Note: Descriptions are shown in the official language in which they were submitted.
~;lff, PIN iN THIS ~B
-- 1:~ TRANSLATION 2114 317
PROCESS FOR PRODUCING POLYOLEFIN
TECHNICAL FIELD
" :
The present invention relates to a process for producing -
a polyolefin. More particularly, it pertains to a process
for producing a polyolefin capable of enhancin~ the powder
morphology of the resultant polymer and facilitating the
regulation of the molecular weight distribution of the
polymer, a process for efficiently producing in a stable
manner a high-molecular weight polyolefin having excellent
particle shapes, and a process for efficiently producing a
polyolefin characterized by any of the aforestated process by
the use of a catalyst enhanced in polymerization activity.
BACKGROVND ART
There has heretofore been known a process for producing
a polyolefin by the use of a solid titanium-based catalyst
and an organoaluminum compound. However, the polyolefin
produced by the above-mentioned process generally has
involved the problem that its transparency is poor when
formed into films because of its being broad in the molecular
weight distribution and compositional distribution.
orl the other hand, there has recently been proposed a
homogeneous catalyst having high activity and capable of
producing a polymer witll narrow molecular-weight ~ ;~
distribution, which catalyst is exemplified by a catalyst
composed of a metallocene compound of a transition metal and
an aluminoxane. (Refer to Japanese Patent Application Laid-
Open No. 19303/1983.) Nevertheless, the aforesaid process
for producing a polyolefin by the use of the above-mentioned
-- 21~4317 : ~
homogeneous catalyst involves the problems that ~1) the
resultant polymer dissolves in a solvent or becomes gel,
thereby making it difficult to separate the polymer from the
solvent, (2~ The polymer is likely to adhere to a reaction
vessel and (3) a high-molecular weight polymer is difficult
to produce.
There is proposed, as a process for producing a high-
molecular weight polymer, a method in which a homogeneous
catalyst composed of an oxygen-containing titanium compound
and an aluminoxane is employed. (~efer to Japanese Patent
Application Laid-Open No.3008/1988). However, the above-
mentioned process suffers the disadvantage that the formed
polymer adheres to a polymerization reactor, thus making it
dlfficult to proceed with the reaction in a stable manner.
As a means for regulating the molecular weight
distribution in the case of a homogeneous catalyst being
used, there are proposed (1) a method in which at least two
kinds of metallocene compounds are employed (Japanese Patent
Application Laid-Open Nos. 35006/1985 and 35008/1985) and (2)
a method in which polymerization is carried out at a specific
temperature by the use of a hafnocene compound (Japane8e
Patent Application Laid-Open No. 75605/1990). However, any
of the aforesaid methods suffers the disadvantage that the
operat:Lon is troublesome or only a specific condition is
utilizable for the method.
On the other hand, there is proposed a technique by
using a solid substance which is obtained by allowing a
homogeneous catalyst to be supported on an inorganic oxide
--" 21143~7
carrier (Japanese Patent Application Laid-Open No.
108610/1985). Nevertheless, the above-proposed technique
involv,es the problems of low activity of the catalyst per
unit a~ount of the carrier and frequent occurrence of film
gelling due to the carrier remainlng in the polymer. There
is also disclosed a catalyst composed of a non-metallocene
transition metal compound and an aluminoxane that are
supported on silica (Japanese Patent Application Laid-Open
No. 503715/1989 through PCT). However, the above-mentioned
catalyst involves the problem of low polymerization-activity
in spite of a high-molecular weight of the polymer to be
obtained.
DISCLOSURE OF THE INVENTION
Under such circumstances, intensive research and
investigation were made by the present inventors in order to
develop a process for producing a polyolefin capable of ~
enhancing the powder morphology of the resultant polymer and ~;
facilitating the regulation of the molecular weight
distribution of the polymer, a process for efficiently
producing in a stable manner a high-molecular weight
polyolefin having excellent particle shapes, and process for
efflciently producing a polyolefin characterized by any of
the above-mentioned process by the use of a catalyst enhanced
in polymerization activity. `~
As a result, it has been found by the present inventors
that the foregoing ob;ects are attained by the use of the
catalyst comprising a specific transition-metal compound, an ~;
aluminoxane and a specific magnesium compound or the catalyst
2114317
further comprising an organoaluminum compound in addition
thereto. The present invention has been accomplished on the
basis of the above-mentioned finding and information.
Specifically, the first aspect of the present invention
provides a process for producing a polyolefin which comprises
polymerizing an olefin by the use of a catalyst comprising
(A) a transition metal compound having a group with
conjugated ~ electron as a ligand, (B) an aluminoxane and (C)
a magnesium compound represented by the general formula
g( )n 2-n (I)
wherein R is an alkyl group, a cycloalkyl group, an aryl
group or an aralkyl group; X1 is a halogen atom; and n is a
number from 1 to 2, the second aspect thereof provides a
process for producing a polyolefin which comprises
polymerizing an olefin by the use of a catalyst comprising
the above-mentioned components (A), (B), (C) and (D) an
organoaluminum compound, the third aspect thereof provides a
process for producing a polyolefin which comprises
polymerizing an olefin by the use of a catalyst comprising
(E) a transition metal compound represented by the general
formula
MlRlaR2bR3CR4d (II)
wherein M1 is a transition metal belonging to the group IVB
in the Periodic table; Rl, R2, R3 and R4 are each a a-bonding
ligand, a chelating ligand or a Lewis base and may be the
same o:r different from each other; and a, b, c and d are each
an integer from 1 to 4, and the aforesaid components (B) and
(C), and the fourth aspects thereof provides a process for
-~~~` 21~1317
produci~g as polyolefin which comprises polymerizing an
olefin by the use of a castalyst comprising the aforesaid
components (E), (B), (C) and (D).
THE MOST PREFERRED EM~ODIMENT TO CARRY OUT THE INVENTION
In the first aspect of the present invention, there is
used as the catalyst the composition comprising the above-
mentioned components (A), (8) and (C). The transltion metal
compound having a group with conjugated ~ electron as a
ligand, that is, the component (A) is exemplified by the
compound represented by the general formula (III), (IV) or ~:
(V) and a derivative thereof.
Cp R eR fR g (III)
Cp2M Re Rf (IV)
(Cp-Ah-Cp)M2Re5Rf6 (V)
wherein M2 is a transition metal belonging to the group IVB ~
of the Periodic Table such as a Ti atom, Zr atom or Hf atom; ~:
Cp is an unsaturated cyclic hydrocarbon radical or an ~ ~
unsaturated chain hydrocarhon radical such as : .
cyclopentadienyl gorup, substituted cyclopentadienyl group,
indenyl group, substituted indenyl group, tetrahydroindenyl -
group, substituted tetrahydroindenyl group, fluorenyl group
or substituted fluorenyl group; R5, R6 and R7, independently
of one another, are each a ligand such as a a-bonding ligand,
a chelating ligand and a Lewis base, specifically exemplified
as a ~-bonding ligand by a hydrogen atom, an oxygen atom, a
halogen atom, an alkyl group having 1 to 20 carbon atoms, an
alkoxy group having 1 to 20 carbon atoms, an aryl group, an
alkylaryl group, an arylalkyl group each having 6 to 20 -
- 5 -
. ` ~
21143~7
carbor, atoms, an acyloxy group having 1 to 20 carbon atoms,
an all.yl group, a substituted allyl group and a substituent
containing a silicon atom and, as a chelating ligand, by an
acetylacetonato group and a substituted acetylacetonato
group; A is crosslinkage by covalent bond: e, f and g,
independently of one another, are each an integer from 0 to
4; h is an integer from 0 to 6; at least two out of R5, R6
and R may together form a ring; and when Cp has a
substituent, the substituent is preferably an alkyl group
having 1 to 20 carbon atoms.
