Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
1 This invention relates to a process for produc-
ing an ethylene copolymer having a density of 0.900 -
0.940 by copolymerizing ethylene with other unsaturated
hydrocarbon monomer in a liquid phase of said unsaturated
hydrocarbon monomer.
Medium-density ethylene polymers can be produced
by copolymerizing ethylene with an ~-olefin such as
l-butene ln the state of slurry in an inert hydrocarbon
solvent by the low-moderate pressure process. However,
10 in this case, the resulting polymer deposits on the
inner wall of reactor to produce troubles about heat
conduction, agitation, discharge of polymer, etc. In
addition, the resulting polymer particles tend to be
bulky and irregular which decreases space yield and
15 incurs troubles about transportation of polymer.
Therefore, a commercial production according to this
process encounters difficulty in respect of cost and
many other problems.
Apart from above, the polymerization of
20 propylene in liquid propylene and its copolymerization
with a samll quantity of other unsaturated hydrocarbon
monomer in liquid propylene (hereinafter referred to as
bulk polymerization) are disclosed and extensively
practised industrially. Homopolymerization of l-butene
; 25 in liquid l-butene and copolymerization of l-butene
1- ~
~ ' f
''': ' ' ~ . ' '' :
,. ' ' ~
' ~, ~ ' ' '' '; :
- ' : ' ' : ,
9fl
1 with a small quantity of unsaturated hydrocarbon monomer
such as propylene, decene, octadecene or the like in
liquid l-butene are also disclosed.
Nevertheless, production of low-density or
medium-density ethylene polymer having an ethylene
content of overwhelming majority by bulk copolymerization
of ethylene with an unsaturated hydrocarbon monomer in
the liquid medium of said unsaturated hydrocarbon
monomer has not yet been practised industrially.
On the other hand, it is well known that a
catalyst system comprising a combination of a compound
of transition metal belonging to Group IVb-VIb of the
periodic table and an organometallic compound of a
metal belonging to Group I-III of the periodic table
(the so-called Ziegler catalyst) is effective for the
polymerization of olefins. Further, many studies have
hitherto been conducted with respect to the catalysts
comprising a transition metal compound supported on a
carrier to reveal that inorganic compounds such as
oxides, hydroxides, chlorides and carbonates of metals
or silicon as well as mixtures or double salts thereof
are effective as the carrier. For example, magnesium
chloride, double oxide of magnesium and aluminum, double
oxide of magnesium and calcium and the like are known
to be effective as the carrier.
; However, the catalyst for use in the production
of polyolefin is desired to have a catalytic activity
as high as possible. In fact, even the catalysts
~ .
, .. . . , . .. .. - . . , , , : . . . -
.
. ~' ' ~' . , . : '
.
l mentioned above are still insufficient in catalytic
activity. When applied to the production of low-
medium density ethylene polymers, these catalysts
cannot prevent the aforementioned difficulties
encountered in the slurry polymerization in an inert
hydrocarbon solvent, so that they cannot be said to be
satisfactory industrially.
Previously (Belg. Pat. No. 849,503) the present
inventors discovered that a catalyst obtainable by
combining an organoaluminum compound with a solid
catalyst component prepared by supporting a titanium
and/or vanadium compound on a solid product obtainable
by reacting an organomagnesium compound with a
halogenated aluminum compound and/or a halogenated
silicon compound can aot as a catalyst of very high
activity for the polymerization of olefins. The
inventors have conducted further advanced studies
concerning the polymerization of olefin by the use of
the above-mentloned high active catalyst. As the result,
it has been found that, if the above-mentioned
catalyst is used, a low-density or medium-denslty
ethylene polymer can be produced with a very high
activity and without any deashing process by bulk-
copolymerizing ethylene with an unsaturated hydrocarbon
~; 25 monomer in a liquid phase comprising said unsaturated
` hydrocarbon monomer, and further that, in the polymeri-
~; ~ zation reaction, a polymer having better slurry
characteristics and a high bulk density can be obtained
- 3 -
-: " '. ' . , , !
i. : ' ~ '
' ' ~ ' ' "'. ~ ' ~ ' , ... ,, '
.
" . ' . . . '
- ~,
~.~1.4~
l with a less adhesion of polymer to the inner wall of
reactor.
