U.S. patent application number 15/284048 was filed with the patent office on 2017-01-26 for method for producing magnesium alcoholate.
The applicant listed for this patent is Nippon Soda Co., Ltd.. Invention is credited to Hitoshi KOBAYASHI.
Application Number | 20170022130 15/284048 |
Document ID | / |
Family ID | 48140841 |
Filed Date | 2017-01-26 |
United States Patent
Application |
20170022130 |
Kind Code |
A1 |
KOBAYASHI; Hitoshi |
January 26, 2017 |
METHOD FOR PRODUCING MAGNESIUM ALCOHOLATE
Abstract
The purpose of the present invention is to provide a spherical
or ellipsoidal magnesium alcoholate having a narrow particle size
distribution even when the particle size is small. The present
invention provides a method for producing a magnesium alcoholate by
adding in a portionwise manner to a reaction system and reacting,
metallic magnesium, an alcohol, and at least one of a halogen or a
halogen atom-containing compound in the reaction system under
alcohol reflux, which is a method for producing a magnesium
alcoholate characterized in that a mixture of metallic magnesium,
an alcohol, and at least one of a halogen or a halogen
atom-containing compound is added to the reaction system at each
portionwise addition.
Inventors: |
KOBAYASHI; Hitoshi;
(Joetsu-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Nippon Soda Co., Ltd. |
Tokyo |
|
JP |
|
|
Family ID: |
48140841 |
Appl. No.: |
15/284048 |
Filed: |
October 3, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14350259 |
Apr 7, 2014 |
9493586 |
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PCT/JP2012/076502 |
Oct 12, 2012 |
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15284048 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 4/06 20130101; C08F
10/00 20130101; C07C 29/70 20130101; C07C 31/30 20130101; C07C
29/70 20130101 |
International
Class: |
C07C 29/70 20060101
C07C029/70; C08F 10/00 20060101 C08F010/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 19, 2011 |
JP |
2011-229527 |
Claims
1. A method for producing a magnesium alcoholate comprising: adding
in a portionwise manner to a reaction system and reacting, metallic
magnesium, an alcohol, and at least one of a halogen or a halogen
atom-containing compound in a reaction system under alcohol reflux,
wherein a mixture of metallic magnesium, an alcohol, and at least
one of a halogen or a halogen atom-containing compound is added to
the reaction system at each portionwise addition.
2. The method for producing a magnesium alcoholate according to
claim 1, wherein a frequency of portionwise addition of said
mixture is less than 10 times.
3. The method for producing a magnesium alcoholate according to
claim 1, wherein a mass ratio of metallic magnesium and alcohol and
a mass ratio of metallic magnesium and halogen or halogen
atom-containing compound in said mixture that is added in a
portionwise manner is set to be substantially constant at each
portionwise addition.
4. The method for producing a magnesium alcoholate according to
claim 1, wherein an interval of portionwise addition of said
mixture is set to be substantially constant.
5. The method for producing a magnesium alcoholate according to
claim 1, wherein the halogen or the halogen-containing compound is
reacted in an amount of 0.0001 gram atom or more, relative to one
gram atom of the metallic magnesium.
6-7. (canceled)
Description
TECHNICAL FIELD
[0001] The present invention relates to a method for producing a
magnesium alcoholate used for preparing a solid catalyst component
for olefin polymerization or the like.
[0002] Priority is claimed on Japanese Patent Application No.
2011-229527, filed Oct. 19, 2011, the content of which is
incorporated herein by reference.
BACKGROUND ART
[0003] As a solid catalyst component for olefin polymerization,
spherical magnesium alcoholates having an average particle diameter
of 60 .mu.m or more, a less number of fine particles, and a
sufficient strength have been desired. As a method for producing
such magnesium alcoholates, for example, there is a method
disclosed in Patent Document 1 that the final ratio of the metallic
magnesium and alcohol used in the reaction system is from 1/4 to
1/25 in mass ratio, and that particulate metallic magnesium having
a diameter of not more than 500 .mu.m and the alcohol are added
continuously or intermittently in a portionwise manner to the
reaction system under alcohol reflux and allowed to react for 100
to 1,200 minutes. In addition, in this method, it has been
described that it is preferable to carry out the addition of each
of the metallic magnesium and alcohol in 10 or more separate
portions, and also in a manner so that the intervals of addition is
a combination of intervals selected arbitrarily from the range of
10 to 120 minutes and the total addition time is within the range
of not more than 1,200 minutes. It has been described that by using
this method, particulate matter of dialkoxymagnesium having
spherical or ellipsoidal particle shapes with an average particle
diameter represented by D.sub.50 in the range of 60 to 200 .mu.m, a
bulk specific gravity of 0.2 to 0.7 g/ml, numerous internal pores
with pore sizes from 0.1 to 5 .mu.m as determined by TEM
observation, and a particle size distribution represented by
(D.sub.90-D.sub.10)/D.sub.50 of not more than 1, can be obtained,
and the breaking strength of the aggregated particulate matter is
from 0.5 to 10 MPa. It has been described that in the synthetic
reaction according to this method, the use of a catalyst is
preferred, while listing iodine and the like as examples of useful
catalysts, and moreover, this catalyst may be initially added
collectively to the reaction system or may be added while adjusting
the amount in accordance with the portionwise addition of raw
materials.