Examples of the substituted cyclopentadienyl group in
the above-mentioned formulae (III) to ~V) include
methylcyclopentadienyl group; ethylcyclopentadienyl group;
isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl
group: tetramethylcyclopentadienyl group; 1,3-
dimethylcyclopentadienyl group; 1,2,3-
trimethylcyclopentadienyl group; 1,2,4-
trimethylcyclopentadienyl group; pentamethylcyclopentadienyl
group and trimethylsilylcyclopentadienyl group. Specific
examples of R5 to R7 in the aforesaid formulae (III) to ~V)
includ~e fluorine atom, chlorine atom, bromine atom and iodine
atom as halogen atom; methyl, ethyl, n-propyl, isopropyl, n-
butyl, octyl and 2-ethylhexyl group as alkyl group having 1
to 20 carbon atoms; methoxy, ethoxy, propoxy, butoxy and
phenoxy group as alkoxy group having 1 to 20 carbon atoms;
phenyl, tolyl, xylyl and benzyl group as aryl, alkylaryl or
arylal'kyl group each having 6 to 20 carbon atoms;
heptadlecylcarbonyloxy group as acyloxy group having 1 to 20
- 6 -
21~4317
, _
carbon atoms; trimethylsilyl and (trimethylsilyl)methyl group
as substituent containing silicon atom; as Lewis base, ethers
such as dimethyl ether, diethyl ether and tetrahydrofuran;
thioethers such as tetrahydrothiophene; esters such as
ethylbenzoate; nitriles such as acetonitrile and
benzonltrile; amines such as trimethylamine, triethylamine,
tributylamine, N,N-dimethylaniline, pyridine, 2,2'-bipyridine
and phenanthroline; phosphine such as triethylphosphine and
triphenylphosphine; unsaturated chain hydrocarbon such as
ethylene, butadien, l-pentene, isoprene, pentadiene, l-hexene
and derivatives thereof; unsaturated cyclic hydrocarbon such
as benzene, toluene, xylene, cycloheptatriene,
cyclooctadiene, cyclooctatriene, cyclooctatetraene and
derivatives thereof. Examples of A, that is, crosslinkage by ~
covalent bond in the above formula (V) include methylene, ~ :
dimethylmethylene, ehtylene, 1,1'-cyclohexylene,
dimethylsilylene, dimethylgermylene and dimethylstannylene
crosslinkage.
Specific examples of the compound represented by the
general formula (III) include
pentamethylcyclopentadienyltrimethyltitanium,
pentamethylcyclopentadienyltriphenyltitanium,
pentamethyloyclopentadienyltribenzyltitanium,
pentam~ethylcyclopentadienyltrichlorotitanium,
pentam~ethylcyclopentadienyltrimethoxytitanium,
cyclop~entadienyltrimethyltitanium,
cyclopentadienyltriphenyltitanium,
cyclopentadienyltribenzyltitanium,
- 2114317
cyclopentadienyltrichlorotitanium,
cyclopentadienyltrimethoxytitanium,
cyclopentadienyldimethylmethoxytitanium,
methylcyclopentadienyltirmethyltitanium,
methylcyclopentadienyltriphenyltitanium
methylcyclopentadienyltribenzyltitanium,
methylcyclopenadienyltrichlorotitanium,
methylcyclopentadienyldimethylmethoxytitanium,
dimethylcyclopentadienyltrichlorotitanium,
trimethylcyclopentadienyltrichlorotitanium,
trimethylcyclopetnadienyltrimethyltitanium,
tetramethylcyclopentadienyltrichlorotitanium, and any of the
above-exemplified compounds in which the titanium atom is
replaced with a zirconium or a hafnium atom.
Specific examples of the compound represented by the
general formula (IV) include
bis(cyclopentadienyl)dimethyltianium;
bis(cyclopentadienyl)diphenyltitanium;
bis(cyclopentadienyl)diethyltianium;
bis(cyclopentadienyl)dibenzyltitanium;
bis(cyclopentadienyl)dimethoxytianium;
bis(cyclopentadienyl)dichlorotitanium;
bis(cyclopentadienyl)dihydridotianium;
bls(cyclopentadienyl)monochlorohydridotitanium;
bis(methylcyclopentadienyl)dimethyltitanium;
bis(methylcyclopentadienyl)dichlorotitanium;
bis(methylcyclopentadienyl)dibenzyltitanium; .
bis(pentamethylcyclopentadienyl)dimethyltitanium;
` :
211~317
bis(pentamethylcyclopentadienyl)dichlorotitanium;
bis(pentamethylcyclopentadienyl)dibenzyltitanium; ~:
bis(pentamethylcyclopentadienyl)chloromethyltitanium; ~:
bis(pentamethylcyclopentadienyl)hydridomethyltitanium;
(cyclopentadienyl)(pentamethylcyclopentadienyl)- :
dichlorotitanium; and any of the above-mentioned compounds in
which the titanium atom is replaced with a zirconium or a
hafnium atom. .
Specific examples of the compound represented by the
formula (V) include ethylenebis(indenyl)dimethyltitanium;
ethylenebis(indenyl)dichlorotitanium;
ethylenebis(tetrahydroindenyl)dimethyltitanium;
ethylenebls(tetrahydroindenyl)dichlorotitanium;
dlmethylsllylenebis(cyclopentadienyl)dimethyltitanium;
dimethylsilylenebis(cyclopentadienyl)dichlorotitanium;
isopropylidene(cyclopentadienyl)(9-fluorenyl)
dimethyltitanium; isopropylidene(cyclopentadienyl)(9-
fluorenyl)dichlorotitanium;
[phenyl(methyl)methylene](9-fluorenyl)(cyclopentadienyl)
dlmethyltitanium;
diphenylmethylene(cyclopentadienyl)(9-fluorenyl)
dimethyltltanium;
ethylene(9-fluorenyl)(cyclopentadienyl)dimethyltitanium;
cyclohexalidene(9-fluorenyl)(cyclopentadienyl)
dimethyltitanium;
cyclopentylidene(9-fluorenyl~(cyclopentadienyl)
dimethyltitanium;
cyclobutylidene(9-fluorenyl)(cyclopentadienyl)
2114317
dimethyltitanium;
dimethylsilylene(9-fluorenyl)(cyclopentadienyl)
dimethyltitanium;
dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)
dichlorotitanium;
dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)
dimethyltitanium;
dimethylsilylenebis(indenyl)dichlorotitanium; any of the
above-mentioned compounds in which the titanium atom is
replaced with a zirconium or a hafnium atom.
Favorably usable titanium compound as the component (A)
among those represented by the general formula (V) is a
transition metal compound having a multidentate ligand in
which two substituted or unsubsituted con~ugated
cyclopentadienyl groups (at least one being substituted
cyclopentadienyl group) are bonded to one another via an
element selected from the group IVA of the Periodic Table.
