Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
1~.2132~
BACKGROU~D OF TH~ INVENTION
This invention relates to a catalyst suitable for polymerizing
an a-olefin and hàving a high activity and to a polymeri~ation process
employing such a catalyst.
Description of the Prior Art
It is known in Japanese Patent No. 233,148 to K. Ziegler that
polyethylene can be produced under a low pressure using a catalyst
comprising an organomagnesium compound and a transition metal compound.
The organomagnesium compound as such, however, is disadvantageously
insoluble in an inert hydrocarbon medium employed for the preparation
of the catalyst and the polymerization of ethylene and as a result, the
catalysts having a high activity have not been obtained.
It is also known in Japanese Patent Publication No. 40959/1972;`
and Japanese Patent Application (OPI) No. 439211971 that when the organo-
magnesium compound is used in a speci-fic form there can be obtained
catalysts having increased activity. Such organomagnesium compounds
include, for example, complexes of an organomagnesium halide, i.e. a
so-called Grignard reagent with an ether, and organomagnesium alkoxides.
The catalysts comprising these organomagnesium compounds have a compara-
tively high activity per transltion metal atom but as for the catalysts
capable of completely omitting the catalyst removal step in a process of
producing polyethylene, the amount of halogen atoms remaining in the
polymers obtained is still large.
Some of the co-inventors of this invention proposed in U.S.
Patent Nos. 3,989,878, 4,004,071 and 4,027,087 a series of complex
compounds soluble in an invert hydrocarbon medium and comprising an
organomagnesium compound and one of an organo~inc compound, an organoboron
compound and an organoberyllium compound in a specific ratio which have
a much higher activity than the conventional catalysts and enable complete
omission of the catalyst removal step.
- 2 -
~.Z~3~Z~
'~
..
As a result of intensified studies on the catalyst system
comprising an organomagnesium compound, the inventors have discovered
that without using the above described complex compounds having a
specific composition, catalysts havirlg a very high activity and suitable
for polymerizing an ~-olefin can be obtained by reacting a solid catalyst
component with an organometal compound, the solid catalyst component
being prepared by reacting an organomagnesium compound soluble in an
inert hydrocarbon medium with a titanium and/or vanadium compound.
According to this invention there is provided a catalyst
suitable for polymerizing an ~-olefin, comprising [Al a solid catalyst
component and [B] an organometal compound, wherein the solid catalyst
component [A] is prepared by reacting (1) an organomagnesium compound
soluble in a hydrocarbon medium and represented by the general formula,
r~. MgRlpR2qXr Zs
wherein
Rl is a hydrocarbon group having 2 to 3 carbon atoms;
R2 is a hydrocarbon group having 4 to 20 carbon atoms
and the difference in number of carbon atoms between Rl
and R2 is at least 2;
X is an electronegative group having an oxygen atom, a
nitrogen atom or a ~ulfur atom;
Z is an organometal compound of aluminum, boron,
~: beryllium, zinc, silicon or lithium,
p and q each is a number above 0 to 1,
: r is a number from 0 to 1,
p + q ~ r = 2, and
s is a number above 0 to below 0.1
with (2) a titanium and/or vanadium compound having at least one halogen
atom.
1~ 6
;,
.
Also~ according to this invention there is provided a process
for the production of polyolefins by using the same catalyst.
One of the characteristic features of this invention is a
very high catalystic efficiency. Owing to this feature, the amount of
catalyst resid~e such as transition metals and halogen atoms remaining
in the polymers produced is small. Accordingly, the catalyst of this
invention is suitable for a polymerization process which does not
require any catalyst removal step.
Another characteristic feature of this invention is that as
excellent particle properties, the polymers produced have a uniform
particle size and do not contain large coarse particles which cause
trouble in a continuous polymerization, and further they have a high
bulk density.
Stlll another characteristic feature of this invention is that
the molecular weight distribution of polymers can be easily controlled
within wide limits.
The polymers obtained by using the above described catalyst
of this invention have high molecular weight, high rigidity, narrow
molecular weight distribution and high impact strength.