[0004] Further, it has been disclosed in Patent Document 2 that by
reacting metallic magnesium, an alcohol, and 0.0001 gram atom or
more of a halogen or halogen-containing compound containing a
halogen, relative to one gram atom of the above metallic magnesium,
it is possible to produce an alkoxy group-containing magnesium
compound having an average particle diameter from 1 to 300 .mu.m
and also a particle size distribution index (P) represented by the
following formula (1) of P<5.0 which indicates a narrow particle
size distribution, and which can be used as it is without particle
size adjusting treatments such as pulverization and classification
(formula (1): P=D.sub.90/D.sub.10, where D.sub.90 denotes a
particle diameter corresponding to the cumulative weight fraction
of 90%, and D.sub.10 denotes a particle diameter corresponding to
the cumulative weight fraction of 10%). In this document, it has
been described that there is no need to introduce the total amount
of each of metallic magnesium, an alcohol, and a halogen and/or
halogen-containing compound into a reaction tank from the
beginning, and the introduction may be conducted in separate
portions.
CITATION LIST
Patent Documents
[0005] Patent Document 1: Japanese Unexamined Patent Application,
First Publication No. 2007-297371
[0006] Patent Document 2: Japanese Unexamined Patent Application,
First Publication No. Hei 4-368391
SUMMARY OF INVENTION
Technical Problem
[0007] Among all the known magnesium alcoholates described above,
although those having a particle size distribution represented by
(D.sub.90-D.sub.10)/D.sub.50 of not greater than 1 have been known,
those having an even smaller distribution of less than 0.78 have
not been known, and thus the magnesium alcoholates with an even
smaller particle size distribution have been desired. In addition,
those having an average particle diameter represented by D.sub.50
of less than 60 .mu.m and a particle size distribution represented
by (D.sub.90-D.sub.10)/D.sub.50 of not greater than 1 have not been
known either, and thus the magnesium alcoholates having a small
particle size distribution even when the particle size is small
have also been desired.
[0008] Further, in Patent Document 1, although it has been
described that the catalyst used may be added to the reaction
system while adjusting the amount in accordance with the
portionwise addition of the raw materials, it has been suggested
that in those cases where the frequency of portionwise addition of
the raw materials is low, for example, when it is about four to
five times, the desired product (magnesium alcoholates having an
average particle diameter represented by D.sub.50 of 60 to 200
.mu.m and also a particle size distribution represented by
(D.sub.90-D.sub.10)/D.sub.50 of not greater than 1) cannot be
obtained.
[0009] In addition, in Patent Document 2, it has been described
that the suitable frequency of portionwise additions is 5 to 10
times, and that a method is preferred in which the total amount of
an alcohol is added from the beginning and metallic magnesium is
then divided into several portions and added.
[0010] Furthermore, there are neither descriptions nor suggestions,
in both Patent Documents 1 and 2, on a specific method for
portionwise addition, for example, the way the portionwise addition
is carried out and the optimal ratio of each of the raw materials
that are added in a portionwise manner.
[0011] The aim of the present invention is to provide a spherical
or ellipsoidal magnesium alcoholate having a narrow particle size
distribution even when the particle size is small.
Solution to Problem
[0012] As a result of intensive studies in order to solve the above
problems, the inventors of the present invention found that it is
possible to solve the above problems by always adding a mixture
containing metallic magnesium, an alcohol, and a halogen or halogen
atom-containing compound at each portionwise addition, thereby
leading to completion of the present invention.
[0013] That is, the present invention relates to a method for
producing a magnesium alcoholate by adding in a portionwise manner
to a reaction system and reacting, metallic magnesium, an alcohol,
and at least one of a halogen or a halogen atom-containing compound
under alcohol reflux, which is a method for producing a magnesium
alcoholate characterized in that a mixture of metallic magnesium,
an alcohol, and at least one of a halogen or a halogen
atom-containing compound is added to the reaction system at each
portionwise addition.
[0014] In the method for producing a magnesium alcoholate according
to the present invention, it is preferable that the frequency of
portionwise addition of the aforementioned mixture be set to less
than 10 times; it is preferable that the mass ratio of metallic
magnesium and alcohol and the mass ratio of metallic magnesium and
halogen or halogen atom-containing compound in the aforementioned
mixture added portionwise be substantially constant at each
portionwise addition; and moreover, it is preferable that the
interval between the portionwise additions be constant.
Advantageous Effects of Invention
[0015] By using the method for producing a magnesium alcoholate
according to the present invention, it is possible to obtain a
magnesium alcoholate having an unprecedented quality in which the
particle size distribution, particle diameter, and particle type
are controlled.
[0016] In other words, by this production method, it is possible to
produce a magnesium alcoholate as a particulate matter having a
particle size distribution represented by
(D.sub.90-D.sub.10)/D.sub.50 of less than 0.78 and a spherical or
ellipsoidal particle shape, or a magnesium alcoholate in the form
of a particulate matter having an average particle diameter
represented by D.sub.50 of less than 60 .mu.m, a particle size
distribution represented by (D.sub.90-D.sub.10)/D.sub.50 of not
greater than 1, and a spherical or ellipsoidal particle shape.