Thus, it is an object of the present invention
to provide a process for producing, with a high activity,
an ethylene polymer having good slurry characteristics
by copolymerizing a large quantity of ethylene with a
small quantity of unsaturated hydrocarbon monomer in
the liquid phase of unsaturated hydrocarbon monomer.
Other ob~ects and advantages of the present
invention will be apparent from the following
descriptions:
According to the present invention, there is
: provided a process for producing a low-denslty or
medium-density ethylene polymer having a density of
0.900 - 0.940 which comprlses copolymerizing ethylene
with other unsaturated hydrocarbon monomer in a liquid
pha~e comprising said unsaturated hydrocarbon monomer
in the presence of a catalyst system comprising an
organo-aluminum compound and a solid catalyst component
prepared by supporting a titanium and/or vanadium
compound on a solid product obtainable by reacting an
organomagnesium compound with a halogenated aluminum
. compound represented by the following general formula:
: R nAlX3_n
.~ 25 wherein Rl is an alkyl, aryl or alkenyl group having up
to 20 carbon atoms, X is a halogen atom and n is a number
defined by O ~ n ~ 3, and/or with a halogenated silicon
4 -
....
:. , , . . : . -
~: , . . . ~ ~ ., .
~, . . . : - , . ~ . . - . , , - - . - . -
.
, . ,,: , , - , , . - : , .
. , . - , . . . . .. :
.. , - .... , - . ..
., - , . ~ . .
4~ ~ ~
l compound represented by the following general formula:
R2mSiX4 m
wherein R2 is an alkyl, aryl or alkenyl group having up
to 20 carbon atoms, X is a halogen atom and m is a number
defined by 0 _ m < 4.
The unsaturated hydrocarbon monomers used in
the liquid state in the present invention are C3-C8
~-olefins. Examples of said unsaturated hydrocarbon
monomer include propylene, l-butene, 1-pentene, l-hexene,
l-octene and the like, among which l-butene is particu-
larly preferable.
me ethylene polymer constructing the ob~ect
of this invention is a copolymer of a major percentage
(preferably, 80 - 99%) by mole of ethylene and a minor
percentage (preferably, l - 20%) by mole of at least
one kind of unsaturated hydrocarbon monomer. Density
of the copolymer can be controlled mainly by varying
the quantity of unsaturated hydrocarbon monomer to be
copolymerized with ethylene. Density of the ethylene
homopolymer obtainable with the catalyst system of this
invention depends on its molecular weight. Roughly
speaking, however, the density is about 0.96. It is
possible to lower the density of copolymer arbitrarily
by lncreasing the content of unsaturated hydrocarbon
monomer used as comonomer. In order to obtain a polymer
having a density falling in the intended range, it is
necessary to introduce l - 20 mole-% of unsaturated
;~: - 5 -
:
., . , ~ . . . ~. , '
: .
. . . ~ .
~ . . . , ~
- . ~ . .
4t~
1 hydrocarbon monomer into the ethylene copolymer. The
amount of unsaturated hydrocarbon monomer to be
introduced necessary for obtaining the same density
varies depending on the species of monomer. mere is
a general tendency that a monomer having a longer side
chain after being polymerized may be introduced into
copolymer in a smaller amount by mole. For example,
when the comonomer is l-butene, one must introduce about
5 - 18 mole-% of l-butene into the copolmer in order to
produce a low-density ethylene polymer having a density
of 0.900 - 0.925, while one must introduce about
2 - 5 mole-~ of l-butene in order to produce a medium-
density ethylene polymer having a density of 0.926 -
0.940. Since C3-C8 ~-olefins show different monomer
reactlvity ratio from species to species in the
;~ copolymerization reaction with ethylene in the presence
of the catalyst of this invention, the partlal pressure
of ethylene to be fed into reactor is greatly dependent
; on the kind of C3-C8 olefin. On the other hand, the
; 20 proportion of unsaturated hydrocarbon monomer to be
copolymerized is dependent on the ratio between an
unsaturated hydrocarbon monomer and ethylene in liquid
phase. In other words, a higher partial pressure o~
, ,
, ~. ~ .,
ethylene gives a higher ethylene content of the copolymer.
Accordingly, a copolymer having an intended content of
the unsaturated hydrocarbon monomer unit can be produced
at will by changing the partial pressure of ethylene
appropriately.