By the use of such a compound, an isotactic polyolefin having
enhanc~ed isotacticity, a high molecular weight and a high
melting point is obtained.
E~amples of such compound include the compound
repres,ented by the general formula (VI) and derivatives
thereof
(R t ~ C5H4-t)"~ / X
9 / "~ 2
R 2Y \ M \ (VI)
(R u ~ C5H4-u) X
wherei;n M is a transition metal belonging to the group IV B
- 10 --
- . ' : . '.: ,
.': .' ' ' ~, ~ ' , ";'.. ' :. . '',,
211~3~7
of the Periodic Table, Y is a carbon atom, silicon atom,
germanium atom or tin atom; R t-C5H4 t and R u~C5H4 u are
each a substituted cyclopentadienyl group in which t and u
are each an integer from 1 to 4; R8 iS a hydrogen atom, silyl ~ :
group or hydrocarbon radical, and may be the same or
differ,ent, provided that at least one cyclopentadlenyl group
has R8 on at least one carbon atom ad~acent to the carbon
atom bonded to Y; R9 is a hydrogen atom, an alkyl group
having 1 to 20 carbon atoms, an aryl group, an alkylaryl
group or an arylalkyl group each having 6 to 20 carbon atoms;
X is a hydrogen atom, a halogen atom, an alkyl group having 1
to 20 carbon atoms, an aryl group, an alkylaryl group or an
arylalkyl group each having 6 to 20 carbon atoms or an
alkoxyl group having 1 to 20 carbon atoms and may be the same
or different.
Examples of the substituted cyclopentadienyl group in
the above-mentioned formula (VI) include
methyl,cyclopentadienyl group; ethylcyclopentadienyl group;
i~opropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl
group; 1,3-dimethylcyclopentadienyl group; 1,2,3-
trimet:hylcyclopentadienyl group; and 1,2,4-
trimethylcyalopentadienyl group. Specific examples of X
include F, Cl, Br and I as halogen atom; methyl, ehtyl n-
propyl, isopropyl, n-butyl, octyl and 2-ethylhexyl group as
alkyl group having 1 to 20 carbon atoms; methoxy, ethoxy,
propoxy, butoxy and phenoxy group as alkoxy group having 1 to
20 carbon atoms; phenyl, tolyl, xylyl and benzyl group as
aryl, alkylaryl or arylalkyl group each having 6 to 20 carbon
-- 1 1 --
-~` 21~43~7
atmos.
Specific Examples of R include methyl, ethyl, phenyl,
toly, xylyl and benzyl group.
Examples of the compounds represented by the general
formula (VI) include dimethylsilylenebis(2,3,5-
trimethylcyclopentadienyl)titanium dichloride and the
compound in which a titanium atom is replaced with a
zirconium atom or a hafnium atom.
In the present invention, the transition mstal compound
may be employed alone or in combination with at least one
other transition metal compound.
In the above-mentioned catalyst, an alumioxane is used
as the component (B), and there are usable the previously
known alumloxanes. Preferable examples thereof lnclude a
cycllc alumlnoxane represented by the general formula (VII)
~, R10
- ~ Al - O ~ (VII)
whereln R10 is a hydrocarbon radical having 1 to 8 carbon
atoms and r ls an integer from 2 to 100, and a chain
aluminoxane represented by the general formula (VIII)
~ ~12
R ~ Al O ~ Al R13 (VIII)
wherein Rl1, R12 and R13, independently of one another, are
each a hydrocarbon radical having 1 to 8 carbon atoms and S
i8 an integer from 2 to 100.
Preferable examples of R10 Rll R12 and R13 i 1 d
alkyl group such as methyl group, ethyl group and isobutyl
group, and r and s are each preferably 7 to 40. The
- 12 -
- 2~43~
alumioxane as the component (B) in the catalyst may be
employed alone or in combination with at least one other
aluminoxane.
Moreover in the above-mentioned catalyst, there is used
as the component (C), a magnesium compound represented by the
general formula (I)
Mg(OR)nX 2-n (I)
wherein R, Xl and n are each as previously deflned.
Preferable examples of the aforementioned magnesium compound
include dimethoxymagnesium, diethoxymagnesium, di-n-
propoxymagnesium, dipheoxyma~nesium, dibenzyloxymagnesium,
ethoxyphenoxymagnesium, chloromethoxymagnesium and
chloroethoxymagnesium. The above-exemplified magnesium
compound may be employed alone or in combination with at
least one other magnesium compound.
As the magnesium compound represented by the foregoing
general-formula (I), there is usable the reaction product
among metallic magnesium, an alcohol and an halogen. The
metallic magneslum to be employed in the reaction is not
specifically limited with regard to its shape, but may be in
any shape including granule, ribbon and powder. Likewise,
the surface condition of the metallic magnesium i9 not
specifically limited, but is preferably free from any coating
such as magnesium oxide formed on the surface.
The alcohol to be employed in the reaction is not
specifically limited with respect to its kind, but is -
preferably a lower alcohol having 1 to 6 carbon atoms,
especially ethanol because of its capability of providlng
- 13 -
-- 21~431 ~
solid catalyst component which enhances the catalytic
performance. There is no particular limitation to the purity
and water content of the alcohol. However, the water content
in the alocohol is desirably 1% by weight or less, more
desirably 2,000 ppm or less, particularly desirably as low as
possible, since the use of an alcohol having a high water
content will lead to the formation of magnesium hydroxide on
the surface of the metallic magnesium.
The usable halogen and/or halogen-containing compound
are not specifically limited in regard to its kind, ~ut may
be any compound provided that the chemical formula thereof
has a halogen atom. In this case, the halogen atom is not
speclfically limited in its ~ind, but is preferably a
chlorine atom, a bromlne atom or an iodine atom. Among the
hologen-containing compounds, a halogen-containing metallic
compound is particularly desirable.
Specific examples of the halogen-containing compound
includ,e MgCl2, MgI2, Mg(OC2H5)Cl, Mg(OC2H5)I, MgBr2, CaCl2,
NaCl and KBr, among which MgCl2 and MgI2 are particularly
dQsirable.
T,he halogen-containing compounds are not specifically
limited with regard to the condition, shape and particle
size, Ibut may be in an arbitrary form, for example, a
solution thereof in an alcohol-based solvent such as ethanol.
The amount of the alcohol to be used in the reaction is
u~ually in the range of 2 to 100 moles, preferably 5 to 50
moles ~er one mole of the metallic magnesium. An excessively
large amount of alcohol to be used is apt to cause difficulty
- 2114317
in providlng a magnesium compound having a faborable
morphology, whereas the use of a too small amount thereof
results in a possible failure to smoothly react wlth the
metallic magnesium. On the other hand, the amount of the
halogen and/or halogen-containing compound to be used in the
reacti,on is usually O.OOO1 g-atom or more, desirably 0.0005
g-atom or more, more desirably 0.001 g-atom or more per one
mole of the metallic magnesium. An amount of the halogen
and/or halogen-containing compound to be used less than
0.0001 g-atom brings about deterioration of the amount of
titaniumu to be supported, catalyst activity and the
stereo~egularity of the polymer to be formed when the
magnesium compound thus obtained is used as such without
being crushed. The result is unfavorable, since the crushing
of the magnesium compound is indispensably needed. The upper
limit of the amount of the halogen and/or halogen-containing
compound to be used is not specifically limited, but may be
suitabLy selected in the range which enables the production
of the desired magnesium compound. A suitahle selection of
the above-mentioned amount of the halogen and/or halogen-
containing compound to be used ma~e it possible to
arbltrarily control the particle size of the magnesium
compound to be produced.