[0017] By preparing a catalyst for olefin polymerization using the
magnesium alcoholate obtained by this method in which the particle
size distribution, particle diameter, and particle type are
controlled, an olefin polymer can be obtained in which the particle
size distribution, particle diameter, and particle type are
controlled.
DESCRIPTION OF EMBODIMENTS
[0018] The values D.sub.10, D.sub.50, and D.sub.90 used in the
present invention denote the particle diameters at 10%, 50%, and
90%, in terms of cumulative particle size. That is, for example,
D.sub.10 indicates a particle diameter at the time when the
particle size distribution of the particulate matter is measured
and the integrated value of the mass of the particulate matter
reached 10% by mass. Accordingly, D.sub.50 denotes an intermediate
value of the particle diameter of the entire particulate matter,
and thus this indicates the average particle diameter.
<Method for Producing Magnesium Alcoholate>
[0019] A method for producing a magnesium alcoholate according to
the present invention (production method of the present invention)
is a method for producing a magnesium alcoholate by adding in a
portionwise manner to a reaction system and reacting, metallic
magnesium, an alcohol, and at least one of a halogen or a halogen
atom-containing compound under alcohol reflux, which is
characterized in that a mixture of metallic magnesium, an alcohol,
and at least one of a halogen or a halogen atom-containing compound
is added to the reaction system at each portionwise addition.
[0020] The metallic magnesium used in the production method of the
present invention may be in any form as long as the reactivity is
favorable. In other words, any of those having a granular, ribbon
or powder form can be used. However, it should be noted that from
the viewpoint of reactivity, the degree of oxidation at the surface
of metallic magnesium particles is preferably as low as possible,
and those in which magnesium oxide is formed on the surface are not
preferable for use. Therefore, for example, those stored under the
atmosphere of an inert gas such as nitrogen, and those having a
metal surface treated with a solvent that does not adversely affect
the reaction to prevent surface oxidation are preferred.
[0021] In order to set the average particle diameter of the
magnesium alcoholate to be produced from 10 to 50 .mu.m, the
particle size of the used metallic magnesium is preferably not
greater than 350 .mu.m, and more preferably from 88 to 350 .mu.m.
The metallic magnesium having a particle size within this range is
suitable in terms of maintaining uniform reactivity.
[0022] In addition, in order to set the average particle diameter
of the magnesium alcoholate to be produced to 60 .mu.m or greater,
it is preferable to use a metallic magnesium in the form of a
particulate matter having a particle size of not greater than 500
.mu.m, and it is more preferable to use a metallic magnesium in the
form of a particulate matter composed of fine particles having an
average particle diameter represented by D.sub.50 of 50 to 500
.mu.m and a particle size distribution represented by
(D.sub.90-D.sub.10)/D.sub.50 of not more than 2. The form of the
particulate matter may be a powder form.
[0023] Any alcohol can be used as the alcohol used in the
production method of the present invention, but it is preferable to
use a lower alcohol of 1 to 6 carbon atoms. In particular, it is
preferable to use ethanol because magnesium compounds with
significantly improved catalytic performance can be obtained.
[0024] Although the purity and water content of alcohol are not
limited, those with a low water content are preferred. More
specifically, it is preferable to use an alcohol having a water
content of not more than 1%, and it is more preferable to use an
alcohol having a water content of not more than 2,000 ppm. When an
alcohol with a high water content is used, magnesium hydroxide
tends to form easily on the surface of metallic magnesium. Further,
in order to obtain a magnesium alcoholate having a more favorable
morphology, the water content in an alcohol is preferably as low as
possible, and in general, it is preferably not more than 200
ppm.
[0025] The ratio of metallic magnesium and alcohol used at the time
of completing the addition of the entire amount of raw materials to
the reaction system is preferably from 1/4 to 1/25 in terms of mass
ratio. By setting the amount of alcohol to not less than 4 relative
to the amount of metallic magnesium, the reaction can be allowed to
proceed sufficiently, the remaining of unreacted magnesium can be
suppressed, and the particle diameter can be controlled easily to
achieve the target value. In addition, by setting the amount of
alcohol to not more than 25 relative to the amount of metallic
magnesium, the amount of alcohol incorporated in the product formed
in the reaction (particulate products are mainly formed) can be
reduced. As a result, it is possible to suppress the number of
voids generated when the alcohol in the product is removed by
evaporation by a drying treatment, and to prevent the bulk specific
gravity from becoming too small.
[0026] Although the type of halogen used in the production method
of the present invention is not particularly limited, chlorine,
bromine, or iodine is preferred, and in particular, iodine is
suitably used.
[0027] In addition, there is no limitation on the type of halogen
atom-containing compound used in the production method of the
present invention either, and any compounds can be used as long as
they are compounds containing a halogen atom within the chemical
formula thereof. More specifically, examples thereof include
MgCl.sub.2, Mg(OEt)Cl, Mg(OEt)I, MgBr.sub.2, CaCl.sub.2, NaCl, and
KBr, and among these, it is preferable to use MgCl.sub.2 or
MgI.sub.2. The state, shape, particle size or the like of the
halogen or halogen atom-containing compound added to the reaction
system are not particularly limited, and any of those may be
selected. For example, those in the form of a solution dissolved in
an alcohol-based solvent such as ethanol can be used.