.. . - :-. . . - - -. : .
.. ~. , ... . . , . - . . . , ~ ..
. . , ... ~ . :. - . - . - ... . .. . , . ~ .
... . . , , . . .. . .: . , . -
,,. . .. - .. ; . . , ~ .. : : ... . , : :
. - . . - , . . , , . . , -. . - . ,
1 The polymer slurry of this invention obtainable
by the bulk copolymerization in an unsaturated hydrocarbon
monomer such as l-butene has a great merit as compared
with a polymer slurry obtainable by conventional suspen-
sion polymerization process (or solvent polymerization)
in which the polymerization is carried out in general -
in the medium of liquid saturated hydrocarbon having
5 - 7 carbon atoms, in that the polymer can be isolated
merely by a simple procedure of removing the unreacted
unsaturated hydrocarbon monomer.
Thus, the necessary procedures are only to
copolymerlze a lique~ied unsaturated hydrocarbon
monomer with ethylene under an elevated pressure and
to recover and reuse the unreacted monomer after the
reaction. In this case, recovery of solvent is
unnecessary unlike conventional solvent polymerization,
and the charge system attached to the polymerization
reactor can be simplified. Therefore, the process
provided herein is considerably simple and economical.
The polymer produced according to the process
of this invention has a variety of advantages over
conventional high-pressure low-density polyethylenes in
that it has a higher strength, a higher stiffness, a
higher softening point, a higher cold resistance
(particularly low-temperature impact resistance), a
higher melt extensibility, a higher stress cracking
resistance, etc., so that it can be put to use in the
application fields of conventional high-pressure
-.
. : ~
~ 7 ~
. ,., , . ~ - .. . .
, . .. .
.
.
: , I . .', ' . ~ ~ ~
. ~ .
..
,
, , . - -.~ ' . '. - :
ofl
1 low-density polyethylenes but also in a wide variety of
novel application fields.
The catalyst used in this invention comprises
a combination of an organoaluminum compound and a
solid catalyst component prepared by supporting a
tltanium compound and/or a vanadium compound on a solid
product obtainable by reacting an organomagnesium
compound with a halogenated aluminum compound represented
by the following general formula:
RlnAlX3 n
whereln R is an alkyl, cycloalkyl, aryl or alkenyl
group having up to 20 carbon atoms, X is a halogen atom .
and n is a number defined by 0 _ n < 3, or with a
halogenated silicon compound represented by the following
general formula:
R msix4-m
wherein R2 is an alkyl, cycloalkyl, aryl or alkenyl
group having up to 20 carbon atoms, X is a halogen atom
and m is a number defined by 0 < m < 4.
In this invention, the organomagnesium
compound used for the synthesis of catalyst may be
selected from any forms of organomagnesium compounds
obtainable by reacting an organic halogen compound with
metallic magnesium.
As said organomagnesium compound, Grignard
compounds represented by the following general formula:
,
. .
:. ... . . ~ .. . . - . . . . ..
, ~ : , , , , - . . :.
., ., .. , . ... , . . .. .. ... ~... ..... . .. - .... ..
, . , . . . . .. ,. . - .
. .
- . . - . . . .. -.: . - . .
- . .. .. . :: . .. .: - . - : :
.. : .. . . . ~ . :, ~ - . .: .- .
fl
l R3MgX
wherein R3 is an alkyl, aryl or alkenyl group having up
to 20 carbon atoms, and X is a halogen atom, and organo-
magnesium compounds represented by the following general
formula:
R32Mg
can be used preferably.
Said organomagnesium compound includes all
the possible compositions expressed by the following
equilibrium equation:
2R3MgX ~ R32Mg + MgX2 ~ R32Mg.MgX2
notwithstanding whether or not said organomagnesium
compound has been prepared in the presence of ether
~W. Shlenk et al., Ber., 62, 920 (1929); ibid. 64, 739
( 19 31 ) ~ 7rct ~,~
Herein, R3 represents an alkyl, aryl~ror
alkenyl group having up to 20 carbon atoms~ such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
tert-butyl, n-amyl, lso-amyl, n-hexyl, n-octyl, 2-
ethylhexyl, phenyl, benzyl and the like. Concrete
~ examples of said organomagnesium compound, expressed
;~ in terms of Grignard compounds, include ethylmagnesium
; chloride, ethylmagnesium bromide, n-propylmagnesium
. .
