Catalyst for polymerizing alpha-olefins and process for polymerization

A prepolymerized solid catalyst for gaseous phase or slurry polymerization of alpha olefins is disclosed. The catalyst comprises a porous carrier having a particle size of 20 to 200 microns onto which has been deposited an aluminoxane and a transition metal compound having at least one cycloalkadienyl group, the transition metal being from group 4 of the Periodic Table. The transition metal is present in an amount of 0.003 to 3 mmol/gm of carrier, and the aluminum to transition metal atomic ratio is from 15 to 1000. This catalyst is then prepolymerized with 0.2 to 30 gm of an alpha olefin per gram of catalyst to form the final prepolymerized solid catalyst having an intrinsic viscosity of 0.2 to 20 dl/gm as measured in decalin at 135 deg C.

TECHNOLOGICAL FIELD 
This invention relates to a catalyst for polymerization of alpha-olefins, 
and to a polymerization process. More specifically, it relates to a 
catalyst for polymerization of alpha-olefins which by a slurry 
polymerization method or a vapor-phase polymerization method, particularly 
the latter, can give a spherical polymer having a good particle size 
distribution and an excellent bulk density, and to a polymerization 
process using the aforesaid catalyst. Furthermore, it relates to a 
catalyst for polymerization of alpha-olefins which when applied to the 
copolymerization of at least two olefins, exhibits high polymerization 
activity and gives an olefin copolymer having a narrow molecular weight 
distribution and a narrow composition distribution, and to a 
polymerization process using the catalyst. 
BACKGROUND TECHNOLOGY 
For the production of an alpha-olefin polymer, particularly an ethylene 
polymer or an ethylene/alpha-olfein copolymer, methods have previously 
been known in which ethylene is polymerized, or ethylene and an 
alpha-olefin are copolymerized, in the presence of a titanium-containing 
catalyst comprising a titanium compound and an organoaluminum compound or 
a vanadium-containing catalyst comprising a vanadium compound and an 
organoaluminum compound. 
On the other hand, catalysts comprising a zirconium compound and an 
aluminoxane have been proposed recently as a new type of Ziegler catalyst 
for olefin polymerization. 
Japanese Laid-Open Patent Publication No. 19309/1983 discloses a process 
which comprises polymerizing ethylene and at least one alpha-olefin having 
3 to 12 carbon atoms at a temperature of -50.degree. C. to 200.degree. C. 
in the presence of a catalyst composed of a transition metal-containing 
catalyst represented by the following formula 
EQU (cyclopentadienyl).sub.2 MR.sup.1 Hal 
wherein R.sup.1 represents cyclopentadienyl, C.sub.1 -C.sub.8 alkyl or 
halogen, M represents a transition metal, and Hal represents halogen, 
with a linear aluminoxane represented by the following formula 
EQU Al.sub.2 OR.sub.4.sup.2 (Al(R.sup.2)--O).sub.n 
wherein R.sup.2 represents methyl or ethyl, and 
n is a number of 4 to 20, 
or a cyclic aluminoxane represented by the following formula 
##STR1## 
wherein R.sup.2 and n are as defined above. 
This patent document states that in order to adjust the density of the 
resulting polyethylene, ethylene should be polymerized in the presence of 
a small amount (up to 10% by weight) of a slightly long-chain alpha-olefin 
or a mixture thereof. 
Japanese Laid-Open Patennt Publication No. 95292/1984 describes an 
invention relating to a process for producing a linear aluminoxane 
represented by the following formula 
##STR2## 
wherein n is 2 to 40 and R.sup.3 is C.sub.1 -C.sub.8 alkyl, and a cyclic 
aluminoxane represented by the following formula 
##STR3## 
wherein n and R are as defined above. 
This Publication states that when an olefin is polymerized using a mixture 
of methylaluminoxane produced by the above process with a 
bis(cyclopentadienyl) compound of titanium or zirconium, polyethylene is 
obtained in an amount of at least 25 million grams per gram of the 
transition metal per hour. 
Japanese Laid-Open Patent Publication No. 35005/1985 discloses a process 
for producing a catalyst for polymerization of olefins, which comprises 
reacting an aluminoxane compound represented by the following formula 
##STR4## 
wherein R.sup.4 represents C.sub.1 -C.sub.10 alkyl, and 
R.sup.o is R.sup.4 or is bonded to represent --O--, with a magnesium 
compound, then chlorinating the reaction product, and treating the 
chlorinated product with a compound of Ti, V, Zr or Cr. The above 
Publication describes that the above catalyst is especially suitable for 
the copolymerization of ethylene with a C.sub.3 -C.sub.12 alpha-olefin 
mixture. 
Japanese Laid-Open Patent Publication No. 35006/1985 discloses a 
combination of (a) a mono-, di- or tri-pentadienyl compound of at least 
two dissimilar transition metals or its derivative with (b) alumoxane 
(aluminoxane) as a catalyst system for polymers blended in a reactor. 
Example 1 of this Publication discloses that polyethylene having a number 
average molecular weight of 15,300 and a weight average molecular weight 
of 36,400 and containing 3.4% of a propylene component was obtained by 
polymerizing ethylene and propylene using bis(pentamethylcyclopentadienyl) 
dimethyl zirconium and alumoxane as a catalyst. In Example 2 of this 
Publication, a blend consisting of polyethylene and an ethylene/propylene 
copolymer and having a number average molecular weight of 2,000, a weight 
average molecular weight of 8,300 and a propylene component content of 7.1 
mole % and consisting of a toluene-soluble portion having a number average 
molecular weight of 2,200, a weight average molecular weight of 11,900 and 
a propylene component content of 30 mole % and a toluene-insoluble portion 
having a number average molecular weight of 3,000, a weight average 
molecular weight of 7,400 and a propylene component content of 4.8 mole % 
was obtained by polymerizing ethylene and propylene using 
bis(pentamethylcyclopentadieneyl)zirconium dichloride, 
bis(methylcyclopentadienyl)zirconium dichloride and alumoxane as a 
catalyst. Likewise, Example 3 of this Publication describes a blend of 
LLDPE and an ethylene/propylene copolymer composed of a soluble portion 
having a molecular weight distribution (Mw/Mn) of 4.57 and a propylene 
component content of 20.6 mole % and an insoluble portion having a 
molecular weight distribution of 3.04 and a propylene component content of 
2.9 mole %. 