[0028] The amount of halogen or halogen atom-containing compound
used in the production method of the present invention is not
particularly limited as long as the amount is sufficient for the
reaction with metallic magnesium and alcohol, but is preferably not
less than 0.0001 gram atom, more preferably not less than 0.0005
gram atom, and even more preferably not less than 0.001 gram atom,
relative to 1 gram atom of metallic magnesium, at the time when the
addition of the entire amount of raw materials to the reaction
system is completed. The halogen or halogen atom-containing
compound acts as a catalyst for the reaction with metallic
magnesium and alcohol, and it is preferable to adjust the total
amount added and the amount added at the time of each portionwise
addition to the reaction system in accordance with the portionwise
addition of other raw materials.
[0029] In the present invention, each of the halogen and halogen
atom-containing compound may be used alone, or two or more types
thereof may be used in combination. In addition, it is also
possible to use a halogen and a halogen atom-containing compound
concurrently. When used in combination, at the time when the
addition of the entire amount of raw materials to the reaction
system is completed, the amount of total halogen in the reaction
system is preferably not less than 0.0001 gram atom, more
preferably not less than 0.0005 gram atom, and even more preferably
not less than 0.001 gram atom, relative to 1 gram atom of metallic
magnesium.
[0030] The upper limit for the use amount of halogen and/or halogen
atom-containing compound added to the reaction system is not
particularly limited, but is preferably less than 0.06 gram atom,
relative to 1 gram atom of metallic magnesium.
[0031] The raw materials such as metallic magnesium, alcohol, and
at least one of a halogen or a halogen atom-containing compound are
divided into two or more portions and added to the reaction system.
The portionwise addition of raw materials to the reaction system is
conducted under the reflux of an alcohol-based solvent, preferably
the same alcohol as the raw material. In the production method of
the present invention, the mixture added in a portionwise manner
must contain all three types of materials, that is, metallic
magnesium, an alcohol, and at least one of a halogen or a halogen
atom-containing compound. By newly adding, not only metallic
magnesium and an alcohol, but also a halogen or halogen
atom-containing compound to the reaction system at each portionwise
addition, the particle density (apparent specific gravity) can be
increased, and moreover, the amount of amorphous fine particles can
be reduced, and accompanied with this, the yield of the product can
be increased. Although the frequency of portionwise addition of the
aforementioned mixture to the reaction system is not particularly
limited as long as it is not less than twice, the addition is
preferably conducted by dividing the mixture into 2 or more
portions but less than 10 portions, and more preferably it is
conducted by dividing the mixture into 2 to 5 portions.
[0032] The mixture added to the reaction system at the time of
portionwise addition may be any one of those containing all of
metallic magnesium, an alcohol and at least one of a halogen or a
halogen atom-containing compound. That is, in the aforementioned
mixture, the mass ratio of metallic magnesium and alcohol and the
mass ratio of metallic magnesium and halogen and/or halogen
atom-containing compound are not particularly limited, and may be
different at each portionwise addition, or the mixtures having the
same composition may be added at the time of all the portionwise
additions. Further, the portionwise addition may be performed with
a material ratio different from the final addition ratio (the ratio
between the total added amounts to the reaction system). For
example, it is possible to increase the ratio of metallic magnesium
in the early stage of the reaction from the final addition ratio
and decrease the ratio of metallic magnesium added in the later
stage. In the production method of the present invention, it is
preferable to set the mass ratio of metallic magnesium and alcohol
and the mass ratio of metallic magnesium and halogen or halogen
atom-containing compound in the aforementioned mixture that is
added in a portionwise manner to be substantially constant at each
portionwise addition.
[0033] Further, the amount of mixture added to the reaction system
in one portionwise addition is also not particularly limited, and
may be different at each portionwise addition, or substantially the
same amount of mixture may be added to the reaction system at each
portionwise addition.
[0034] For example, the addition may be conducted by sequentially
increasing the added amount. In the production method of the
present invention, it is preferable to add a constant amount of
mixture every time.
[0035] In the production method of the present invention, it is
preferable to add the raw materials so that the following synthetic
reaction is allowed to proceed only after the primary particles of
the dialkoxymagnesium produced in the reaction system deposit on
the dialkoxymagnesium that is already present in the system. The
interval of the portionwise addition differs depending on other
conditions such as the size of the reaction apparatus and the
temperature, but is preferably adjusted so as to be an interval of
10 to 120 minutes. In other words, it is preferable to add the next
raw material at a stage where dialkoxymagnesium is produced by the
reaction and the generation of H.sub.2 is almost completed (stage
where unreacted metallic magnesium is substantially absent) after
the portionwise addition in the previous stage. It is preferable to
add, at the time point where the reaction of added magnesium is
almost completed, the next portion of magnesium, and it is
preferable to add, so that the final ratio of metallic magnesium
and alcohol be within the range from 1/4 to 1/25 in terms of weight
ratio.
[0036] Note that in order to allow the reaction to proceed
smoothly, it is preferable to react metallic magnesium in a
relatively small amount of alcohol at an early stage of the
reaction, and to adjust the concentration by further adding alcohol
after adding all of metallic magnesium.