~ chloride, n-butylmagnesium chloride, tert-butylmagnesium
., ........... . . ... -
`;~ - . - ~ .. ' .. . . :
.: . . . . . . . . .
~ .. ~......... . . . ~ .
l chloride, n-amylmagnesium chloride, phenylmagnesium
bromide and the like.
Organomagnesium compounds represented by the
general ~ormula R32Mg are also included in the organo-
magnesium compounds of this invention, as indicated bythe aforementioned equilibrium equation. Their concrete
examples include diethylmagnesium, dipropylmagnesium,
dibutylmagnesium, diamylmagnesium, dihexylmagnesium~
dioctylmagnesium, diphenylmagnesium, dibenzylmagnesium
and the li~e.
These organomagnesium compounds are synthesized
and used in the presence of an ethereal solvent such as
ethyl ether, propyl ether, butyl ether, amyl ether,
tetrahydrofuran, dioxane and the like; hydrocarbon
solvents such as hexane, heptane, octane, cyclohexane,
benzene, toluene, xylene and the like; or a mixture of an
ethereal solvent and a hydrocarbon solvent. Among these
solvents, ethereal solvents are particularly preferable.
The halogenated aluminum compound represented
by general formula R nAlX3 n includes all the compounds
having an aluminum-halogen bond (Al-X). A compound having
a larger number of halogen atoms gives a better result,
and anhydrous aluminum chloride is most preferable. m e
halogenated silicon compound represented by general
formula R2mSiX4 m includes all the compounds having a
silicon-halogen bond (Si-X). A compound having a larger
number of halogen atoms gives a better result, and
silicon tetrachloride is most preferable. In the general
-- 10 --
. ~ . . - - .
. , . .. : : . .: .. .: .. . - . . : , . : :
.. .: .: . ~ - . : ~ .
. ~ : . . , . ' ' ' ' -. ~
.
4~?~
1 formulas~ R~ and ~2 represent an alkyl, cycloalkyl,
¦ aryl~or alkenyl group having up to 20 carbon atoms.
Concrete examples of Rl and R2 include methyl, ethyl,
n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl,
n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, vinyl,
allyl, cyclopentyl, cyclohexyl, phenyl, benzyl and the
like. X represents halogen atom, of which concrete
examples include chlorine, bromine and iodine. n
represents a number defined by 0 < n < 3, and m represents
a number defined by 0 < m < 4. Concrete examples of said
halogenated aluminum compound include anhydrous aluminum
chloride, aluminum bromide, aluminum iodide, diethyl-
aluminum chloride, ethylaluminum dichloride, ethylaluminum
sesquichloride, dibutylaluminum chloride, butylaluminum
dichloride, dihexylaluminum bromide, hexylaluminum
dlbromide and the like. Concrete examples of said
halogenated silicon compound include silicon tetra-
chloride, silicon tetrabromide, methylsilyl trichloride,
dimethylsllyl dichloride, trimethylsilyl chloride,
ethylsilyl trichloride, diethylsilyl dichloride,
triethylsilyl chloride, propylsilyl tribromide,
dipropylsilyl dibromide, tripropylsilyl bromide,
dibutylsilyl dichloride, tributylsilyl chloride,
vinylsilyl trichloride and the like.
The synthetic reactions of the catalyst are
all carried out in an atmosphere of inert gas such as
nitrogen, argon or the like. The reaction between the
organomagnesium compound and the halogenated aluminum
-- 1 1 --
.
.
.
::~ , . . - : - -
- , . ' :
- ~ . , . . ~ -
'
1 compound and/or halogenated silicon compound is prefer-
ably carried out in a solvent at a temperature of 0 -
100C, though the reaction may be carried out at a high
temperature of 100C or above. The solvents usable in
this reaction include aliphatic hydrocarbons such as
pentane, hexane, heptane, octane and the like; aromatic
hydrocarbons such as benzene, toluene, xylene and the
like, alicyclic hydrocarbons such as cyclohexane,
cyclopentane and the like; ethereal solvents such as
ethyl ether, butyl ether, amyl ether, tetrahydrofuran,
dioxane and the like; and mixtures of hydrocarbon
solvents and ethereal solvents Among these solvents,
ethereal solvents are particularly preferable.