The reaction among the metallic magnesium, the alcohol
and the halogen and/or halogen-containing compound can be put
into pxactice by using a conventional process, for example, a
process in which the metallic magnesium, the alcohol and the
halogen are reacted with each other under reflu~ usually for
- 15 -
2114317
2 to 30 hours until the generation of hydrogen gas is no
longer observed, thus producing the desired magnesium
product. Specifically usable process is exemplified by a
process wherein solid iodine is used as the halogen and
poured in a mixture of metallic magnesium and an alcohol,
followed by heating with reflux, a process wherein a
solution of iodine in an alcohol is added dropwise to a
mixture of metallic magnesium and an alcohol, followed by
heating with reflux, and a process wherein a solution of
iodine in an alcohol is added dropwise to a mixture of
metallic magnesium and an alcohol while being heated. In any
of the above-mentioned processe~q, it is preferable that the
reactlon be put into practice in an atmosphere of an inert
gas such as nitrogen gas and argon gas and, as the case may
be, by the use of an inert organic solvent such as a
saturated hydrocarbon exemplified by n-hexane. There is no
need to place the total amounts of both the metallic
magnesium and the alcohol in a reaction vessel at the start
of the reaction, but each of them may be dividedly placed
therein, for example, by a method in which the total amount
of the alcohol is placed at the start of the reaction,
followed by the addition of the metallic magnesium dividadly
into several times. The method is extremely desirable from
the viewpoint of safety, since the sudden generation of a
large amount of hydrogen gas is prevented thereby, and
further it is advantageous in that it can miniaturize a
reaction vessel and prevent the entrainment of the alcohol
and halogen caused by the sudden generation of a large amount
- 16
211 4317
of hydrogen gas. The number of times of divided addition may
be determined taking into consideration the scale and size of
the reaction vessel without specifical limitation, but ls
usually selected in the range of 5 to lO times in view of the
tediousness in the operation.
The reaction system may be any of batchwise and
continuous systems or a modified system in which a small
amount of metallic magnesium is placed in the alcohol which
has been put in a reaction vessel in a whole amount in
advance, the reaction product is removed by separatin~ into
another vessel, a small amout of metallic magnesium is again
placed in the remaining alcohol, and the above-mentioned
procedures are repeated.
The magnesium compound thus obtained can be used in the
subsequent step with crushing or classification procedure for
the purpose of uniformizing particle size.
By the use of the catalyst which comprises the
aforestated components (A), (B) and (C), it is possible to
contrive to improve the powder morphology of the polymer to
be produced and facilitate the regulation of the molecular
weight distribution of the polymer.
In the second aspect of the present lnvention, there is
employed the catalyst composition which comprises an
organoaluminum compound as the component (D) in addition to
the components of the catalyst in the aforestated first
aspect of the present invention. The combination of the
organoaluminum compound can enhance the polymerization
activity in addition to the above-mentioned properties.
:::
- 17 -
~ 21~317
Examples of the organoaluminum compound include the
compound represented by the general formula (IX)
R14mAlX 3 m (IX)
wherein R14 is an alkyl group having 1 to 20 carbon atoms or
an aryl group having 6 to 20 carbon atoms, x2 is a halogen
atom, an alkoxy group having 1 to 20 carbon atoms or an
aryloxy group having 6 to 20 carbon atoms and m is a real
number greater than 0 and not greater than 3. Specific
examples of such organoaluminum compound include
trimethylaluminum, triethylaluminum triisobutylaluminum, tri~
n-butylaluminum, tri-n-hexylaluminum, tri-n-octyl-aluminum,
triisopropylaluminum, diethylaluminum ethoxide,
diisobutylaluminum ethoxide, diethylaluminum chloride and
ethylaluminum dichloride. The preferable compound among them
i8 a trialkylaluminum represented by the general formula (X)
AlRl 5R1 6R1 7 ( X )
wherein R15, R16 and R17are each an alkyl group having 1 to
20 carbon atoms and may be the same or different from one
another. The organoaluminum compound may be used alone or in
combination with at least one of the other ones.
Next, in the third aspect of the present invention,
there Ls employed the catalyst composition which comprlses
the above-mentioned components (E), (B) and (C). The
transition metal compound as the component (E) is represented
by the general formula (II)
MlR1aR2bR3cR4d (II)
wherein M1, Rl, R2, R3, R4, a, b, c, and d are each as ~
previously defined. In the general formula (II), M is a --
: ::
- 18 -
'
~` 211~317
transition metal belonging to the group IVB of the Periodic
Table such as Ti atom, Zr atom or Hf atom; R1, R , R and R ,
independently of one another, are each a a-bonding ligand, a
chelating ligand or a Lewis base, specifically exempli~ied as
a a-bonding ligand by a hydrogen atom, an oxygen atom, a
halogen atom, an alkyl group havlng 1 to 20 carbon atoms, an
alkoxy group having 1 to 20 carbon atoms, an aryl group, an
alkylaryl group, an arylalkyl group each having 6 to 20
carbon atoms, an acyloxy group having 1 to 20 carbon atoms, a
substituted allyl group and a substituent containing a
silicon atom and, as a chelating ligand, by an
acetylacetonato group and a substituted acetylacetonato
group, at least two out of R , R , R and R may together
form a ring; and a, b, c and d, independently of one another,
are each an integer from 0 to 4.
Specific examples of the compound represented by the
general formula (II) inol~de tetramethyltitanium,
tetrab~enzyltitanium, tetramethoxytitanium,
tetraethoxytitanium, tetrapropoxytitanium,
tetrabutoxytitanium, titanium tetrachloride, titanium
tetrabromide, butoxytitanium trichloride, butoxytitanium
di.chlo:ride, bis(2,6-di-tert-butylphenoxy)dimethyltitanium,
bis( 2,6-di-tert-butylphenoxy)titanium dichloride, titanium
bis(ac,etylacetonato), bis(acetylacetonato)titanium
dichlo:ride, bis(acetylacetonato)titanium dipropoxide and any
of the above-mentioned compound in which titanium atom is
replaced with a zirconium or a hafnium atom. The above-
mentioned transition compound may be used alone or in
-- 19 -
combination with at least one of other one~1 14 3
The components (s) and (C) as described in the first
aspect of the present inven-tion can be used as the component
(B) and (C), respectively in the above-described catalyst.
The use of the catalyst comprising the aforesaid
components (E), ~B) and (C) enables a high molecular weight
polyolefin excellent in particle morphology to be effiaiently
produced in a stable manner with minimized adhesion of the
produced polymer to a polymerization reactor.
Next, in the fourth aspect of the present invention,
there is employed the catalyst composition which comprlses an
organoaluminum compound as the component (D) in addition to
the component8 of the catalyst in the aforestated third
aspect of the present invention. The combination of the
organoaluminum compound can enhance the polymerization
activi-ty in addition to the above-mentioned properties.