Japanese Laid-Open Patent Publication No. 35007/1985 describes a process 
which comprises polymerizing ethylene alone or with an alpha-olefin having 
at least 3 carbon atoms in the presence of a catalyst system comprising a 
metallocene and a cyclic alumoxane represented by the following formula 
##STR5## 
wherein R.sup.5 represents an alkyl group having 1 to 5 carbon atoms, and 
n is an integer of 1 to about 20, 
or a linear alumoxane represented by the following formula 
##STR6## 
wherein R.sup.5 and n are as defined above. The Publication describes that 
the polymer obtained by the above process has a weight average molecular 
weight of about 500 to about 1,400,000 and a molecular weight distribution 
of 1.5 to 4.0. 
Japanese Laid-Open Patent Publication No. 35008/1985 describes that 
polyethylene or a copolymer of ethylene and a C.sub.3 -C.sub.10 
alpha-olefin having a wide molecular weight distribution is produced by 
using a catalyst system comprising at least two types of metallocenes and 
alumoxane. The Publication states that the above copolymer has a molecular 
weight distribution (Mw/Mn) of 2 to 50. 
These catalysts formed from transition metal compounds and aluminoxanes 
have much higher polymerization activity than the catalyst systems known 
heretofore. 
On the other hand, methods using catalysts formed from solid catalyst 
components composed of the above transition metal compounds supported on 
porous inorganic oxide carriers such as silica, silica-alumina and alumina 
and aluminoxanes are proposed in Japanese Laid-Open Patent Publications 
Nos. 35006/1985, 35007/1985 and 35008/1985 which are cited above. Japanese 
Laid-Open Patent Publications Nos. 31404/1986, 108610/1986 and 106808/1985 
propose methods using solid catalyst components supported on similar 
porous inorganic oxide carriers. 
It is an object of this invention to provide a catalyst for polymerizing 
alpha-olefins, which has excellent polymerization activity and gives an 
ethylene polymer or an ethylene/alpha-olefin copolymer having excellent 
powder characteristics and a narrow molecular weight distribution or 
composition distribution, and when applied to the copolymerization of at 
least two olefins, gives an olefin copolymer having a narrow molecular 
weight distribution and composition distribution. 
Another object of this invention is to provide a process for producing an 
ethylene polymer or an ethylene/alpha-olefin copolymer having the 
aforesaid properties by polymerizing or copolymerizing alpha-olefins using 
the catalyst of this invention. 
According to this invention, these objects and advantages are firstly 
achieved by a catalyst for polymerization of alpha-olefins, said catalyst 
being formed by using a solid catalyst comprising 
(A) a solid catalyst component composed of a compound of a transition metal 
of Group IVB of the periodic table supported on a carrier, and 
(B) an aluminoxane, 
in pre-polymerization of an olefin. 
The catalyst of this invention is formed from the solid catalyst component 
(A) and the aluminoxane (B). 
The catalyst component (A) is a solid catalyst component composed of a 
compound of a transition metal of Group IVB of the periodic table 
supported on a carrier. 
The transition metal of Group IVB of the periodic table in the catalyst 
component (A) is preferably selected from the group consisting of 
titanium, zirconium and hafnium. Titanium and zirconium are more 
preferred, and zirconium is especially preferred. 
The compound of a transition metal of Group IVB of the periodic table in 
the catalyst component (A) preferably has a group having a conjugated .pi. 
electron as a ligand. 
Examples of the transition metal compound having a group with a conjugated 
.pi. electron as a ligand are compounds represented by the following 
formula (I) 
EQU R.sub.k.sup.1 R.sub.l.sup.2 R.sub.m.sup.3 R.sub.n.sup.4 M (I) 
wherein R.sup.1 represents a cycloalkadienyl group, R.sup.2, R.sup.3 and 
R.sup.4 are identical or different and each represents a cycloalkadienyl 
group, an aryl group, an alkyl group, a cycloalkyl group, an aralkyl 
group, a halogen atom, a hydrogen atom, or a group of the formula 
--OR.sup.a, --SR.sup.b or --NR.sub.2.sup.c in which each of R.sup.a, 
R.sup.b and R.sup.c represents an alkyl group, a cycloalkyl group, an aryl 
group, an aralkyl group or an organic silyl group, M represents zirconium, 
titanium or hafnium, k is 1, 2, 3 or 4, l, m and n are each 0, 1, 2 or 3, 
and k+l+m+n=4. 
Examples of the cycloalkadienyl group represented by R.sup.1 are a 
cyclopentadienyl group, a methylcyclopentadienyl group, an 
ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, an indenyl 
group and a tetrahydroindenyl group. Examples of the cycloalkadienyl group 
represented by R.sup.2, R.sup.3 and R.sup.4 may be the same as above. 
The aryl group represented by R.sup.2, R.sup.3 and R.sup.4 is preferably a 
phenyl or tolyl group, for example. 
Likewise, preferred examples of the aralkyl group are benzyl and neophile 
groups. 
Examples of preferred alkyl groups are methyl, ethyl, propyl, isopropyl, 
butyl, hexyl, octyl, 2-ethylhexyl, decyl and oleyl groups. 
Preferably, the cycloalkyl group may be, for example, a cyclopentyl, 
cyclohexyl, cyclooctyl, or norbornyl group. 
The halogen atom may be, for example, fluorine, chlorine or bromine. 
Specific examples of the groups --OR.sup.a, --SR.sup.b and --NR.sub.2.sup.c 
where R.sup.a, R.sup.b and R.sup.c are alkyl cycloalkyl, aryl and aralkyl 
will be clear from the above specific examples of these groups. 
Examples of the organic silyl group for R.sup.a, R.sup.b and R.sup.c are 
trimethylsilyl, triethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl 
and triphenylsilyl groups. 