Said organomagnesium compound is reacted with
sald halogenated aluminum compound and/or said halogenated
silicon compound in a proportion of 0.1 - 10.0 and
preferably 0.5 - 2.0, by mole. The reaction product is
precipitated in the form of a solid.
The reaction product obtained as above is
isoIated and then used as a carrier. Concretely speaking,
the reaction product is used after being filtered, or
subsequently thoroughly washed with a purified hydro- -
carbon diluent, or further dried. Then, a titanium
compound and/or a vanadium compound is supported on the
carrier synthesized as above.
Examples of the titanium compound and the
vanadium compound to be supported on the carrier include
titanium trichloride, titanium compounds represented by the
- 12 -
, ~: : - . .. . - .. . : .
; ` ' ~'', ' ,' . ~ ' ' ' ' . '
. . : ,
.: . , ' - . - .
l general formula Ti(oR4)4 pXp, vanadium tetrachloride,
vanadium oxytrichloride and the like.
In the general formula Ti(oR4)4 pXp, R4
represents an alkyl or cycloalkyl group having up to 20
carbon atoms, or phenyl group, X represents a halogen
atom, and p represents a number defined by 0 < p < 4.
Concrete examples of titanium compound represented by
this general formula include titanium tetrachloride,
titanium tetrabromide, titanium tetraiodide,
tetraethoxytitanium, ethoxytitanium trichloride,
diethoxytitanium dichloride, triethoxytitanium chloride,
propoxytitanium trichloride, butoxytitanium trichloride,
phenoxytitanium trichloride, ethoxytitanium tribromide,
dipropoxytitanium dibromide, tributoxytitanium bromide
and the like, among which titanium tetrachloride is
particularly preferable in respect of activity and
particle characteristics.
In supporting said titanium compound and/or
vanadium compound on the carrier, one may adopt disclosed
processes such as lmpregnation, kneading, co-precipitation
and the like. A particularly superior process for this
purpose comprises contacting said titanium compound
and/or vanadium compound with said carrier in the absence
of solvent or in the presence of appropriate inert
solvent. Preferably, this supporting reaction is
conducted at a temperature ranging from room temperature
(about 20C) to 150C. After completion of the reaction,
the reaction product is collected by filtration,
. .
- 13 -
~ 4~
1 thoroughly washed with a purified hydrocarbon diluent
and then put to use directly, or put to use after an
additional drying. The amount o~ said titanium compound
~nd/or vanadium compound to be supported on the carrier
is controlled so that the amount of titanium and/or
vanadium atoms contained in the resulting solid product
falls within the range of 0.1 - 30% by weight usually,
and pre~erably in the range o~ 0.5 - 15% by weight.
In this invention, a greater specific surface area of
the solid catalyst component is more desirable. The
solid catalyst component obtainable according to the
above-mentioned process has a great speci~ic surface
area, which sometimes exceeds 200 m2/g.
me organoaluminum compound which constitutes
a catalyst system ln the polymerizatlon reaction in
combination with the above-mentioned solid catalyst
component includes trialkylaluminums such as triethyl-
aluminum, tri-n-propylaluminum, tri-n-butylaluminum,
tri-n-hexylaluminum and the like; dialkylaluminum
monohalides such as diethylaluminum monochloride,
di-n-propylaluminum monochloride, di-n-butylaluminum
monochloride, di-n-hexylaluminum monochloride and the
llke; alkylaluminum dihalides such as ethylaluminum
dichloride, n-propylaluminum dichloride, n-butylaluminum
dichloride, n-hexylaluminum dichloride and the like;
and alkylaluminum sesquihalides such as ethylaluminum
sesquichloride, n-propylaluminum sesquichloride,
1 .
n-butylaluminum sesquichloride~ n-hexylaluminum
: - 14 -
... ,. . . . ~
~J 14~
1 sesquichloride and the like. These organoaluminum
compounds may be used either alone or in combination of
two or more.
The molar ratio between ~he solid catalyst
component and the organoaluminum compound (Ti and/or
V : Al) used for the polymerization of olefins can
vary widely from about 10 : 1 to 1 : 1000, pre~erably
from 2 : 1 to 1 : 100.