[0037] The interval of the portionwise addition of the
aforementioned mixture to the reaction system is not particularly
limited, and can be adjusted as appropriate by taking into
consideration the amount, composition, or the like of the mixture
that is added in a portionwise manner. In the production method of
the present invention, it is preferable to sequentially add at a
constant interval.
[0038] By the addition interval of the mixture described above, the
D.sub.50 value of the obtained magnesium alcoholate can be
controlled. For example, it is possible to obtain a magnesium
alcoholate having a small particle size by shortening the addition
interval, and it is possible to obtain a magnesium alcoholate
having a large particle size by increasing the addition interval,
respectively.
[0039] Although the total reaction time depends on the scale
thereof, the time point at which the reaction is completed can be
determined by the completion of hydrogen generation.
[0040] After the final addition of the aforementioned mixture, it
is preferable to further conduct an aging process at a temperature
from 70.degree. C. to the reflux temperature of the solvent,
following the completion of hydrogen generation, to thereby
stabilize the produced particles. The aging time can be altered as
appropriate in accordance with the intended particle diameter,
particle size distribution and bulk specific gravity of magnesium
alcoholate. The reaction temperature at the time of aging may be
from 70.degree. C. to the reflux temperature of the solvent, and
the stirring speed is from 50 to 500 rpm, and the reaction
temperature and the stirring speed can be selected in accordance
with the intended particle diameter, particle size distribution and
bulk specific gravity of magnesium alcoholate.
[0041] More specifically, by reducing the stirring speed (the
transfer rate of the reaction solution), the particle diameter of
magnesium alcoholate can be increased, and by increasing the
stirring speed, the particle diameter of magnesium alcoholate can
be decreased.
<Magnesium Alcoholate>
[0042] According to the production method of the present invention,
a magnesium alcoholate in which the particle size distribution,
particle diameter and particle type are controlled can be produced.
For example, it is possible to produce a magnesium alcoholate in
the form of particulate matter having the D.sub.50 particle
diameter within the range from 10 to 200 .mu.m, in particular,
particulate matter having a large particle diameter from 80 to 200
.mu.m which enables the omission of a pelleting process at the time
of molding the olefin polymers produced when used in a
polymerization catalyst.
[0043] In addition, according to the production method of the
present invention, a magnesium alcoholate can be produced as
particulate matter having a relatively uniform particle diameter
distribution. For example, it is possible to obtain particulate
matter of a magnesium alcoholate having a particle size
distribution represented by (D.sub.90-D.sub.10)/D.sub.50 of not
more than 1, preferably less than 0.78. In particular, even when
the D.sub.50 particle size is less than 60 .mu.m, it is possible to
make the aforementioned value of particle size distribution to less
than 1.
[0044] That is, the magnesium alcoholate according to the present
invention is characterized as being a particulate matter with a
particle size distribution represented by
(D.sub.90-D.sub.10)/D.sub.50 of less than 0.78 and having a
spherical or ellipsoidal particle shape. In addition, as another
aspect, the magnesium alcoholate according to the present invention
is characterized as being a particulate matter having an average
particle diameter represented by D.sub.50 of less than 60 .mu.m, a
particle size distribution represented by
(D.sub.90-D.sub.10)/D.sub.50 of not more than 1, and a spherical or
ellipsoidal particle shape.
[0045] Further, the magnesium alcoholate of the present invention
may be composed of porous aggregates of the spherical, ellipsoidal,
scale-like, or needle-like primary particles of magnesium
alcoholate having a particle diameter of 1 to 10 .mu.m, and
preferably does not substantially contain particles having a
particle diameter of 10 .mu.m or less. The pores present inside the
particulate matter and having a pore diameter of 0.1 to 5 .mu.m as
observed by a transmission electron microscope (TEM) are thought to
be those composed of gaps between the particles that are formed
when the primary particles aggregated as described above. When
these gaps between the particles become 10 .mu.m or greater, there
are some cases where the bonds between the primary particles are
weak, thereby making the strength of the particulate matter
insufficient.
[0046] As described above, the magnesium alcoholate of the present
invention is a particulate matter having a narrow particle size
distribution and a spherical or ellipsoidal particle shape even
when the particle size is small. For this reason, in particular, it
can be used suitably as a solid catalyst component for olefin
polymerization.
[0047] In order to prepare a catalyst for olefin polymerization by
using the magnesium alcoholate of the present invention as a
starting material, the magnesium alcoholate (particulate matter of
dialkoxymagnesium) is brought into contact with a halide of
tetravalent titanium and an electron donating compound by a known
method to produce a catalyst component, and then an organic
aluminum compound is allowed to act thereon. Examples of the halide
of tetravalent titanium include titanium tetrachloride and alkoxy
titanium halides. Examples of the electron donating compounds
include alcohols, ethers, esters, and organic silicon compounds
such as alkoxysilane. Examples of the aluminum compounds include
triethylaluminum and diethylalminum chloride.
EXAMPLES
[0048] A more detailed description of the present invention is
presented below based on a series of examples, although the present
invention is in no way limited by these examples.