Examples of zirconium compounds corresponding to formula (I) in which Me is 
zirconium are listed below: 
bis(cyclopentadienyl) zirconium monochloride monohydride, 
bis(cyclopentadienyl)zirconium monobromide monohydride, 
bis(cyclopentadienyl)methylzirconium hydride, 
bis(cyclopentadienyl)ethylzirconium hydride, 
bis(cyclopentadienyl)cyclohexylzirconium hydride, 
bis(cyclopentadienyl)phenylzirconium hydride, 
bis(cyclopentadienyl)benzylzirconium hydride, 
bis(cyclopentadienyl)neopentylzirconium hydride, 
bis(methylcyclopentadienyl)zirconium monochloride monohydride, 
bis(indenyl)zirconium monochloride monohydride, 
bis(cyclopentadienyl)zirconium dichloride, 
bis(cyclopentadienyl)zirconium dibromide, 
bis(cyclopentadienyl)methylzirconium monochloride, 
bis(cyclopentadienyl)ethylzrconium monochloride, 
bis(cyclopentadienyl)cyclohexylzirconium monochloride, 
bis(cyclopentadienyl)phenylzirconium monochloride, 
bis(cyclopentadienyl)benzylzirconium monochloride, 
bis(methylcyclopentadienyl)zirconium dichloride, 
bis(indenyl)zirconium dichloride, 
bis(indenyl)zirconium dibromide, 
bis(cyclopentadienyl)diphenylzirconium, 
bis(cyclopentadienyl)benzylzirconium, 
bis(cyclopentadienyl)methoxyzirconium chloride, 
bis(cyclopentadienyl)ethoxyzirconium chloride, 
bis(cyclopentadienyl)butoxyzirconium chloride, 
bis(cyclopentadienyl)2-ethylhexoxyzirconium chloride, 
bis(cyclopentadienyl)methylzirconium ethoxide, 
bis(cyclopentadienyl)methylzirconium butoxide, 
bis(cyclopentadienyl)ethylzirconium ethoxide, 
bis(cyclopentadienyl)phenylzirconium ethoxide, 
bis(cyclopentadienyl)benzylzirconium ethoxide, 
bis(methylcyclopentadienyl)ethoxyzirconium chloride, 
bis(indenyl)ethoxyzirconium chloride, 
bis(cyclopentadienyl)ethoxyzirconium, 
bis(cyclopentadienyl)butoxyzirconium, 
bis(cyclopentadienyl)2-ethylhexoxyzirconium, 
bis(cyclopentadienyl)phenoxyzirconium chloride, 
bis(cyclopentadienyl)cyclohexoxyzirconium chloride, 
bis(cyclopentadienyl)phenylmethoxyzirconium chloride, 
bis(cyclopentadienyl)methylzirconium phenylmethoxide, 
bis(cyclopentadienyl)trimethylsiloxyzirconium chloride, 
bis(cyclopentadienyl)triphenylsiloxyzirconium chloride, 
bis(cyclopentadienyl)thiophenylzirconium chloride, 
bis(cyclopentadienyl)thioethylzirconium chloride, 
bis(cyclopentadienyl)bis(dimethylamide)zirconium, 
bis(cyclopentadienyl)diethylamidezirconium chloride, 
ethylenebis(indenyl)ethoxyzirconium chloride, 
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, 
ethylenebis(indenyl)dimethylzirconium, 
ethylenebis(indenyl)diethylzirconium, 
ethylenebis(indenyl)dibenzylzirconium, 
ethylenebis(indenyl)methylzirconium monobromide, 
ethylenebis(indenyl)ethylzirconium monochloride, 
ethylenebis(indenyl)benzylzirconium monochloride, 
ethylenebis(indenyl)methylzirconium monochloride, 
ethylenebis(indenyl)zirconium dichloride, 
ethylenebis(indenyl)zirconium dibromide, 
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium, 
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium monochloride, 
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, 
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dibromide, 
ethylenebis(4-methyl-1-indenyl)zirconium dichloride, 
ethylenebis(5-methyl-1-indenyl)zirconium dichloride, 
ethylenebis(6-methyl-1-indenyl)zirconium dichloride, 
ethylenebis(7-methyl-1-indenyl)zirconium dichloride, 
ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, 
ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, 
ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride, 
ethylenebis(4,7-dimethoxy-1-indenyl)zirconium dichloride, 
ethylenebis(indenyl)zirconium dimethoxide, 
ethylenebis(indenyl)zirconium diethoxide, 
ethylenebis((indenyl)methoxyzirconium chloride, 
ethylenebis(indenyl)ethoxyzirconium chloride, 
ethylenebis(indenyl)methylzirconium ethoxide, 
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethoxide, 
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium diethoxide, 
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methoxyzirconium chloride 
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, and 
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium ethoxide. 
Examples of titanium compounds corresponding to formula (I) in which Me is 
titanium are listed below: 
bis(cyclopentadienyl)titanium monochloride monohydride, 
bis(cyclopentadienyl)methyltitanium hydride, 
bis(cyclopentadienyl)phenyltitanium chloride, 
bis(cyclopentadienyl)benzyltitanium chloride, 
bis(cyclopentadienyl)titanium chloride, 
bis(cyclopentadienyl)dibenzyltitanium, 
bis(cyclopentadienyl)ethoxytitanium chloride, 
bis(cyclopentadienyl)butoxytitanium chloride, 
bis(cyclopentadienyl)methyltitanium ethoxide, 
bis(cyclopentadienyl)phenoxytitanium chloride, 
bis(cyclopentadienyl)trimethylsiloxytitanium chloride, 
bis(cyclopentadienyl)thiophenyltitanium chloride, 
bis(cyclopentadienyl)bis(dimethylamide)titanium, 
bis(cyclopentadienyl)ethoxytitanium, 
ethylenebis(indenyl)titanium dichloride, and 
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)titanium dichloride. 