The component (D) as described in the second aspect of
the present invention can be used as the component (D) in the
catalyst of the fourth aspect thereof.
The amount of each of the components to be used in each
catalyst ls not specifically limited, but may be 8uitably
8elected according to the situation. It is usually selected
so that the amount of the component (A) or (E) is 10 4 to one
(1) mole, preferably 10 3 to 10 1 mole per mole of the
component (C), the amount of the component (B) is one (1) to
106 mo:les, preferably 10 to 105 moles per mole of the
component (A) or (E) expressed in terms of aluminum atom, and
the amount of the component (D) is 10 1 to 105 moles
- 20 -
21~ ~
preferably one (1) to 10 moles per mole of the component (A)
or (E)- : ~
The order of bringing each o~ the components of the
catalyst into contact with each other is not specifically
limited, but may be arbitrarily selected. The reac~ion
product after contact treatment may be used as such, or
cleaned with an inert solvent prior to using, or distilled to
distil away the preparation solvent and dispersed in another
solvent, followed by using.
Examples of the inert solvent to be used in bringing
each component into contact with one another include
aliphatic hydrocarbons each having 5 to 18 carbon atoms,
alicyclic hydrocarbons and aromatic hydrocarbons, whlch are
specifically enumerated by n-pentate, isopentane, hexane,
heptane, octane, nonane, decane, tetradecane, cyclohexane,
benzene, toluene and xylene. Any of the above-enumerated
solvents may be used alone or as a mixture with at least one
other one. The contact temperature and reaction time are not
specifically limited.
The contact treatment may be carried out in a manner
similar to preliminary polymerization in the presence of a
small amount of a monomer, or under the condition including a
remarkably low rate of polymerization reactlon.
The contact-treated product thus prepared can be
preserved in an atmosphere of an inert gas.
There is usable in the present invention, an arbitrary
olefin as the monomer such as an a-olefin and a cyclic
olefin, which are enumerated as a-olefin, ethylene,
21 ~31~
propylene, l-butene, 1-hexene, l-octene and 1-decene, and as
cyclic olefin, cyclobutene, cyclopentene, cyclohexene,
cycloheptene and cyclooctene. In the present invention, an
olefin can be copolymerized with an unsaturated monomer
component other than olefin which component
is copolymerizable with the olefin.
The process according to the present invention is
particularly preferably applicable to the production of an
ethylenic polymer. In this case, ethylene may be
homopolymerized or copolymerized with an a-olefin other than
ethylene or a diene compound. Examples of such a-olefin
include straigh-chain or branched monoolefin having 3 to 18
carbon atoms and a-olefin replaced with an aromatic group.
Specific examples of such a-olefin include straight-chain
monoolefin such as propylene; butene-1; hexene-1; octene-1;
nonene-1; decene-1; undecene-1; and dodecene-1, branched
monoolefin such as 3-methylbutene-1; 3-methylpentene-1; 4-
methylpentene-l; 2-ethylhexene-1; and 2,2,4-trimethylpentene-
1 and monoolefin replaced with a benzene ring such as
styrene.
Examples of the preferable diene compound include a
8traight chain or branched non-con~ugated diolefin such as
1,5-hexadiene; 1,6-heptadiene; 1,7-octadiene; 1,8-nonadiene;
1,9-decadiene; 2,5-dimethyl-1,5-hexadiene; and 1,4-dimethyl-
4-tert-butyl-2,6-heptadiene, polyene such as 1,5,9-decatriene
and end-methylene series cyclic diene such as 5-vinyl-2-
norbornene.
The polymerization method in the present invention is
- 22 -
2~431~
not specifically limited, but is usually any of slurry, hot
solution, gas-phase or bulk polymerization method, etc.. As
the polymerization solvent, an inert slovent such as an
aliphatic hydrocarbon, an alicyclic hydrocarbon or an
aromatic hydrocarbon is employed, among which is preferable
an aliphatic hydrocarbon exemplified by hexane and heptane.
It is preferable that the amount of the polymerization
catalyst to be used be selected in the range of 10 8 to 10 2
mole/liter, preferably 10 7 to 10 3 mole/liter expressed in
terms of the atoms of the transition metal belonging to the
group IVB of the Periodic Table.
The polymerization temperature is not specifically
limited, but is usually selected in the range of O to 350C,
prefer,ably 20 to 250C. On the other hand, the
polymerization pressure is not specifically limited as well,
but is usually selected in the range of O to 150 kg/cm2G,
preferably O to 100 kg/cm2G.
The modification of the molecular weight and the
molecular weight distribution of the polyolefin to be
produced can be carried out with case by adding hydrogen into
the re~sction system at the tlme of polymerization. The
addition of hydrogen is effective particularly in the first
and second aspects of the present invention.
In the following, the present invention will be
described in more detail with reference to examples and
comparative examples.
Preparation Example 1 : Preparation of solution of
methylaluminoxane in toluene
- 23 -
21~317
A solution of mehtylaluminoxane (produced by TOSOH AKUZO
CORPORATION ) in toluene was made into the form of thick malt
syrup by reducing the pressure at room temperature.
Subsequently, the pressure was further reduced at 90~C for
one (1) hour to produce methylaluminoxane crystal in solid
form, which was then dispersed in toluene to prepare 1.9
mole/liter solution of methylalumioxane in toluene expressed
in terms of ~1 atom.
Preparation Example 2 : Preparation of dispersion liquid of
methylalumioxane in hexane
A solution of methylalumioxane (produced by Shelling
Corporation) in toluene was made into the form of thick malt
syrup by reducing the pressure at room temperature.
Subsequently, the pressure was further reduced at 90C for
one (1) hour to produce methylaluminoxane crystal in solid ~`
form, wh$ch was then dispersed in hexane to prepare 1.0
mole/liter dispersion liguid of methylaluminoxane in hexane ;
expressed in terms of Al atom.
Example 1
(1) Preparation of solid product
A 6 liter glass-made reactor equipped with a stirrer
which had sufflciently been purged with nitrogen gas was
charged with 2430 g of ethanol, 16 g of iodine and 160 g of
metallic magnesium. The mixture in the reactor was allowed
to react with stirring under heating and reflux condition
until the generation of hydrogen gas was no longer observed
to produce a reaction product in solid form. The reaction
liquid containing the reaction product was dried under
- 24 -
~` 2ll43l7
reduced pressure to afford a solid product.
(2) Preparation of solid catalyst components
To 10 g of the solid product (62 ~m average particle
size) as produced in the preceding item (1) were added in
turn a solution of 0.17 mmol of bis
(cyclopentadienyl)zirconium dichloride in 50 ml of tol~ene
and 1.9 mole/liter solution of methylaluminoxane in toluene
in an amount of 35 mmol in terms of methylaluminoxane. The
mixture was allowed to react at room temperature with gentle
stirring for one hour. Then, the toluene solvent was removed
by reducing the pressure with gentle stirring at room
temperature. Subsequently heptane was added to the reaction
system to form a slurry in a total amount of 400 ml. All o$
the aforesaid procedure was carried out in an atmosphere of
dry nitrogen.
(3) Polymerization of ethylene
A one (1) liter dry polymerization reactor equipped with
a stirrer the inside of which had been purged with dry
nitrogen was charged with 400 ml of dry heptane and further
with 2.6 ml of solution of methylaluminoxane in toluene (1.9
mmol/llter) and 0.003 mmol of the solid catalyst component as
prepared in the preceding item (2) expres~ed in terms of
zirconium.