The catalyst of this invention has a very
hlgh activity and, at the same time, the polymerization
reaction is carried out in the state of bulk copolymeri-
zation. Owing to these facts, the catalyst can exhibit
a very high efficiency throughout the operation.
It is not difficult to make the content of
transltlon metal ln the polymer produced by the process
of thls lnventlon as low as about 10 ppm or less, and
sometimes it can be lessened to about 2 ppm or less,
so that one can omit the catalyst removal process
without lncurrlng any problem about product quality.
When the buIk copolymerization of this
lnvention is carried out in a lower unsaturated
hydrocarbon monomer havlng 4 - 6 carbon atoms such as
l-butene, the resulting polymer has only a small
quantlty of fraction soluble into the liquid phase so
that there is observed neither increase of viscosity
nor stlckiness of cake due to the formation of low
molecular weight soluble fraction in the plymerization
reactor. me polymer particles have good characteristics
5 -
;. . ~ " . . .
- .
. .
.
. - . -
. - ` ` ` .. .. . . .
. ~ . . . . .
" . . . .. .
, . . . . ` . . ` .
~ ~4q~
1 and the production efficiency per unit volume of
reaction space can be enhanced. Therefore, a more
advantageous result can be obtained.
In the process of this invention, the
polymerization temperature may be selected arbitrarily
from temperature range of -20 to 120C. A temperature
range of 50 to 70C is particularly preferable.
The reaction pressure is preferably in the
range of 1 - 100 kg/cm2 and particularly in the range
of 10 - 50 kg/cm2.
Molecular weight of the resulting polymer
can be controlled by introducing hydrogen into the
polymerization reaction system. Since the amount of
hydrogen to be introduced varies depending upon
polymerization conditions and intended molecular weight
of polymer, it is necessary to control its supply
appropriately in accordance with the object.
It is conventional to use an inert solvent
as a carrier for supplying catalyst. Examples of said
inert solvent include aliphatic hydrocarbons such as
pentane, hexane, heptane, octane and the like; alicyclic
hydrocarbons such as cyclohexane, cycloheptane and the
like; and aromatic hydrocarbons such as benzene, -
toluene, xylene and the like.
The following examples will illustrate this
invention in more detail. The examples are presented
in no 11mitative way, unless the essentiality of this
invention is exceeded.
- 16 -
, , , .. , ,.... ,- :
. . , :. ., . , : :
: ... . . - : . :
: , .... - . , ,-, ~.. . , - ,
- . . .: . -
,. , . . . - - :. . . . . .
. , , ., , . - ,, . ,.. . , , . ,, , . . ,., .... " . . .
1 In the examples, the characteristics of
polymer were measured by the following procedure.
Content of l-butene in copolymer was
determined by measuring infrared absorption spectrum
of a film, evaluating the absorbance with regard to
the peak of 762 cm 1, and then calculating the content
of ethyl group according to the following equation:
C2H5/1000C = td x log(Io/I) - 18.4
wherein t is thickness o~ specimen (cm), d is density
(g/cm3), I is intensity of transmittent light, Io is
lntensity of incident light, and C2H5/1000C is the
number of ethyl group per 1000 carbon atoms.
Density and melt index (MI) were determined
according to JIS K-6760. Bulk density was determined
according to JIS K-6721.
;
Example 1
.~ .
(1) Synthesis of Organomagnesium Compound
16.0 g of chipped magnesium for the prepa-
ration of Grignard reagent was placed in a four-necked
flask having a capacity of 500 ml and equipped with a
stirrer, a reflux condenser and a dropping funnel, and
the inner atmosphere of the system was thoroughly
replaced with nitrogen to remove air and moisture
completely. 0.65 mole of n-butyl chloride and 300 ml
of n-butyl ether were charged into the dropping funnel,
:
-
~ - 17 -
,. . .~ ,.. , , . , .. .- " . .. .
:,, ~ , -
, . :, , , . . , , ~ . , : :,
. . ,., ,, -., . :. ,. . : ., . - ~ - ,
... .,: . , - . : : : -: - - .
,, .,: , . . . .
: ,.. , . . - , . . : - . :: ~: : : - . -
" :. : - . : , -
, . . . ~ . , . , , -
-. : ., . ~ ,: . , , , .: - . . . .