Examples of hafnium compounds corresponding to formula (I) in which Me is 
hafnium are listed below: 
bis(cyclopentadienyl)hafnium monochloride monohydride, 
bis(cyclopentadienyl)ethylhafnium hydride, 
bis(cyclopentadienyl)phenylhafnium chloride, 
bis(cyclopentadienyl)hafnium dichloride, 
bis(cyclopentadienyl)hafnium dibenzil 
bis(cyclopentadienyl)ethoxyhafnium chloride, 
bis(cyclopentadienyl)butoxyhafnium chloride, 
bis(cyclopentadienyl)methylhafnium ethoxide, 
bis(cyclopentadienyl)phenoxyhafnium chloride, 
bis(cyclopentadienyl)thiophenylhafnium chloride, 
bis(cyclopentadienyl)bis(diethylamide)hafnium, 
ethylenebis(indenyl)hafnium dichloride, and 
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride. 
In the catalyst component (A), the IVB transition metal compound may be 
treated with an organic metal compound prior to supporting. The organic 
metal compound may be, for example, an organoaluminum compound, an 
organoboron compound, an organomagnesium compound, an organozinc compound 
or an organolithium compound. The organoaluminum compound is preferred. 
Examples of the organoaluminum compound include trialkylaluminums such as 
trimethylaluminum, triethylaluminum and tributylaluminum; alkenylaluminums 
such as isoprenylaluminum; dialkyl aluminum alkoxides such as dimethyl 
aluminum methoxide, diethyl aluminum ethoxide and dibutyl aluminum 
butoxide; alkyl aluminum sesquialkoxides such as methyl aluminum 
sesquimethoxide and ethyl aluminum sesquiethoxide; partially alkoxylated 
alkylaluminums having an average composition of the formula 
R.sub.2.5.sup.1 Al(OR.sup.2).sub.0.5 ; dialkyl aluminum halides such as 
dimethyl aluminum chloride, diethyl aluminum chloride and dimethyl 
aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum 
sesquichloride and ethyl aluminum sesquichloride; partially halogenated 
alkylaluminums, for example alkyl aluminum dihalides such as methyl 
aluminum dichloride and ethyl aluminum dichloride. 
The trialkylaluminums and dialkyl aluminum chlorides are preferred, and 
above all trimethylaluminum, triethylaluminum and dimethyl aluminum 
chloride are preferred. 
Triethylboron is a preferred example of the organoboron compound. 
Examples of the organomagnesium compound are ethylbutylmagnesium, 
di-n-hexylmagnesium, ethyl magnesium bromide, phenyl magnesium bromide and 
benzyl magnesium chloride. 
Diethylzinc is a preferred example of the organozinc compound. 
Methyllithium, butyllithium and phenyllithium are examples of the 
organolithium compound. 
In the catalyst of this invention, the solid catalyst component (A) is 
composed of the compound of the transition metal of Group IVB of the 
periodic table supported on a carrier. 
The carrier may be organic or inorganic, and is advantageously a granular 
or particulate solid having a particle diameter of, for example, 10 to 300 
micrometers, preferably 20 to 200 micrometers. A porous oxide is preferred 
as the inorganic carrier. Specific examples include SiO.sub.2, Al.sub.2 
O.sub.3, MgO, ZrO.sub.2, TiO.sub.2, B.sub.2 O.sub.3, CaO, ZnO, BaO and 
ThO.sub.2 and mixtures of these, such as SiO.sub.2 --MgO, SiO.sub.2 
--Al.sub.2 O.sub.3, SiO.sub.2 --TiO.sub.2, SiO.sub.2 --V.sub.2 O.sub.5, 
SiO.sub.2 --Cr.sub.2 O.sub.3 and SiO.sub.2 --TiO.sub.2 --MgO. A catalyst 
containing at least one component selected from the group of SiO.sub.2 and 
Al.sub.2 O.sub.3 as a main component is preferred. 
The inorganic oxide may contain a small amount of a carbonate, nitrate, 
sulfate or an oxide component such as Na.sub.2 CO.sub.3, K.sub.2 CO.sub.3, 
CaCO.sub.3, MgCO.sub.3, Na.sub.2 SO.sub.4, Al.sub.2 (SO.sub.4).sub.3, 
BaSO.sub.4, KNO.sub.3, Mg(NO.sub.3).sub.2, Al(NO.sub.3).sub.3, Na.sub.2 O, 
K.sub.2 O and Li.sub.2 O. 
The porous inorganic carrier preferably used in this invention has a 
specific surface area of 50 to 1000 m.sup.2 /g, preferably 100 to 700 
m.sup.2 /g and a pore volume of 0.3 to 2.5 cm.sup.2 /g, although its 
characteristics vary depending upon its type and the method of production. 
The carrier is used after it is calcined usually at 150.degree. to 
1000.degree. C., preferably 200.degree. to 800.degree. C. 
Granular or particulate solids of organic compounds having a particle 
diameter of 10 to 300 micrometers may also be used in the present 
invention. Examples of the organic compounds are (co)polymers containing 
alpha-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 
1-butene, 4-methyl-1-pentene and 1-decene as a main component, and 
polymers or copolymers containing vinylcyclohexane or styrene as a main 
component. 
The mixing weight ratio of the Group IVB transition metal compound to the 
carrier (transition metal/carrier) in the supporting reaction in this 
invention is 0.5 to 15%, preferably 0.8 to 10% by weight, more preferably 
1 to 7% by weight. 
The supporting may be carried out, for example, by mixing the carrier and 
the transition metal compound in the presence of an inert solvent, and 
removing the solvent by using an evaporator, for example, at room 
temperature or at an elevated temperature under atmospheric pressure or 
elevated pressure. 
It can also be achieved by the following methods, for example. 
(1) A method which comprises treating the carrier with an organoaluminum 
compound such as trimethylaluminum, dimethyl aluminum chloride and 
aluminoxane or a halogen-containing silicon compound such as 
trichlorosilane, and mixing the treated carrier with the Group IVB 
transition metal compound. 
(2) A method which comprises treating the Group IVB transition metal 
compound with an organoaluminum compound such as trimethylaluminum or 
dimethyl aluminum chloride and then mixing the treated compound with the 
carrier in the presence of an inert solvent. 
