,220
1,250 1,280 1,080 Size (D.sub.50) PDDI(P') 3.1 2.9 3.1 3.3 4.6 4.8
3.942 Sphericity(S') 1.29 1.28 1.32 1.31 1.52 1.55 1.64 Ex.:
Example Com. Ex.: Comparative Example Halogen Comp.: Halogen and/or
Halogen-containing Compound PDDI: Particle size Distribution
Index
INDUSTRIAL UTILITY
[0380] The invention can provide a magnesium compound, a solid
catalyst component for olefin polymerization, a catalyst for olefin
polymerization and a method for producing a polyolefin. A
polyolefin with a narrow particle size distribution and/or a nearly
spherical form can be obtained without reducing stereoregularity
and catalyst properties such as polymerization activity by using
the magnesium compound of the invention.
* * * * *