~ ~ Furthermore, in order to broaden the molecular weight distri-
-~ bution of polymers with a high catalytic activity, the solid catalyst
component [A] before being reacted with the organometal compound [B] is
additionally reacted with an inorganic or organic compound (3) of
aluminum, silicon, tin or antimony or a titanium or vanadium compound (4)
to give a solid type catalyst component [A']. This solid type catalyst
component [A'~ is employed together with the organometal compound [B] as
the catalyst of this invention. Or the solid catalyst component [A] or
the solid type catalyst component [A'] together with the organometal
compound [B] is further combined with a halogenated hydrocarbon [C].
By employing the solid type catalyst component [A'] together with the
1~.2~6
organometal compound [B] or the solid catalyst com~onent ~A] or the
solid type catalyst component [~'] together with the organometal
compound [R] in combination with the halogenated hydrocarbon [C],
there can be obtained polymers having a broader molecular weight
distribution suitable for blow-molding or film- or sheet- molding.
Detailed Desc~ption of the Preferred Embodiments
Each of the component materials and reaction conditions
employed for the preparation of the catalyst of this invention will
be described hereinafter in detail.
The organomagnesium compound (1) which can be employed for
preparing the solid catalyst component [A] of this invention is repre-
sented by the general formula,
gRlpR2qXr- Zs
wherein
Rl, R2, X, Z, p, q, r and s are the same as defined above.
In this formula, Rl is a hydrocarbon group having 2 to 3
carbon atoms. Exemplary hydrocarbon groups include an ethyl group, a
propyl group and an isopropyl. Of these groups, an ethyl group is
preferred. In the above describe formula, R2 is a hydrocarbon group
having 4 to 20 carbon atoms. Exemplary hydrocarbon groups include a
butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl
group, a nonyl group, a decyl group, a dodecyl and a hexadecyl group.
Of these groups, a butyl group, a pentyl group and a hexyl group are
preferred. The difference in number of carbon atom between Rl and R2
of at least 2 is an important factor for rendering the organomagnesium
compound (1) soluble in an inert hydrocarbon medium at high concent~
rations. Suitable examples of the electronegative group having an
oxygen atom, a nitrogen atom or a sulfur atom include an alkoxy group
having 1 to 20 carbon atoms, a siloxy group, a phenoxy group, a sub-
stituted phenoxy group, an amino group, an amide group, a -N=C~R4 group
-- 5 --
l~.Z~I 3~6
wherein R3 and R4 may be the same or different and each is a hydrocarbon
group having 1 to 20 carbon atoms, a -SRS group wherein RS is a hydro-
carbon group having 1 to 20 carbon atoms, and ~-ketoacid group.
Of these groups, an alkoxy group having 1 to 20 carbon atoms
and a siloxy group are preferred.
Exe~plary organometal compounds of aluminum, boron, beryllium,
zinc, silicon or lithium represented by Z include a trialkylaluminum, an
alkylaluminum alkoxide, a trialkoxyaluminum, a dialkylberyllium, a
trialkylboron, a dialkylzinc, a tetralkylsilane, a trialkylhydroxysilane
and an alkyllithium. Of these organometal comPounds, an organoaluminum
compound of the general formula,
AQR6(0R7)3
wherein
R6 and R7 may be the same or different and each is a
hydrocarbon group having 1 to 20 carbon atoms,
and
n is a number from 0 to 3
is preferred. ~ trialkylaluminum, an alkylaluminum alkoxide and a
trialkoxyaluminum are more prefeTred. p and q are numbers above zero
to 1 and r is a number from zero to 1 and p + q + r = 2. When r ranges
from zero to 0.6, the catalytic activity is increased. r is an important
factor for rendering the molecular weight distribution of a polymer
narrow, and when r ranges from 0.2 to 0.6, the effect of imparting a
narrow molecular weight distribu~ion to the polymer produced with a high
catalytic activity can be achieved. s is a number above 0 below 0.1 and
a preferred range is 0.09 to 0.02 in order to render the solution viscosity
of the organomagnesium compound (1) decreased, resulting in ease in
handling, and to obtain a high activity.