(3) A method which comprises mixing the carrier, the Group IVB transition 
metal compound and the aluminoxane as catalyst component (B), and removing 
the solvent from the mixture using an evaporator, for example, under 
atmospheric pressure or reduced pressure. 
The catalyst component (B) is an aluminoxane. The aluminoxane used as the 
catalyst component (B) may be, for example, an organoaluminum compound 
represented by the following formula (II) 
##STR7## 
wherein R represents a hydrocarbon group, X represents a halogen atom, and 
a and b, independently from each other, are a number of 0 to 80 provided 
that a and b are not simultaneously zero (in this formula, a+b+2 is the 
degree of polymerization), 
or by the following formula 
##STR8## 
wherein R, X, a, and b are as defined with regard to formula (II) above 
(in this formula, a+b is the degree of polymerization). 
In the above formulae (II) and (III), R represents a hydrocarbon group such 
as an alkyl, cycloalkyl, aryl or aralkyl group. The alkyl group is 
preferably a lower alkyl group such as a methyl, ethyl, propyl or butyl 
group. The cycloalkyl group is preferably a cyclopentyl or cyclohexyl 
group. The aryl group is preferably a phenyl or tolyl group. Benzyl and 
neophile groups are preferred examples of the aralkyl group. Among them, 
the alkyl groups are especially preferred. 
X is a halogen atom such as fluorine, chlorine, bromine or iodine. Chlorine 
is especially preferred. 
a and b, independently from each other, represent a number of 0 to 80, 
provided that a and b are not simultaneously zero. 
When b is 0, formula (II) can be written as (II)-1 
##STR9## 
wherein R and a are as defined above. 
The formula (III) above may be written as the following formula (III)-1 
##STR10## 
wherein R and a are as defined above. 
In formula (II)-1, a is preferably 2 to 50, more preferably 4 to 30. In 
formula (III)-1, a is preferably 4 to 52, more preferably 6 to 32. 
a is preferably 0 to 40, more preferably 3 to 30, and b is preferably 1 to 
40, more preferably 3 to 30. 
The a+b value is preferably 4 to 50, more preferably 8 to 30. 
In formulae (II) and (III), the two units --O--Al and 
##STR11## 
may be bonded in blocks or at random. 
When a is 0 in formulae (II) and (III), it is desirable to use an 
organoaluminum compound of the following formula (V) 
EQU AlR.sub.f.sup.7 Z.sub.3-f (V) 
wherein R.sup.7 represents an alkyl group having 1 to 10 carbon atoms or a 
cycloalkyl group having 3 to 12 carbon atoms, Z represents a halogen atom, 
and f is a number of 1 to 3, 
together with the halogenated aluminoxane. Examples of the organoaluminum 
compound are trimethylaluminum, triethylaluminum, tributylaluminum, 
trihexylaluminum, diethylaluminum chloride and ethyl aluminum 
sesquichloride. 
At this time, it is desirable to use 0.1 to 10 moles, preferably 0.3 to 3.0 
moles, especially preferably 0.5 to 2.0 moles, of the organoaluminum 
compound per mole of the aluminum atom of the halogenated aluminoxane. 
The following methods may be cited as examples of producing the aluminoxane 
or the halogenated aluminoxane. 
(1) A method which comprises reacting a compound containing water of 
adsorption or a salt containing water of crystallization, such as 
magnesium chloride hydrate, nickel sulfate hydrate or cerous chloride 
hydrate, with a trialkylaluminum or a dialkyl aluminum monohalide while 
the former is being suspended in a medium such as benzene, toluene, ethyl 
ether or tetrahydrofuran. 
(2) A method which comprises the action of water directly on a 
trialkylaluminum and/or a dialkyl aluminum monohalide in a medium such as 
benzene, toluene, ethyl ether or tetrahydrofuran. 
Of these, the method (1) is preferably employed. The aluminoxane may 
contain a small amount of an organometallic component. 
The catalyst of this invention may be prepared by contacting the prepared 
carrier-supported solid catalyst component (A) and aluminoxane catalyst 
component (B) in an inert medium, or by supporting the Group IVB 
transition metal compound and the aluminoxane simultaneously on a carrier, 
prior to pre-polymerization. Preferably, prior to pre-polymerization, the 
catalyst components (A) and (B) are mixed in an inert hydrocarbon medium. 
When the inert hydrocarbon medium dissolves the catalyst component (B), 
the resulting mixture is preferably subjected to an evaporator at room 
temperature or at an elevated temperature under atmospheric or reduced 
pressure to remove the solvent. It is alternatively preferred to deposit 
the catalyst component (B) by, for example, adding a solvent in which the 
catalyst component (B) is insoluble, thereby to form a solid catalyst at 
least comprising (A) and (B). 
The catalyst of this invention contains the transition metal compound in an 
amount of usually 0.003 to 3 mg-atom, preferably 0.005 to 2 mg-atom, 
especially preferably 0.01 to 1 mg-atom, as the transition metal atom per 
gram of the carrier. The proportion of the aluminoxane catalyst component, 
whether prior to the pre-polymerization of an olefin, the catalyst is a 
solid catalyst formed from the components (A) and (B) in an inert 
hydrocarbon medium or a solid catalyst formed by supporting the transition 
metal component and the aluminoxane catalyst component, is such that the 
atomic ratio of aluminum atom to the transition metal atom of the 
transition metal compound (Al/M) is from 1 to 1000, preferably from 10 to 
700, especially preferably from 15 to 500. 
The catalyst of this invention may contain an electron donor in addition to 
the carrier component, transition metal compound and the aluminoxane. 
Examples of the electron donor include carboxylic acids, esters, ethers, 
ketones, aldehydes, alcohols, phenols, acid amides, oxygen-containing 
compounds such as compounds containing a metal--O--C bond (the metal is, 
for example, aluminum or silicon), nitriles, amines, and phosphines. The 
proportion of the electron donor is usually 0 to 1 mole, preferably 0.1 to 
0.6 mole, per gram of the transition metal atom (M). 