Subsequently the reaction system was heated to raise the
temperature up to 80C, charged with hydrogen so as to attain
a hydrogen partial pressure of 0.06 kg/cm2G and pressurized
with ethylene so as to maintain the internal pressure in the
polymerization reactor at 8 kg/cm2G, and ethylene was further
2114~7
introduced there$n so as to maintain the internal pressure at
8 kg/cm2G to proceed wi~h polymerization at 80C for one
hour.
After the completion of polymerization, the reactor was
opened and the resultant polymer slurry was poured in 2 liter
of mixed liquid of methanol and hydrochloric acid. The
polymer was filtered off, washed with methanol and dried at
80C under reduced pressure for 4 hours.
As the result, there was obtained 23.0 g of polymer
powder with favorable fluidity at a polymerization activity
:. :
of 84 kg/g-Zr, which polymer had an apparent bulk density of
0.17 g/ml, a weight-average molecular weight (Mw) of 46000
and a ratio of welght-average molecular weight(Mw) to number-
average molecular weight(Mn)(Mw/Mn) of 4.9.
Comparative Example 1
The procedure in Example 1 was repeated to polymerize
ethylene except that 0.003 mmol of
bis(cyclopentadienyl)zirconium dichloride expressed in terms
of zirconium(Zr) and 1.3 ml of 1.9 mol/liter solution of
methylaluminoxane in toluene were added to the reaction
system at the time of polymerization without preparing a
solid catalyst component, and hydrogen partial pressure was
set to 0.10 kg/cm2G.
As a result, 23.7 g of polymer was obtained in the form
of agglomerate and had a Mw of 38000 and a Mw/Mn ratio of
2.6.
Example 2
The procedure in Example 1 was repeated to polymerize
~ 26 -
21~ 4317
ethylene except that the solid catalyst component in an
amount of 0.0015 mmol expressed in terms of zr and 1.3 ml of
1.9 mole/liter solution of methylaluminoxane in toluene were
used and hydrogen was not added to the reaction system.
As a result, 22.4 g of polymer was obtalned at a
polymerlzation activity of 164 kg/g-Zr and had an apparent
bulk density of 0.07 g/ml, a Mw of 220,000 and a Mw/Mn ratio
Of 2.6.
Comparative Example 2
(1) Preparation of catalyst components
The procedure in Example 1 (2) was repeated to prepare
catalyst components except that the solid product was not
lncorporated.
(2) Polymerization of ethylene
The procedure in Example 2 was repeated to polymerlze
ethylene except that the catalyst components as prepared in
the preceding item (1) were used in place of the solid
catalyst components.
However, after an elapse of 25 minutes from the start of
polymerization, the polymerization was discontinued because
of impossibility of the temperature control. On opening the
polymerization reactor, there was observed remarkable
adhesion of the polymer to the inside wall of the reactor.
Example 3
Tlhe procedure in Example 2 was repeated to polymerize
ethylene except that 5.3 ml of l.9 mole/liter solution of
methylaluminoxane in toluene was used.
A~3 a result, 32.0 g of polymer was obtained at a
- 27 -
21~ 4317 ~
polymerization activity of 234 kg/g-Zr and had a Mw of
220,000 and a Mw/Mn ratio of 2.6.
Examplle 4
(1) Preparation of solid catalyst components
The procedure in Example 1 (2) was repeated to prepare
solid catalyst components except that methylaluminoxane was
not incorporated. ;~
(2) Polymerization of ethylene
The procedure in Example 3 was repeated to polymerize
ethylene except that the solid catalyst components as
prepared in the preceding item (l) were used in place of ~
those ln Example 3.
A~3 a result, 25.3g of polymer was obtained at a
polymerlzation activity of 185 kg/g-Zr and had an lntrinsic
viscosity [nl of 3.1 dl/g.
Example 5
(l) Preparation of solid catalyst components
The procedure in Example 1 (2) was repeated to prepare
solid aatalyst components except that one (1) g of the solid
product was used.
t2) PoLymerization of ethylene
The procedure in Example 3 was repeated to polymerlze
ethylene except that the solid catalyst components as
prepared in the preceding item (1) were used in place of
those :Ln Example 3 and that the polymerization was carried
out for 30 minutes.
As a result, 47.7 g of polymer was obtained at a
polyme:rization activity of 349 kg/g-Zr and had an intrinsic
- 2~ -
21i4317
viscosity [ n ] of 4.1 dl/g.
Example 6
Ethylene was polymerized through preliminary
polymerization.
A one (1) liter dry polymerization reactor equipped
with a stirrer the inside of which had been purged with dry
nitrogen was charged with 400 ml of dry heptane and further
with 1.3 ml of solution of methylaluminoxane in toluene (1.9
mmol/liter) and 0.0015 mmol of the solid catalyst component
as prepared in Example 1 (2) expressed in terms of zirconium.
Then, 0.17 Nl of ethylene was introduced into the reactor to
carry out preliminary polymeri7ation at 17C for 30 minutes.
Subsequently the reaction system was heated to raise the
temperature up to 80C and pressurized with ethylene so as to
maintain the internal pressure in the polymerization reactor
at 8 kg/cm2G, and ethylene was further introduced therein so
as to maintain the internal pressure at 8 kg/cm2G to proceed
with polymerization at 80C for one hour.
After the completion of polymerization, the reactor was
opened and the resultant polymer slurry was poured in 2 liter
of mix~ed liquid of methanol and hydrochloric acid. The
polymer was filtered off, washed with methanol and dried at
80C under reduced pressure for 4 hours.
As the result, there was obtained 9.5 g of polymer
powder with favorable fluidity at a polymerization activity
of 69 kg/g-Zr.
Exampl~e 7
Ethylene was copolymerized with 1-octene.
- 29 -
'~
-` 21~43~7
A one (1) liter dry polymerization reactor equipped
with a stirrer the inside of which had been purged with dry
nitrogen was charged with 370 ml of dry heptane and further
with 30 ml of 1-octene, 1.3 ml of solution of
methylaluminoxane in toluene (1.9 mmol/liter) and 0.0015 mmol
of the solid catalyst component as prepared in Example 1 (2)
expressed in terms of zirconium. Immediately thereafter, the
reaction system was heated to raise the temperature up to
60C and pressurized with ethylene so as to maintain the
internal pressure in the polymerization rea~tor at 8 kg/cm2G,
and ethylene was further introduced therein so as to maintain
the internal pressure at 8 kg/cm G to proceed with
polymerization at 60C for one hour.
After the completion of polymerization, the reactor was
opened and the resultant polymer slurry was poured ln 2 liter
of mixed liquid of methanol and hydrochloric acid. The
polymer was filtered off, washed with methanol and dried at
80C under reduced pressure for 4 hours.
As the result, there was obtained 25.4 g of polymer
powdsr with favorable fluidity at a polymerization activity
of 186 kg/g-Zr, which polymer had a density of 0.925 g/ml, 1-
octene unit content of 4% by weight, a weight-average
molecular weight (Mw) of 140,000 and a ratio of weight-
average molecular weight (Mw) to number-average molecular
weight (Mn)(Mw/Mn) of 2.7.