These organomagnesium compounds can be prepared by reacting
a reaction product between an organohalide of the formula RlW wherein
~.Z~3~6
Rl is the same as defined above and ~ is a halogen atom and magnesium
metal, i.e., a so-called Grignard reagent with an organolithium
compound of the formula R2Li wherein R2 is the same as defined above
or by reacting an equimolar mixture of an organohalide of the formula
RlW and an organohalide oE the formula R2W wherein ~1 and R2 are the
same as defined above and W is a halogen atom with magnesium metal in
the method as described in U.S. Patent No. 4,127,507.
The introduction of an electronegative group oE X: is conducted
by reacting an organomagnesium compound of the formula,
MgRlpR2q
wherein
Rl, R2, p and q are the same as defined above,
with a reagent selected from the group consisting of oxygen, an alcohol,
an organic acid, an ester of an organic acid, an aldehyde, a ketone,
a silanol, a siloxane, an amine, a nitrile and a mercaptan. Exemplary
reagents include, in addition to oxygen, ethanol, propanol, butanol,
hexanol, octanol, acetic acid, propionic acid, butanoic acid, benzoic
acid, methyl acetate, butyl propionate, acetaldehyde, acetone, methyl
ethyl ketone, acetylacetone, trimethylsllanol, triphenylsilanol,
dimethyldihydrodisiloxane, cyclic methylhydrotetrasiloxane, methyl~
hydropolysiloxane, phenylhydropolysiloxane, acetonitrile, ben~onitrile,
methylam me, dimethylamine, ethylamine, diethylamine, phenylamine,
methyl mercaptan, propyl merçaptan and butyl mercaptan.
The method of introducing the e]ectronegative group of:X which
can be employed is descrlbed in G.E. Coats and K. Wade, Organometal Com-
pounds, Vol. 1, published by Methuen & Co., Ltd.
~ xemplary titanlum and/or vanadium compounds (2) having at
least one halogen atom which can be employed for preparing the solid
catalyst component [~] of this invention include the halides, the
oxyhalides and the alkoxyhalides of titanium or vanadium such as titanium
~\ ~
26
tetrachloride, titanium tetrabromide, titanium tetraiodide, ethoxy-
titanium trichloride, propoxytitanium trichloride, butoxytitanium
trichloride, dibutoxytitanium dichloride, tributoxytitanium monochloride,
vanadium tetrachloride, vanadyl trichloride, monobutoxyvanadyl dichloride,
dibutoxyvanadyl dichloride, and mixtures thereof. Of these compounds, the
compounds of titanium and/or vanadium having at least 3 carbon atoms are
preferred. More preerred compounds are titanium tetrachloride and
vanadium tetrachloride.
The reaction between the organomagnesium compound (1) and the
titanium and/or vanadium compound (2) is conducted in an inert reaction
medlum including an aliphatic hydrocarbon such as hexane or heptane,
an aromatic hydrocarbon such as benzene, toluene or xylene, and an
alicyclic hydrocarbon such as cyclohexane or methylcyclohexane at a
h temperature of from about -30C to about 100C, preferably from about
-20C to about 50C. In order to achieve high activity it is recommended
that the reaction ratio of the two components ranges from 0.05 mole to
50 moles, especially from 0 2 mole to 10 moles of the organomagnesium
compound (1) per mole of the ti-tanium and/or vanadium compound (2).
The composition and the structure of the solid catalyst com-
ponent [A~ obtained ln the above described reaction may be varied within
wide limits depending upon factors such as the starting materials selected
and the reaction conditions employed. Typlcally the mole ratio of
Mg/(Ti and/or V~ of the solid catalyst component [A3 in the range of
from 0.2 to 10. A preferred mole ratio of Mg/(Ti and/or V) is in the
range of 0.5 to S. The solid catalyst component [A] thus obtained has
a very large specific surface area. In accordance with the measurement
by the B.E.T. method, the speclfic surface area ranges from about 50 m2¦g
to about 400 m2/g.