The solid catalyst component in this invention has an average particle 
diameter of usually 10 to 300 micrometers, preferably 20 to 200 
micrometers, more preferably 25 to 100 micrometers and a specific surface 
area of usually 20 to 1000 m.sup.2 /g, preferably 50 to 500 m.sup.2 /g, 
specially preferably 100 to 300 m.sup.2 /g. 
The catalyst of this invention is formed by pre-polymerizing an olefin in 
the presence of the solid catalyst component formed from the catalyst 
components (A) and (B) prior to the main polymerization of an olefin. The 
pre-polymerization is carried out by polymerizing 0.05 to 30 g, preferably 
0.1 to 20 g, more preferably 0.2 to 10 g, of the olefin per gram of the 
solid catalyst component formed from the catalyst components (A) and (B). 
Examples of the olefin are ethylene, and alpha-olefins having 3 to 20 
carbon atoms such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 
1-octene, 1-decene, 1-dodecene and 1-tetradecene. Ethylene is especially 
preferred. 
The pre-polymerization is carried out (1) in the absence of a solvent, or 
(2) in an inert hydrocarbon medium. The mole ratio of the aluminum atom of 
the catalyst component (B) to the transition metal atom of the catalyst 
component (A) (Al/transition metal atom) in the pre-polymerization 
treatment is from 1 to 1000, preferably from 10 to 700, more preferably 
from 15 to 500. The pre-polymerization temperature is from -20.degree. C. 
to 70.degree. C., preferably -10.degree. C. to 60.degree. C., more 
preferably 0.degree. C. to 50.degree. C. 
The pre-polymerization treatment may be carried out batchwise or 
continuously under reduced, atmospheric or elevated pressure. A molecular 
weight controlling agent such as hydrogen may be caused to be present in 
the pre-polymerization. Its amount, however, is preferably limited to 
those values in which a prepolymer having an intrinsic viscosity [.eta.], 
measured in decalin at 135.degree. C., of at least 0.2 dl/g, preferably 
0.5 to 20 dl/g, can be produced. 
By using the catalyst of this invention described above, alpha-olefins can 
be advantageously polymerized or copolymerized. 
Investigations of the present inventors have shown that when a porous 
inorganic oxide treated with a compound selected from the group consisting 
of organometallic compounds, halogen-containing silicon compounds and 
aluminoxanes is used as a carrier for the solid catalyst component (A) in 
the catalyst component (A) and the alumilnoxane (B) before 
pre-polymerization treatment, the resulting catalyst shows excellent 
activity equivalent to the catalyst of this invention without subjecting 
it to pre-polymerization treatment. 
Accordingly, the objects and advantages of the present invention are 
achieved secondly by a catalyst for polymerization of alpha-olefins, said 
catalyst comprising 
(A') a solid catalyst component composed of a compound of a transition 
metal of Group I of the periodic table supported on a porous inorganic 
oxide carrier treated with a compound selected from the group consisting 
of organometallic compounds, halogen-containing silicon compounds and 
aluminoxanes, and 
(B) an aluminoxane. 
In the catalyst of this invention for polymerization of alpha-olefins, the 
porous inorganic oxide carrier is treated with a compound selected from 
the group consisting of organometallic compounds, halogen-containing 
silicon compounds and aluminoxanes. 
The porous inorganic oxide carrier may be any of those which are 
exemplified hereinabove. 
The organometallic compounds as the treating agent may be the same as those 
exemplified hereinabove. 
In the above treatment, the mixing ratio of the organometallic compound to 
the carrier, as the ratio of the millimoles of the organometallic compound 
to the grams of the carrier, is from 0.5 to 50, preferably from 1 to 30, 
preferably from 1.5 to 20. 
The treatment of the porous inorganic oxide carrier with the organometallic 
compound in the catalyst component (A') may be carried out by dispersing 
the carrier in an inert solvent, adding at least one organometallic 
compound mentioned above, and maintaining the mixture at a temperature of 
0.degree. to 120.degree. C., preferably 10.degree. to 100.degree. C., more 
preferably 20.degree. to 90.degree. C., for a period of 10 minutes to 10 
hours, preferably 20 minutes to 5 hours, more preferably 30 minutes to 3 
hours, under atmospheric, reduced or elevated pressure. 
Examples of the inert solvent are aromatic hydrocarbons such as benzene, 
toluene and xylene, aliphatic hydrocarbon such as pentane, hexane and 
isooctane, and alicyclic hydrocarbons such as cyclohexane. 
The Group IVB transition metal compound is supported in a proportion of 
3.times.10.sup.-3 to 3 mg-atom, preferably 5.times.10.sup.-3 to 2 mg-atom, 
more preferably 1.times.10.sup.-2 to 1 mg-atom, as the transition metal 
atom, per gram of the porous inorganic oxide carrier treated with the 
organometallic compound. 
The supporting of the transition metal compound may be carried out by, for 
example, adding the porous inorganic oxide carrier treated with the 
organometallic compound and the transition metal compound in an inert 
hydrocarbon medium, and working up the mixture in the following manner. 
The treating temperature is usually 0.degree. to 100.degree. C., preferably 
20.degree. to 90.degree. C., and the treating time is usually 5 minutes to 
5 hours, preferably 10 minutes to 2 hours. After the supporting, the inert 
hydrocarbon medium is removed by filtration or evaporated under 
atmospheric or reduced pressure to give a solid catalyst component. 
Preferably, the halogen-containing silicon compound as the treating agent 
is, for example, a compound represented by the following formula (IV) 
EQU SiY.sub.d R.sub.e.sup.5 (OR.sup.6).sub.4-d-e (IV) 
wherein Y represents a chlorine or bromine atom, R.sup.5 and R.sup.6, 
independently from each other, represent an alkyl group having 1 to 12 
carbon atoms, an aryl group, or a cycloalkyl group having 3 to 12 carbon 
atoms, d is a number of 1 to 4, and e is a number of 0 to 4, provided that 
the total of d and e is a number of 1 to 4. 