Example 1
[0049] A reflux condenser connected with an integrating-type gas
meter, a thermometer, a dropping funnel for ethanol, as well as a
nitrogen inlet tube interposed with a gas flow meter were installed
onto a 500 ml four-necked flask equipped with a stirrer. After
sufficiently replacing the inside of the reaction system with
nitrogen, 60 g of anhydrous ethanol (water content: 200 ppm) and
0.4 g of iodine were charged and dissolved therein. 6.1 g of
metallic magnesium (particle size: 300 to 149 .mu.m) was charged
thereinto, and under stirring at a stirring intensity of
2.60.times.10.sup.11 rpm.sup.3mm.sub.2, the temperature was raised
up to the reflux temperature of the alcohol in an oil bath. The
reaction was stabilized within 10 minutes from the charging of the
metallic magnesium, and thereafter, 40 g of ethanol, 6.1 g of
metallic magnesium and 0.3 g of iodine were charged at a time every
10 minutes and in three separate portions to allow the reaction to
continue. The total amount of the charged metallic magnesium was
24.4 g, and the amount of ethanol used at this point was 180 g.
Further, when 183 g of ethanol of the same quality as that of the
one used earlier was added dropwise over 1 hour to allow the ageing
reaction to continue until no hydrogen gas was detectable in the
exhaust gas, it took 8 hours in total from the initial
charging.
[0050] The ethanol/metallic magnesium ratio (mass ratio of the
total amount of ethanol and the total amount of metallic magnesium
that were charged into the reaction system) was 16/1. After the
completion of the reaction, the liquid in the reaction system was
dried under reduced pressure in a rotary evaporator to obtain 107 g
(yield: 94%) of magnesium ethylate. As a result of observing the
thus obtained magnesium ethylate using a scanning electron
microscope (JSM-5300 manufactured by JEOL Ltd. DATUM Solution
Business Operations) at 1,000-fold magnification with an
accelerating voltage of 20 kV, subspherical particles made of
those, each one of which is a strip-like particle, that were
densely overlapping were obtained, although the particle surface
was smooth. The degree of sphericity (S) as determined from the
pictures taken was 1.01. When the particle size distribution was
measured using a laser diffraction type particle size distribution
measuring apparatus (HELOS & RODOS manufactured by Sympatec
GmbH), D.sub.50 was 40.98 .mu.m, D.sub.10 was 25.14 .mu.m, D.sub.90
was 55.58 .mu.m, and the particle size distribution had a narrow
distribution width of 0.743. In addition, the measurement result of
bulk specific gravity (looseness) (apparent specific gravity) was
0.301 g/ml. The above results are summarized and shown in Table
2.
Examples 2 to 7
[0051] The measurements in these Examples were carried out in the
same manner as in Example 1 with the exception that the numerical
values corresponding to each of the conditions used in Example 1
were changed to the numerical values set forth in Table 1. The
results are summarized and shown in Table 2. In Table 1, "Mg"
represents magnesium, "I" represents iodine, and "frequency" of the
"portionwise addition" represents the frequency of portionwise
addition, respectively.
TABLE-US-00001 TABLE 1 Total amount Amount of portionwise addition
(g) Stirring Addition used (g) Charging Portionwise addition
intensity interval Mg I Mg I Mg I Frequency (rpm.sup.3 mm.sub.2)
(minutes) Ex. 1 24.4 1.3 6.1 0.4 6.1 0.3 3 2.60 .times. 10.sup.11
10 Ex. 2 18.4 1.3 6.1 0.4 4.1 0.3 3 2.60 .times. 10.sup.11 10 Ex. 3
24.4 1.5 6.1 0.6 6.1 0.3 3 2.60 .times. 10.sup.11 15 Ex. 4 24.4 1.5
6.1 0.6 6.1 0.3 3 1.60 .times. 10.sup.11 15 Ex. 5 24.4 1.5 6.1 0.6
6.1 0.3 3 1.60 .times. 10.sup.11 20 Ex. 6 24.4 1.98 6.1 0.6 6.1
0.46 3 6.75 .times. 10.sup.10 20 Ex. 7 24.4 1.98 6.1 0.6 6.1 0.46 3
6.75 .times. 10.sup.10 20
TABLE-US-00002 TABLE 2 Product Particle size Apparent specific
yield (%) D.sub.50 (.mu.m) distribution gravity (g/ml) Example 1
93.8 40.98 0.743 0.301 Example 2 93.2 46.64 0.536 0.311 Example 3
94.5 48.49 0.501 0.295 Example 4 96.3 51.75 0.566 0.291 Example 5
94.8 67.77 0.511 0.301 Example 6 93.5 73.83 0.562 0.31 Example 7
94.0 71.34 0.487 0.301
Example 8
[0052] A reflux condenser connected with an integrating-type gas
meter, a thermometer, a dropping funnel for ethanol, as well as a
nitrogen inlet tube interposed with a gas flow meter were installed
onto a 500 ml four-necked flask equipped with a stirrer. After
sufficiently replacing the inside of the reaction system with
nitrogen, 100 g of anhydrous ethanol (water content: 200 ppm) and
0.6 g of iodine were charged and dissolved therein. 8.1 g of
metallic magnesium (particle size: 300 to 149 .mu.m) was charged
thereinto, and under stirring, the temperature was raised up to the
reflux temperature of the alcohol in an oil bath. Since the
reaction was stabilized within 10 minutes from the charging of the
metallic magnesium, 10 g of ethanol, 4.1 g of metallic magnesium,
and 0.3 g of iodine were additionally added after 10 minutes from
the point of charging the metallic magnesium, and after another 10
minutes, 40 g of ethanol, 7.1 g of metallic magnesium, and 0.2 g of
iodine were additionally added, and after another 10 minutes, 30 g
of ethanol, 5.1 g of metallic magnesium, and 0.1 g of iodine were
additionally added, thereby dividing the addition into three
separate portions to allow the reaction to continue. The total
amount of the charged metallic magnesium was 24.4 g, and the amount
of ethanol used at this point was 180 g. Further, when 183 g of
ethanol of the same quality as that of the one used earlier was
added dropwise over 1 hour to allow the ageing reaction to continue
until no hydrogen gas was detectable in the exhaust gas, it took 5
hours in total from the initial charging.