The inorganic or organic compound (3) of aluminum, silicon,
tin or antimony which is additionally reacted with the solid catalyst
-- 8 --
component [A] before being reacted ~ith the organometal component [B]
is a compound having a halogen atom, a hydrogen atom, a hydrocarbon
group, an alkoxy group or an aryloxy group. Suitable examples of such
compounds include an alkoxyaluminum dihalide, an allcylaluminum dihalide,
a monoalkoxysilicon halide, a monoalkylsilicon halide, a silicon
tetrahalide, a monoalkoxytin halide, a monoalkyltinhalide, a tin
tetrahalide, antimony pentachloride and a monoalkylantimony halide.
Of these compounds, an alkylaluminum dihalide~ silicon tetrachloride and
tin tetrachloride are preferred.
The titanium or vanadium compound (4) which is additionally
reacted with the solid catalyst component [A] before being reacted with
the organometal component [B] may be the same as the titanium and/or
vanadium compound (2). It is preferred that the titanium or vanadium
si
compound (4) has at least 3 halogen atoms. Titanium tetrachloride and
vanadium tetrachloride are more preferred.
The reaction between the solid catalyst [A] and the inorganic
or organic compound (3) or the titanium or vanadium compound (4) is
conducted in a ratio of 1 g of ~A] to 1 mmole to 100 mmoles of the
compound (3) or the compound (4), preferably 1 g of [A] to 2 mmoles to
50 mmoles of the compound (3) or the compound (4) in the presence or
absence of an inert hydrocarbon medium at a temperature of from about
10C to about 150C for about 1 to about 50 hours. After completion of
the reaction, it is preferred that the solid type catalyst component [A']
formed is isolated and washed with the inert hydrocarbon medium. The
above described reaction can be conducted multi-step-wise, i.e.~ in two
or three steps by using the same or different compound (3) or compound (4).
~xemplary inert hydrocarbon media include an aliphatic hydrocarbon such
as hexane or heptane, an aromatic hydrocarbon such as benzene or toluene
and an alicyclic hydrocarbon such as cyclohexane or methlcyclohexane.
3~6
The solid catalyst component ~A] or the solid type catalyst
component ~ of this invention as such is useful as a catalyst for
polymerizing ~-olefins. ~lowever, the solid catalyst component [A] or
the solid type catalyst component [~'] of this invention in combination
with an organometal compound [B] becomes a more improved catalyst.
The organometal compound [B] which can be employed in this
invention is a compound of a metal of Groups I to III of the Periodic
Table, and especially an organoaluminum compound and an organomagnesium
complex are preferred. ~s the organoaluminum compounds, those repre-
sented by the general formula,
~QRamY3-m
wherein
R8 is a hydrocarbon group having 1 to 20 carbon atoms,
Y is a member selected from a hydrogen atom, a halogen
atom, an alkoxy group having 1 to 20 carbon atoms, a
phenoxy group, a substituted phenoxy group, and a siloxy
group, and
m is a number from 2 to 3,
can be employed individually or as a mixture. In the above formula, the
hydrocarbon groups having 1 to 20 carbon atoms represented by R8 include
aliphatic hydrocarbons, aromatic hydrocarbons~and alicyclic hydrocarbons.
Exemplary organoaluminum compounds include triethylaluminum,
tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum,
triisobutylaluminum, trihexylaluminum,trioctylalumlnum, tridecylaluminum,
tridodecylaluminum, trihexadecylaluminum, diethylaluminum hydride,
diisobutylaluminum hydride, diethylaluminum ethoxide, diisobutylaluminum
ethoxide, dioctylaluminum butoxide, diisobutylaluminum octyloxide,
diethylaluminum chloride, diisobutylaluminum chloride, dimethylhydro-
siloxyaluminum dimethyl, ethymethylhydrosi]oxyaluminum diethyl and
ethyldimethylsiloxyaluminum diethyl and mixtures thereof.