Examples of this compound include silicon tetrachloride, silicon 
tetrabromide, silicon trichloride, methylsilicon trichloride, ethylsilicon 
trichloride, propylsilicon trichloride, phenylsilicon trichloride, 
cyclohexylsilicon trichloride, silicon tribromide, ethylsilicon 
tribromide, dimethylsilicon dichloride, methylsilicon dichloride, 
phenylsilicon dichloride, methoxysilicon trichloride, ethoxysilicon 
trichloride, propoxysilicone trichloride, phenoxysilicon trichloride, 
ethoxysilicon tribromide, methoxysilicon dichloride, methoxysilicon 
dichloride, and silanol trichloride. They may be used singly or in 
combination. Among them, silicon tetrachloride, silicon trichloride and 
methylsilicon trichloride are preferred. 
The mixing ratio of the halogen-containing silicon compound and the porous 
inorganic oxide in the above treatment is such that the proportion of the 
halogen-containing silicon compound is 0.001 to 10 moles, preferably 0.01 
to 5 moles, more preferably 0.05 to 1 mole, per gram of the carrier 
compound. Preferably, after the treatment, the liquid portion containing 
the excess of the halogen-containing silane compound, for example is 
removed from the reaction mixture by filtration, decantation or the like. 
In the preparation of the catalyst component (A'), the treatment of the 
porous inorganic oxide carrier with the halogen-containing silicon 
compound is carried out at a temperature of -50.degree. to 200.degree. C., 
preferably 0.degree. to 100.degree. C., more preferably 20.degree. to 
70.degree. C., for a period of 10 minutes to 10 hours, preferably 20 
minutes to 5 hours, under atmospheric, reduced or elevated pressure. 
In the above treatment, an inert solvent may be used. Examples of the inert 
solvent are aromatic hydrocarbons such as benzene, toluene and xylene, 
aliphatic hydrocarbons such as pentane, hexane, isooctane, decane and 
dodecane, alicyclic hydrocarbons such as cyclohexane, and halogenated 
hydrocarbons such as chlorobenzene and ethylene dichloride. 
In the preparation of the catalyst component (A'), if the Group IVB 
transition metal compound to be supported on the porous inorganic oxide 
carrier treated with the halogen-containing silane compound in the 
catalyst component (A') is liquid, it is not necessary to use an inert 
solvent. When the transition metal compound is a normally solid substance, 
it is generally preferred to use an inert solvent capable of dissolving 
the transition metal compound. 
The inert solvent that can be used at this time may be the same as those 
exemplified hereinabove with regard to the treatment of the porous 
inorganic oxide carrier. Aromatic hydrocarbons such as benzene and toluene 
and halogenated hydrocarbons such as chlorobenzene are especially 
preferred. 
The amount of the transition metal compound used in the above supporting 
reaction is preferably 0.001 to 500 millimoles, preferably 0.01 to 100 
millimoles, especcally preferably 0.1 to 50 millimoles, per gram of the 
porous inorganic oxide carrier treated with the halogen-containing silane 
compound. 
The amount of the inert solvent used in the above supporting reaction is 
0.5 to 1000 ml, preferably 1 to 100 ml, especially preferably 2 to 50 ml, 
per gram of the porous inorganic oxide carrier treated with the 
halogen-containng silane compound. 
The above supporting reaction may be carried out by contacting and mixing 
the transition metal compound with the porous inorganic oxide carrier 
treated with the halogen-containing silane compound at a temperature of 
0.degree. to 200.degree. C., preferably 0.degree. to 100.degree. C., 
especially 20.degree. to 80.degree. C., for 1 minute to 10 hours, 5 
minutes to 5 hours, or 10 minutes to 3 hours. 
After the supporting reaction is carried out by the above method, the 
liquid portion of the reaction mixture is removed by, for example, 
filtration or decantation, and preferably the residue is washed several 
times with an inert solvent. 
The solid catalyst component (A') prepared by the above method contains the 
transition metal compound in an amount of usually 0.005 to 5 millimoles, 
preferably 0.01 to 1 millimole, especially preferably 0.03 to 0.3 
millimole, per gram of the component (A'). 
Examples of the aluminoxanes as the treating agent may be the same as those 
exemplified above as the catalyst component (B). 
In the treatment of the porous inorgnaic oxide carrier with the alumioxane, 
the mixing ratio of both is such that the proportion of the aluminoxane is 
0.001 to 100 millimoles, preferably 0.01 to 10 millimoles, preferably 0.05 
to 5 millimoles, per gram of the carrier compound. Preferably, the liquid 
portion containing the excess of the aluminoxane after the above treatment 
is removed from the reaction mixture by such a method as filtration or 
decantation. 
The treatment of the porous inorganic oxide carrier with the aluminoxane in 
the preparation of the catalyst component (A') may be carried out at a 
temperature of -50.degree. to 200.degree. C., preferably 0.degree. to 
100.degree. C., more preferably 20.degree. to 70.degree. C. under 
atmospheric, reduced or elevated pressure for a period of 10 minutes to 10 
hours, preferably 20 minutes to 5 hours. 
The above treatment is preferably carried out in an inert solvent. Examples 
of the inert solvent may include aromatic hydrocarbons such as benzene, 
toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, 
isooctane, decane and dodecane, alicyclic hydrocarbons such as cyclohexane 
and halogenated hydrocarbons such as chlorobenzene and ethylene 
dichloride. Of these, the aromatic hydrocarbons are preferred. 
When the Group IVB transition metal compound is liquid in depositing it on 
the porous inorganic oxide carrier treated with the aluminoxane, an inert 
solvent may or may not be used. When the transition metal compound is a 
normally solid substance, it is generally preferred to use an inert 
solvent capable of dissolving the transition metal compound. 
The inert solvent that can be used at this time may be the same as those 
used in treating the porous inorganic oxide carrier with the aluminoxane. 
Aromatic hydrocarbons such as benzene and toluene and halogenated 
hydrocarbons such as chlorobenzene are especially preferred. 
The amount of the transition metal compound used in the above supporting 
reaction is 0.001 to 10 millimoles, preferably 0.005 to 5 millimoles, 
especially preferably 0.01 to 1 millimole, per gram of the porous 
inorganic oxide carrier treated with the aluminoxane. 