[0053] The ethanol/metallic magnesium ratio was 15/1. After the
completion of the reaction, the liquid in the reaction system was
dried under reduced pressure in a rotary evaporator to obtain 105 g
(yield: 92.1%) of magnesium ethylate. When the particle size
distribution was measured in the same manner as in Example 1,
D.sub.50 was 48.34 .mu.m, D.sub.10 was 36.36 .mu.m, d.sub.90 was
60.12 .mu.m, and the particle size distribution had a narrow
distribution width of 0.492. In addition, the measurement result of
bulk specific gravity (looseness) was 0.288 g/ml.
Example 9
[0054] A reflux condenser connected with an integrating-type gas
meter, a thermometer, a dropping funnel for ethanol, as well as a
nitrogen inlet tube interposed with a gas flow meter were installed
onto a 500 ml four-necked flask equipped with a stirrer. After
sufficiently replacing the inside of the reaction system with
nitrogen, 60 g of anhydrous ethanol (water content: 200 ppm) and
0.4 g of iodine were charged and dissolved therein. 6.1 g of
metallic magnesium (particle size: 210 to 149 .mu.m) was charged
thereinto, and under stirring, the temperature was raised up to the
reflux temperature of the alcohol in an oil bath. Since the
reaction was stabilized within 10 minutes from the charging of the
metallic magnesium, 40 g of ethanol, 6.1 g of metallic magnesium,
and 0.3 g of iodine were additionally added after 10 minutes from
the point of charging the metallic magnesium, and after another 15
minutes, 40 g of ethanol, 6.1 g of metallic magnesium, and 0.3 g of
iodine were additionally added, and after another 5 minutes, 40 g
of ethanol, 6.1 g of metallic magnesium, and 0.3 g of iodine were
additionally added, thereby dividing the addition into three
separate portions to allow the reaction to continue.
[0055] The total amount of the charged metallic magnesium was 24.4
g, and the amount of ethanol used at this point was 180 g. Further,
when 183 g of ethanol of the same quality as that of the one used
earlier was added dropwise over 1 hour to allow the ageing reaction
to continue until no hydrogen gas was detectable in the exhaust
gas, it took 5 hours in total from the initial charging.
[0056] The ethanol/metallic magnesium ratio was 15/1. After the
completion of the reaction, the liquid in the reaction system was
dried under reduced pressure in a rotary evaporator to obtain 107 g
(yield: 93.8%) of magnesium ethylate. When the particle size
distribution was measured in the same manner as in Example 1,
D.sub.50 was 57.1 .mu.m, D.sub.10 was 43.03 .mu.m, D.sub.90 was
71.06 .mu.m, and the particle size distribution had a narrow
distribution width of 0.491. In addition, the measurement result of
bulk specific gravity (looseness) was 0.319 g/ml.
Examples 10 to 27
[0057] The measurements in these Examples were carried out in the
same manner as in Example 1 with the exception that the numerical
values corresponding to each of the conditions used in Example 1
were changed to the numerical values set forth in Table 3. The
results are summarized and shown in Table 4.
[0058] In Example 17, the amount of ethanol used was 183 g at the
time of charging and was 120 g at the time of each portionwise
addition, the amount of ethanol at the point where all of the
charging had been completed was 543 g, and another 549 g was
further added as a diluent.