- 10 -
~ ~ Z~326
.~:
As the organomagnesium complexes, those represented by the
general formula,
MgdMeR9fRl0h
wherein
M is a metal atom selected from the group consisting of
aluminum, boron, beryllium and zinc;
R9 and Rl may be the same or difEerent and each is a
hydrocarbon group having 1 to 10 carbon atoms;
d7 e, f and h, each is zero or a number above zero;
d/e = 1 to 8; and
2d ~ ~e = f ~ h, wherein ~ is the valence of M,
can be employed individually or as a mixture.
Of these groups, preferred hydrocarbon groups represented by
R9 and Rl are alkyl groups, cycloalkyl groups and aryl groups such as a
methyl group, an ethyl group, a propyl group, a butyl group, an amyl
groups, a hexyl group, a decyl group, a cyclohexyl group and a phenyl
group. An alkyl group is especially preferred as R9. Of the metal
atomsS aluminum and zinc are preferred.
These organomagnesium complexes are easily prepared by using
the method disclosed in patents such as U.S. Patents 4,004,071, 4,027,089,
3,989,878 and 4,120,883, and the documents such as Annalen der Chemie,
605, 93 - 97 ~1957), J. Chem. Soc., 1964, 2483 - 85, Chemical Communi-
cation, 1966, 559, and J. Org. Chem., 34, 1116 (1969).
A combination of these organometal compounds [B] with the above
mentioned solid catalyst component [A] or solid type catalyst component
[A'] provides a highly active catalyst, and especially a trialkylaluminum
and a dialkylaluminum hydride as the organometal compound [B] are pre-
ferred because they show the highest activity. The activity tends to
decrease upon introduction oE an electronegative group represented by Y
into the trialkylaluminum or the dialkylaluminum hydride. However, such
-- 11 --
3~;
organoaluminum compounds containing the Y group show unique polymeri-
zatlon behaviors, respectively, to produce useful polymers with a high
activity. For example, introduction of an alkoxy group render control of
the molecular weight of polymers easy. Since the presence of halogen
atoms in the polymeri~ation system and in the polymers produced is not
desirable, an alkoxy group and an siloxy group is preferred as the Y
group.
The solid catalyst component [A] and the organometal component
[B] may be added under the polymerization conditions to the polymerization
system or may be combined prior to the polymerization.
It is preferred that the ratio of these two components ranges
from 1 mmole to 3000 mmoles of the organometal compound [B] per gram of
the solid catalyst component [A].
The halogenated hydrocarbons which can be employed in combi-
nation with the solid catalyst component [A] or the solid type catalyst
component [A'] together with the organometal compound [B] in order to
give polymers having a broad molecular weight distribution with high
catalytic activity are saturated or unsaturated halogenated hydrocarbons
having 1 to 15 carbon atoms. It is preferred that the number of halogen
atom of the halogenated hydrocarbons is at most twice that of carbon
atom of the halogenated hydrocarbons. Exemplary halogenated hydrocarbons
include dichloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane,
1,1,2,2-tetrachloroethane, 1,2-dichloropropane, 1,3-dichloropropane,
15 2,3-trichloropropane, n-butyl chloride, isobutyl chloride, l,~-dichloro-
butane, 2,3-dichlorobutane, 1,2,3,~-tetrachlorobutane, n-hexyl chloride,
1,6-dichlorohexane, 1,2-dichlorooctane, dibromomethane, 1,2-dibromoethane,
n-butyl bromide, chloroben~ene, phenethyl chloride, allyl chloride~
bromoben~ene and ethyl iodide.