Example 8
(l) Preparation of solid catalyst
To 32 ml of toluene were added l.0 ml of l.0 mole/liter
_ 30 -
2~317
solution of triisobutylaluminum in toluene, 10.7 ml of 1.9
mole/liter solution of methylaluminoxane in toluene and 7.6
ml of 13 mmol/liter solution of
bis(cyclopentadienyl)zirconium dichloride in toluene with
stirring for 20 minutes. To the resultant mixture was
further added 50 ml of the dispersion liquid (1.0 mole/liter)
of the solid product which was obtained in Example 1 (1) in
toluene as the dispersant with further stirring for 2 hours.
The toluene contained in the slurry thus obtained was
distilled away and 100 ml of hexane was added to the
remaining slurry to prepare solid catalyst slurry.
(2) Polymerization of ethylene
A one (1) liter dry polymerization reactor equipped
with a stirrer the inside of which had been purged with dry
nitrogen was charged with 400 ml of dry heptane and further
with 1.3 ml of solution of methylaluminoxane in toluene (1.9
mmol/liter) and 2.0 ml of the solid catalyst slurry as
prepared in the preceding item (1)(2 micromol of Zr).
Immediately thereafter the reaction system was heated to
raise the temperature up to 80C and pressurized with
ethylene so as to maintain the total internal pressure in the
polymerization reactor at 8 kg/cm2G to proceed with
polymerization a 80C for one hour.
After the completion of polymerization, the reactor was
immediately depressurized and charged with methanol to arrest
polymerization, and the resultant polymer slurry was poured
in a large amount of mixed liquid of methanol and
hydrochloric acid for deashing. The polymer was filtered off
- 31 ~
' . ; , . ' : . : ~ ` . '
2~4317
and dried at 80C under reduced pressure for 4 hours.
As the result, there was obtained 31.9 g of polymer
granul,e. Table 1 gives the polymerization activity, apparent
bulk density [ n ]and Mw/Mn.
Examplle 9 :
(1) Preparation of solid catalyst
The procedure in Example 8 (1) was repeated to prepare
solid ,-atalyst slurry except that 1.0 ml of 1.0 mole/liter
solution of triisobutylaluminum in toluene was not
incorporated.
(2) Polymerization of ethylene
The procedure in Example 8 was repeated to polymerize
ethyle;ne except that the solid catalyst slurry as prepared in
the pr~eceding item (1) was used. The results are given in
Table 1.
Compar,ative Example 3
The procedure in Example 8 was repeated to polymerize
ethylene except that the preparation of the solid catalyst
slurry was omitted and there were used
bis(cyclopentadienyl)zirconium dichloride in an amount of 0.5
micromol as Zr and 1.3 ml of 1.9 mole/liter solution of
methylaluminoxane in toluene at the time of polymerization.
The results are given in Table 1. Afte the polymerization
there was observed the polymer which adhered to the agitation
impellers and the walls of the reactor.
Example 10 ~ ~;
(l) Polymerization of ethylene
The procedure in Example 8 was repeated to polymerize ~ -
- 3~
2114317
ethylene except that hydrogen was introduced in the reaction
system so as to attain 0.10 kg/cm2G. The results are glven
in Table 1.
Comparative Example 4
The procedure in Example 10 was repeated to polymerize
ethylene except that the preparation of the solid catalyst
slurry was omitted and there were used
bis(cyclopentadienyl)zirconium dichloride in an amount of 1.0
micromol as zr and 1.3 ml of 1.9 mole/liter solution of
methylaluminoxane in toluene at the time of polymerization.
The re~ults are given in Table 1.
Example ll
(1) Preparation of solid catalyst
The procedure in Example 8 was repeated to prepare
solid oatalyst slurry except that 6.7 ml of 15 mmol/liter
solution of cyclopentadienylzirconium trichloride in toluene
was used in place of 7.6 ml of 13 mmol/liter solution of
bis(cyclopentadienyl)zirconium dichloride in toluene.
(2) Polymerization of ethylene ~ -
The procedure in Example 8 was repeated to polymerize
ethylene except that there was used 10.0 ml of the solid
catalyst slurry (10 micromol as Zr) as prepared in the
preced:ing item (1). The results are given in Table 1.
Example 12
(1) Preparation of solid catalyst
rhe procedure in Example ll (1) was repeated to prepare
solid catalyst slurry except that 1.0 ml of 1.0 mol/liter
solution of trilsobutylaluminum in toluene was not
- . .. . . . . . ..
21 14317
incorporated.
(2) Pc,lymerization of ethylene
The procedure in Example 11 was repeated to polymerize
ethylene except that the solid catalyst slurry as prepared in
the preceding item (1) was used. The results are given in
Table 1.
Example 13
The procedure in Example 11 was repeated to polymerize
ethylene except that hydrogen was introduced in the reaction
system so as to attain 0.10 kg/cm2G. The results are given
in Table 1.
Comparative Example 5
The procedure in Example 10 was repeated to polymerize
ethylene except that the preparation of the solid catalyst
slurry was omitted and there were used
cyclopentadienylzirconium trichloride in an amount of 3.0
micromol as Zr and 1.3 ml of 1.9 mole/liter solution of
methylaluminoxane in toluene at the time of polymerization.
The results are given in Table 1. ~ -
:, ~ ~''
,.
'''
- 34 -
Table 1 21~3~ 7
Polymer yield Polymer.ization Bulk density [ ]
activity n
(g)(kQ /~-Zr) (g/ml) (dl/g)
Example 8 31.9 175 0.08 3.8
Example 9 24.1 132 0.06 3.3
Comparative 21.8 478 0.03 3.9
Example 3
Example 10 15.1 83 0.18 1.0
Comparative 29.6 325 not measurable 0.9
Example 4
Example 11 34.5 38 0.06 4.2
Example 12 19.2 21 0.06 3.8
Example 13 22.8 25 0.15 1.1
Comparative 18.1 66 not measurable 1.0
Example 5
Table 1 (continued)
Mw/Mn Remarks :
Example 8 2.5
Example 9 2.6
- ,: .. . .::
Comparative 2.6 adhesion of polymer to agitation
Example 3 impellers, etc. : ;
Example 10 4.5
Comparative 2.6 agglomerate polymer
Example 4
Example 11 2.5
Example 12 2.6
Example 13 4.8
Comparative 2.5 agglomerate polymer
Example 5 ~ :
- 35 -
2114317
Example 14
(1) Preparation of solid catalyst
To 129 ml of toluene were added 3 ml of 0.1 mole/liter
solution of tetra-n-butoxytitanium in hexane and 15 ml of 1.0
mole/liter dispersion liquid of the above-mentioned
methylaluminoxane in hexane with stirring for one (1) hour.
To the resultant mixture was further added 34.3 ml of the
dispersion liquid (lOOgJliter) of the solid product which was
obtained in Example 1 (1) in hexane as the dispersant with
further stirring for one (1) hour. The slurry thus obtained
was washed three times each with 400 ml of hexane and diluted
with hexane to a total volume of 150 ml to prepare solid
catalyst slurry, which had a titanium concentration of 1.9 ~;
mmol-T:L/liter. No titanium component was detected in the
supernatant hexane of the slurry. ~ ~
(2) Po:Lymerization of ethyLene ~ -
A one (1) liter dry polymerization reactor equipped
with a stirrer the inside of which had been purged with dry
nitrogen was charged with 400 ml of dry n-hexane, and the
mixture was heated to raise the temperature to 60C.