TABLE-US-00003 TABLE 3 Metallic Mg apparent Total specific amount
Amount of portionwise addition (g) Stirring Addition gravity used
(g) Charging Portionwise addition intensity interval (g/ml) Mg I Mg
I Mg I Frequency (rpm.sup.3 mm.sub.2) (minutes) Ex. 10 0.838 24.4
1.3 6.1 0.4 6.1 0.3 3 2.60 .times. 10.sup.11 10 Ex. 11 0.838 24.4
1.3 6.1 0.4 6.1 0.3 3 6.75 .times. 10.sup.10 10 Ex. 12 0.838 24.4
1.3 6.1 0.4 6.1 0.3 3 2.60 .times. 10.sup.11 20 Ex. 13 0.838 24.4
1.3 6.1 0.4 6.1 0.3 3 6.75 .times. 10.sup.10 20 Ex. 14 0.855 24.4
1.3 6.1 0.4 6.1 0.3 3 2.60 .times. 10.sup.11 10 Ex. 15 0.855 24.4
1.3 6.1 0.4 6.1 0.3 3 6.75 .times. 10.sup.10 10 Ex. 16 0.855 24.4
1.98 6.1 0.6 6.1 0.46 3 2.60 .times. 10.sup.11 15 Ex. 17 0.855 73.2
5.94 18.3 1.8 18.3 1.38 3 6.75 .times. 10.sup.10 15 Ex. 18 0.855
24.4 1.3 6.1 0.4 6.1 0.3 3 2.60 .times. 10.sup.11 25 Ex. 19 0.769
24.4 1.3 6.1 0.4 6.1 0.3 3 2.60 .times. 10.sup.11 10 Ex. 20 0.769
24.4 1.3 6.1 0.4 6.1 0.3 3 1.60 .times. 10.sup.11 10 Ex. 21 0.769
24.4 1.3 6.1 0.4 6.1 0.3 3 2.60 .times. 10.sup.11 15 Ex. 22 0.769
24.4 1.3 6.1 0.4 6.1 0.3 3 1.60 .times. 10.sup.11 15 Ex. 23 0.769
24.4 1.3 6.1 0.4 6.1 0.3 3 1.60 .times. 10.sup.11 15 Ex. 24 0.769
24.4 1.3 6.1 0.4 6.1 0.3 3 2.60 .times. 10.sup.11 20 Ex. 25 0.769
24.4 1.3 6.1 0.4 6.1 0.3 3 1.60 .times. 10.sup.11 20 Ex. 26 0.769
24.4 1.3 6.1 0.4 6.1 0.3 3 6.75 .times. 10.sup.10 20 Ex. 27 0.769
24.4 1.3 6.1 0.4 6.1 0.3 3 6.75 .times. 10.sup.10 25
TABLE-US-00004 TABLE 4 Product Particle size Apparent specific
yield (%) D.sub.50 (.mu.m) distribution gravity (g/ml) Example 10
94.3 57.1 0.458 0.27 Example 11 94.6 67.51 0.459 0.302 Example 12
95.1 67.62 0.467 0.303 Example 13 96.3 76.58 0.539 0.292 Example 14
93.2 46.64 0.536 0.311 Example 15 96.8 57.75 0.466 0.27 Example 16
88.7 55.74 0.807 0.29 Example 17 93.1 64.26 0.523 0.3 Example 18
97.3 59.19 0.513 0.26 Example 19 94.3 45.15 0.553 0.302 Example 20
94.3 50.54 0.578 0.303 Example 21 99.11 48.72 0.485 0.28 Example 22
96.3 51.75 0.566 0.291 Example 23 94.2 52.9 0.571 0.293 Example 24
93.8 51.2 0.576 0.32 Example 25 95.7 54.43 0.521 0.296 Example 26
92 58.63 0.481 0.283 Example 27 93.1 60.33 0.521 0.298
Comparative Example 1
[0059] Using the same apparatus as in Example 1, 181 g of anhydrous
ethanol, 1.3 g of iodine, and 24.4 g of metallic magnesium (350 to
210 .mu.m) were charged thereto, and the temperature was raised
under alcohol reflux to initiate the reaction. The aging reaction
was conducted for 5 hours to complete the reaction. The particles
obtained by drying had a degree of sphericity (S) of 1.25, D.sub.50
was 46.69 .mu.m, D.sub.10 was 24.23 .mu.m, D.sub.90 was 70.87
.mu.m, the particle size distribution had a wide distribution width
of 0.999, the particle surface was not dense, and the degree of
sphericity was somewhat low with a large number of irregularities.
In addition, the bulk specific gravity (looseness) was 0.203
g/ml.
Comparative Example 2
[0060] A 500 ml four-necked, round-bottom flask was mounted with a
stirring device, a dropping funnel and a thermometer, and 61 g of
ethanol, 1.3 g of iodine and 6.1 g of granular metallic magnesium
were first charged thereto under a stream of nitrogen, and were
heated to reflux at a bath temperature of 80.degree. C. After 10
minutes, 40 g of ethanol and 6.1 g of metallic magnesium were
additionally added, and after another 10 minutes, 40 g of ethanol
and 6.1 g of metallic magnesium were additionally added, and after
another 10 minutes, 40 g of ethanol and 6.1 g of metallic magnesium
were additionally added, and after another 10 minutes, 185 g of
ethanol was added dropwise over 1 hour, followed by 5 hours of
aging process to complete the reaction. Then, after being cooled to
room temperature, ethanol was removed by evaporation under reduced
pressure, followed by drying to obtain 79.9 g of magnesium ethylate
(yield: 75.9%), which was the intended product.
[0061] The thus obtained particles had a D.sub.50 of 46.69 .mu.m, a
D.sub.10 of 24.23 .mu.m, and a D.sub.90 of 70.87 .mu.m, and the
particle size distribution had a wide distribution of 0.999. The
bulk specific gravity (looseness) was a small value of 0.203
g/ml.
INDUSTRIAL APPLICABILITY
[0062] By using the method for producing a magnesium alcoholate
according to the present invention, it is possible to obtain a
magnesium alcoholate having an unprecedented quality in which the
particle size distribution, particle diameter, and particle type
are controlled.
[0063] By preparing a catalyst for olefin polymerization using the
magnesium alcoholate obtained by this method, an olefin polymer can
be obtained in which the particle size distribution, particle
diameter, and particle type are controlled. From the above results,
the present invention is extremely useful industrially.
* * * * *