The combination of these halogenated hydrocarbons [C] with the
above described solid catalyst component [A] or solid type catalyst
- 12 -
326
component ~A'] and the organometal compound ~] may be conducted under
the reaction conditions with the passage of the polymerization or may be
conducted prior to the polymerization. Also, the polymerization can be
carried out by USillg the reaction product obtained by reacting the solid
catalyst component [A] or solid type catalyst component [A'] with the
halogenated hydrocarbon [C] and isolating the solid formed, and the
organometal compound with or without further addition of the same or
different halogenated hydrocarbon. It is preferred that the ratio of
these catalyst components ranges from 1 mmole to 3000 mmoles of the
organometal compound [B] per gram of the solid catalyst component [A]
and 1 mmole to 3000 mmoles of the halogenated hydrocarbon per gram of
the solid catalyst component [A] and the mole ratio of the halogenated
hydrocarbon [C] to the organoaluminum compound 1A] ranges 0.01 to 100,
especially 0.1 to 20.
Detailed Description of the Polymerization
The olefins polymerized by using the present catalyst may be
~-olefins, especially ethylene. Further, the present catalysts may be
employed for copolymerlzing ethylene and other monoolefins such as
propylene, butene-l and hexene-l and dienes such as butadiene and
isoprene. Also propylene may be polymerized with good efEiciency by
employing the present catalysts.
As for the polymerization method, there may be employed the
usual suspension-, solution- and gas phase-polymerizations. In the cases
of suspension- and solution-polymerizations, the catalyst is introduced
into a reactor to~ether with a polymerizat;on medium including an aliphatic
hydrocarbon such as hexane or heptane; an aromatic hydrocarbon such as
benzene, toluene or xylene; or an alicyclic hydrocarbon such as cyclohexane
or methylcyclohexane, and, an ~-olefin is added under a pressure of about
l to about 200 Kg/cm2 in an inert atmosphere and allowed to polymerize
at a temperature from about 10C to about 300C.
- 13 -
3~
For gas phase-plymerization, it is possible to carry out poly-
merization under an ~-olefin pressure of about 1 to about 50 Kg/cm2 and
a temperature from about 10C to about 120C, using a fluidized bed,
moving bed or mixing with a stirrer to provide better contact between
the ~-olefin and the catalyst.
There may be employed single stage polymerization having one
polymerization zone or multistage polymerization having a plurality of
polymerization zones.
When multiple stage polymerization is effected in at least two
polymerization zones having different polymerization conditions, by using
the present catalyst it is possible to produce a polymer whose molecular
weight distribution is much broader.
In order to control the molecular weight of the polymer, it is
also possible to add hydrogen, a halogenated hydrocarbon or an organo-
metalic compound which can cause chain transfer.
The following examples of preferred embodiments further
illustrate the principle and practice of ~he invention.
In the following e~ample
Mw is the weight average molecular weight determined according
to the following equation;
[~] = 6.8 x lo-4Mwo. 6 7
[see Journal of Polymer Science, 36, 91 ~1957)],
~w/Mn is the index of molecular weight distribution measured by
gel permeation chromatography, and
the term "catalytic efficiency" shows the amount of polymer
formed per gram of catalyst per hour of reaction time per
Kg/cm2 of ~-olefin pressure.
3~
Example 1
(I) Synthesis of Organomagnesium Compound (1)
In a 1 Q flask purged with nitrogen were charged 6.1 g (250
mmoles) oE magnesium powder, and then 1/10 of 300 mQ of a n-heptane solution
containing 250 mmoles of C2H5Br was added thereto. On stirring at an
internal temperature of the flask o 90C~ the reaction was started after
about 10 minutes. To the reaction mixture solution was added the rest of
the n-heptane solution over 2 hours with stirring while keeping the inter-
nal temperature of the flask at 90C, and further the reaction was con-
tinued at 90C for one hour. Then 200 mQ of a heptane solution containing
1 mole/Q of n-butyllithium to the reaction solution and the mixture was
refluxed under heating for 6 hours. After completion of the reaction,
the reaction solution was left to stand and the supernatant liquid was
r collected. On analysis of Mg and Br, this liquid contained 0.37 mole/Q
of Mg and less thon 0.01 mole/Q of Br. Also, the liquid was reacted
with iodine in two equivalent amount of iodine to magnesium atom and
the alkyl iodide formed had a C2H5I to n-C4HgI mole ratio of 1.05
according to the analysis~by gas chromatography. The organomagnesium
compound obtained was C2HsMgn-C4H9.