;. . ~ .. - . . . . . . . .
.. .. : :~: .. : . . . . . ..
1 after which their about 30 ml was dropped onto the
magnesium in the flask to start the reaction (when
the reaction did not start, the bottom of flask was
gently heated in order to start the reaction).
After start of the reaction, the dropping was continued
so as to keep a mild progress of the reaction.
After completion of the dropping, the reaction was
eontinued for an additional about one hour at
60 C. Then the reaction mixture was cooled to
room temperature and the unreacted magnesium was
filtered off by means of a glass filter.
The n-butylmagnesium chloride present in
n-butyl ether was hydrolyzed with 1 N sulfuric acid
and back-titrated with 1 N sodium hydroxide to
determine lts concentration by the use of phenol-
phtalein as an indicator. Thus, its concentration
was found to be 2.00 moles/liter.
(2) Synthesis of Solid Catalyst Component
The inner atmosphere of a four-necked flask
having a capacity of 500 ml and equipped with a
stirrer, a dropping funnel and a thermometer was
thoroughly replaced with nitrogen to remove air and
moisture.
35 g of anhydrous aluminum chloride, which
had been purified by sublimation in advance, was
introduced into the flask and dissolved into 150 ml
of n-butyl ether while cooled with ice. Then, 132 ml
(0.264 ~ole) of the ethereal solution of n-butylmagnesium
:
- 18 -
. : , , , ~. . ,, .. , . . ... . , - . ~-
.'.: .: . ,' :. . . '.. ' . '. '. ' . .
, ., .. - .. ...
.. . . . . . . . .
,: : - . . :
. . - .. . ~, . ; . . ,
1 chloride synthesized in (1) was slowly dropped from
the dropping funnel to yield a white precipitate.
The mixture was reacted at an ice-cooled temperature
for one hour, and then at 50C for an additional
3 hours. After the reaction, the resulting white
colored solid was separated, washed and dried
under reduced pressure to give 32.5 g of a white
colored solid. Its 10 g was taken in a four-necked
flask having a capacity of 100 ml, dipped in 50 ml
of titanium tetrachloride, and reacted at 130C
for one hour with stirring. After completion of
the reaction, it was repeatedly washed with n-heptane
until the washing became free from titanium
tetrachloride, and then it was dried under reduced
pressure to give 7.5 g of a solid catalyst
component. In 1 g of the resulting solid product,
25 mg of titanium atom was supported, and the solid
product had a specific surface area of 230 m2/g.
(3~ Polymerization
Inner atmosphere of a stainless-made
autoclave having a capacity of 5 liters and equipped
with an electromagnetic stirrer was replaced with
dry nitrogen completely, after which 1,250 g of
l-butene was charged into the autoclave. Then,
hydrogen was fed up to a partical pressure of
2 kg/cm and 15 mmoles of triethylaluminum was added.
m e temperature was elevated to 50C, ethylene was
` fed up to a partial pressure of 18 kg/cm2, and then
.
19 -
, , . , . .. , , '' , ~ , . ' ': ' - .. .
.. . , . . . , . : - :
, . .. : . .. . :: -
- . ~ :-. . .- - . .. . .
1 9.9 mg of the aforementioned solid catalyst
component suspended with 20 ml of heptane was added
to start the polymerization. me polymerization was
continued at 50C for 4.9 hours, while keeping the
total pressure constant by supplying ethylene.
After the polymerization was continued for an appointed
period o~ time, the polymerization was stopped with
isopropyl alcohol and the unreacted monomer was purged.
The resulting polymer was washed with methanol and
dried under reduced pressure at 60C to give 559 g
of a copolymer. The copolymer contained 5.5 mole-%
of l-butene. It had a density of 0.923 g/cm3, MI of
0.24 g/10 min. and a bulk density of 0.33 g/cm3.
In this reaction, the catalyst exhibited an activity
of 11,500 g copolymer/g solid.hr or 461,000 g
copolymer/g Ti-hr.
Examples 2-6
Using the same solid catalyst compnent as
in Example 1, polymerization was carried out by the
same procedure as above. m e results obtained were
as shown in Table 1.
Examples 7-9
Catalyst was prepared and polymerization -
was carried out in the same manner as in Example 1.
m e results obtained were as shown in Table 2.
.
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