Subsequently 21.0 ml (40 micromol of Ti) of the solid
catalyst slurry as prepared in the preceding item (1) was
placed in the polymerization reactor, immediately followed by
raisin~a the temperature of the mixture in the reactor to
80C. Then ethylene was introduced into the reactor to carry
out po:Lymerization at 80C for one (1) hour so as to maintain
the total internal pressure in the polymerization reactor at
8 kg/cm2G.
- 36 -
21 14 ~ t I
After the completion of polymerization, the reactor was
immediately depressurized and charged with methanol to arrest
polymerization, and the content in the reactor was poured in
a large amount of mixed liquid of methanol and hydrochloric
acid. The polymer was filtered off, and dried at 80C under
reduced pressure for 4 hours. There was not observed any
polymer adhesion to the reactor.
As the result, there was obtained 5.6 g of polyethylene
powder in particulate form having a [ n ] of 35 dl/g.
Example 15
A one (1) liter dry polymerization reactor equipped
with a stirrer the inside of which had been purged with dry
nitrog~en was charged with 400 ml of dry n-hexane and 1.0 ml
of 1.0 mol/liter solution of triisobutylaluminum in hexane,
and thle resultant mixture was heated to raise the temperature
up to 60C.
Then, by the use of the solid catalyst slurry as
prepared in Example 14 (1), ethylene was polymerized in the
same manner as in Example 14. There was not observed any
polymer adhesion to the walls of the reactor.
As the result, there was obtained 7.0 g of polyethylene
powder in particulate form having a [ n ] of 39 dl/g.
Comparative Example 6
(1) Pr,sparation of mixed liquid of catalyst components
To 132 ml of toluene were added 3 ml of 0.1 mol/liter
solution of tetra-n-butoxytitanium in hexane and 15 ml of 1.0
mol/liter dispersion liquid of the above-mentioned
methylaluminoxane in hexane as the dispersant, with stirring
:
. ~
- 37 - ~
211~317
for one (1) hour.
(2) Polymerization of ethylene
A one (1) liter dry polymerization reactor equipped
with a stirrer the inside of which had been purged with dry
nitrogen was charged with 400 ml of dry n-hexane and 1.0 ml
of 1.0 mole/liter of triisobutylaluminum in hexane followed
by raising the temperature of the mixture in the reactor to
60C. Subsequently 20.0 ml (40 micromol of Ti) of the mixed
liquid of the catalyst component as prepared in the preceding
item (1) was placed in the polymerization reactor.
Immediately thereafter the reaction system was heated to
raise the temperature up to 80C and pressurized with
ethylene so as to maintain the total internal pressure in the .
polymerization reactor at 8 kg/cm2G to proceed with
polymerizatlon at 80C for one hour.
After the completion of polymerization, the reactor was
immediately depressurized and charged with methanol to arrest
polymerizaiton.
As the result, there was obtained 8.0 g of agglomerate
polymer whlch adhered to the agitation impellers and the
walls of the reactor.
Example 16
(1) Preparation of solid catalyst
To 126 ml of toluene were added 3.0 ml of 1.0
mole/liter solution of triisobutylaluminum in hexane and 3 ml
of 0.1 mole/liter solution of tetra-n-butoxytitanium in
hexane with stirring for 10 minutes, and then 15 ml of 1.0
mole/liter dispersion liquid of the above-mentioned
~ 21~3~ ~
methylaluminoxane in hexane as the dispersant with stirring
for one (1) hour. To the resultant mlxture was fur-ther added
34.3 mmol of the dispersion liquid (100 g/liter) of the solid
product which was obtained in Example 1 (1) in hexane as the
dispersant with further stirring for one (1) hour. The
slurry thus obtained was washed three times each with 400 ml
of hexane and diluted with hexane to a total volume of 150 ml
to prepare solid catalyst slurry, which had a titanium
concentration of 1.6 mmol-Ti/liter. No titanium component
was detected in the supernatant hexane of the slurry.
(2) Polymerization of ethylene
The procedure in Example 15 was repeated except the use
of 25.0 ml (40 micromol of Ti) of the solid catalyst slurry
as prepared in the preceding item (1).
There was not observed any polymer adhesion to the
reactor.
As a result, there was obtained 43.6 g of polyethylene
powder in particulate form~having a [ n ] Of 46 dl/g a bulk
density of 0.13 g/ml.
Examp_e 17
(1) Copolymerization of ethylene and 1-octene
A one (1) liter dry polymerization reactor equipped
with a stirrer the inside of which had been purged with dry
nitrogen was charged with 360 ml of dry n-hexane, A0 ml of 1-
octene and 1.0 ml of 1.0 mol/liter of triisobutylaluminum in
hexane, followed by raising the temperature of the mixture in
the reactor to 60~C. Subsequently, 25.0 ml (40 micromol of
Ti) of the solid catalyst slurry as prepared in Example 16
- 39 ~
~ 21 ~43~r~
(1) was placed in the polymeriæation reactor. Immediately
thereafter, the reaction system was heated to raise the
temperature up to 80C and pressurized with ethylene so as to
maintaln the total internal pressure in the polymerization
reactor at 8 kg/cm G, to proceed with polymerization at 80C
for one hour.
After the completion of polymerization, the reactor was
immediately depressurized and charged with methanol to arrest
polymerization.
There was not observed any polymer adhesion to the
reactor.
As a result, there was obtained 42.9 g of
ethylene/octene copolymer in particulate form having a [ n ] f
41 dl/g, a bulk density of 0.15 g/ml, 1-octene unit content
of 0.5 mole% and a melting point of 127C.
Comparative Example 7
(1) Pr~aparation of mixed liquid of catalyst components
To 129 ml of toluene were added 3.0 ml of 1.0
mole/liter solution of triisobutylaluminum in hexane and 3 ml
of 0.1 mole/liter solution of tetra-n-butoxytitanium in
hexane with stirring for 10 minutes, and then 15 ml of 1.0
mole/lLter dispersion liquid of the above-mentioned
methylaluminoxane in hexane as the dispersant wlth stirring
for one (1) hour.
(2) Copolylmerization of ethylene and 1-octene
The procedure in Example 17 was repeated except the use
of 20.0 ml (40 micromol of Ti) of the mixed liquid of
catalyst components as prepared in the preceding item (1~.
-- ~0 --
211431 1
However, after an elapse of 30 minutes from the start
of the polymerization, the polymerization was discontinued
because of impossibility of the temperature control. On
opening the polymerization reactor, there was observed 35.2 g
of agg:Lomerate polymer which adhered to the walls and
impellers of the reactor.
INDUSTRIAL APPLICABILITY
As described hereinbefore, the present invention
enables to contrive to improve the powder morphology of the
produced polymer and facilitate the regulation of the
molecular weight distribution thereof and besides to
efficiently and stably produce a high molecular weight
polyolefin having excellent particle shape with minimized
adhesion of the resultant polymer to the polymerization
reactor.
Thus, the process according to the present invention is
preferably applicable to the production of ethylenic polymers
such as polyolefin, especially low-density linear polyolefin,
thereby rendering itself extremely valueable in utilization.
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