(II) Synthesis of Solid Catalyst Component [A]
The oxygen and moisture present inside a 500 mQ flask equipped
with two dropping funnels were purged with dry nitrogen, and to the
flask were charged 160 mQ of n-heptane and cooled to -5C. Then 80 mQ of
a heptane solution containing 40 mmoles of the above-obtained C2HsMgn-C~Hg
and 80 mQ of a n-heptane solution containing 60 mmoles of titanium
tetrachloride were accurately measured and separately charged in the
dropping funnels, respectively. Both components were simultaneously
added to the flask at -5C with stirring over two hours, and further
the aging reaction was continued at 5C. The solid catalyst component [A]
.2~3~
formed which was insoluble in the hydrocarbon medium was isolated, washed
with n-heptane and dried.
(III) Polymerization
In a 1.5 Q autoclave evacuated and purged with nitrogen were
charged 5 mg of the solid catalyst component ~A] and 0.4 mmole of
triisobutylaluminum with 0.8 Q of dehydrated and deaerated n-heptane.
While keeping the internal temperature of the autoclave at 85C, hydrogen
was added up to a gauge pressure of 1.6 Kg/cm2. Then ethylene was added
up to a total gauge pressure of 4.0 Kg/cm2. While maintai-ning the total
gauge pressure of 4.0 Kg/cm2 by adding additional ethylene~ the polymeri-
zation was carried out for one hour to give 134 g of a polymer. The
polymer had Mw of 125000, Mw/Mn of 10.3, a catalytic efficiency of
11200 and a bulk density of 0.39 g!c.c.
:~ `
Examples 2 to 12
Solid catalyst component [~] were prepared by reacting (1) the
organomagnesium compounds as set forth in Table I with (2) the titanium
and/or vanadium compounds having at least one halogen atom as set forth
in Table I under the reaction conditions as set forth in Table I in the
same manner as described in Example 1. Using these solid catalysts (1)
and triisobutylaluminum, polymerization of ethylene was carried out under
the same polymerization conditions as in Example 1. The results are
shown in Table I.
:
Examples 13 to 21
Polymerization of ethylene was carried out under the same
polymerization conditions as in Example l, except that the organometal
compounds [B] and the halogenated hydrocarbons [C] as set forth in
Table II were used instead of the triisobutylaluminum. The results are
shown in Table II.
- 16 -
1~.2~;~26
Examples 22 to 31
2 g of the same solid catalyst component [A] as prepared in
Example 2 were reacted with the component (3) and/or the component (4) as
set forth in Table III under the reaction conditions as set forth in Table
III to give solid type catalyst component9 [A']. Polymerization of ethylene
was carried out under the same polymerization conditions as in Example 1,
by using 5 mg of the solid type catalyst as obtained above and the
organoaluminum compound [B] and the halogenated hydrocarbon [C] as set
forth in Table III. The results are shown in Table III.
Example 32
2 g of the same solid catalyst component [A] as prepared in
Example 8 were reacted with 8 mmoles of AQ(C2H5)CQ2 in 100 mQ of n-heptane
at 80C for 2 hours. After completion oE the reaction, the supernatant
liquid was removed from the reaction mixture solution and the residue was
washed twice with n-heptane. Then 10 mmoles of TiCQ4 and 50 mQ of n-heptane
were added to the residue, and the reaction was carried out at 80C for one
hour and the solid type catalyst component [A'] formed was isolated.
Polymerization of ethylene was carried out under the same polymerization
conditions as in Example l, by using the above obtained solid catalyst to
give 87 g of a polymer.~ The polymer had a catalytic efficiency of 7250, a
Mw of 193000, a Mw/~n of 16.3 and a bulk density of 0.~17 glc-c-
It will be appreciated that the instant specification andexamples are set forth by way of illustration and not limitation, and
that various modifications and changes may be made without departing
from the spirit and scope of the present invention.
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