The amount of the inert solvent, the reaction temperature, the reaction 
time and the after-treatment used in the above supporting reaction may be 
the same as those described above with regard to the porous inorganic 
oxide carrier treated with the halogen-containing silicon compound. 
The solid catalyst component (A') prepared by the above method contains the 
transition metal compound in an amount of usually 0.005 to 5 millimoles, 
preferably 0.01 to 1 millimole, especially preferably 0.03 to 0.3 
millimole, per gram of the component (A'). 
The above catalyst of this invention comprises the solid catalyst component 
(A') prepared as above and the aluminoxane (B). 
The catalyts of the invention described above can be used advantageously in 
the homopolymerization or copolymerization of alpha-olefins, and are 
particularly effective for the production of an ethylene polymer and a 
copolymer of ethylene and an alpha-olefin. Examples of the olefins that 
can be used in this invention are ethylene and alpha-olefins having 3 to 
20 carbon atoms such as 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 
1-eicosene. 
In the process of this invention, olefin polymerization is usually carried 
out in the vapor phase or the liquid phase, for example in slurry. In the 
slurry polymerization, an inert hydrocarbon may be used as a solvent, or 
an olefin itself may be used as the solvent. 
Specific examples of the hydrocarbon medium include aliphatic hydrocarbons 
such as butane, isobutane, pentane, hexane, octane, decane, dodecane, 
hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane, 
methylcyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons 
such as benzene, toluene and xylene; and petroleum fractions such as 
gasoline, kerosene and light oil. Of these, the aliphatic hydrocarbons, 
alicyclic hydrocarbons and petroleum fractions are preferred. 
In carrying out slurry polymerization in the process of this invention, the 
polymerization temperature is usually -50.degree. to 120.degree. C., 
preferably 0.degree. to 100.degree. C. 
In carrying out the process of this invention by a slurry or vapor-phase 
polymerization technique, the proportion of the transition metal compound 
is usually 10.sup.-8 to 10.sup.-2 gram-atom/liter, preferably 10.sup.-7 to 
10.sup.-3 gram-atom/liter, as the concentration of the transition metal 
atom in the polymerization reaction system. 
In the main polymerization reaction, the aluminoxane may, or may not, be 
used additionally. But to obtain a polymer having excellent powder 
characteristics, it is preferred not to use the aluminoxane additionally. 
The polymerization pressure is usually atmospheric pressure to an elevated 
pressure of 100 kg/cm.sup.2, preferably 2 to 50 kg/cm.sup.2. The 
polymerization may be carried out batchwise, semi-continuously or 
continuously. 
The polymerization may also be carried out in two or more steps in which 
the reaction conditions are different. 
When a slurry polymerization technique or a vapor-phase polymerization 
technique is employed in the polymerization of olefins, particularly the 
polymerization of ethylene or the polymerization of ethylene with an 
alpha-olefin, no polymer adhesion to the reactor occurs, and a polymer 
having excellent powder characteristics and a narrow molecular 
distribution can be obtained. In particular, when the catalyst of this 
invention is applied to the copolymerization of two or more olefins, an 
olefin copolymer having a narrow molecular weight distribution and a 
narrow composition distribution can be obtained.

EXAMPLES 
The following examples specifically illustrate the process of this 
invention. 
In Examples and Comparative Examples, MFR was measured at a temperature of 
190.degree. C. under a load of 2.16 kg. The Mw/Mn was measured by the 
following procedure in accordance with "Gel Permeation Chromatography", 
written by Takeuchi, and published by Maruzen Co., Ltd. 
(1) Using standard polystyrene having a known molecular weight 
(monodisperse polystyrene produced by Toyo Soda Co., Ltd.), molecular 
weight M and its GPC (gel permeation chromatography) count are measured, 
and a calibration curve of the molecular weight M and EV (elution volume) 
is prepared. The concentration at this time is set at 0.02% by weight. 
(2) A GPC chromatograph of the sample is taken by GPC measurement. On the 
basis of (1) above, the number average molecular weight Mn and the weight 
average molecular weight Mw of the sample are calculated for polystyrene, 
and the Mw/Mn is determined. The sample preparation conditions and the GPC 
measurement conditions are as follows: 
Sample Preparation 
(a) The sample and o-dichlorobenzene as a solvent are taken into an 
Erlenmeyer flask so that the concentration of the sample is 0.1% by 
weight. 
(b) The Erlenmeyer flask is heated at 140.degree. C. and the mixture is 
stirred for about 30 minutes to dissolve the sample. 
(c) A filtrate of the solution is subjected to GPC. 
GPC Measurement Conditions 
GPC was performed under the following conditions. 
(a) Device: 150C-ALC/GPC made by Waters Co. 
(b) Column: GMH type made by Toyo Soda Co., Ltd. 
(c) Amount of the sample: 400 microliters 
(d) Temperature: 140.degree. C. 
(e) Flow rate: 1 ml/min. 
The amount of an n-decane-soluble portion of the copolymer (as the amount 
of the soluble portion is smaller, the composition distribution of the 
copolymer is narrower) is measured by adding about 3 g of the copolymer to 
450 ml of n-decane, dissolving it at 145.degree. C., gradually cooling the 
solution to 23.degree. C., removing the n-decane-insoluble portion by 
filtration, and recovering the n-decane-soluble portion from the filtrate. 
Example 1 
Preparation of Aluminoxane 
A 400 ml fully nitrogen-purged flask was charged with 37 g of Al.sub.2 
(SO.sub.4).sub.3.14H.sub.2 O and 125 ml of toluene. The flask was cooled 
to 0.degree. C., and 500 millimoles of trimethylaluminum diluted with 125 
ml of toluene. The mixture was then heated to 40.degree. C., and reacted 
at this temperature for 10 hours. After the reaction, the reaction mixture 
was subjected to solid-liquid separation by filtration. The toluene was 
removed from the filtrate to give 13 g of aluminoxane as a white solid. 
The molecular weight of the product, determined by freezing point 
depression in benzene, was 930. It had an average degree of polymerization 
of 16. 
Preparation of a Zirconium Catalyst 
2.3 g of calcined silica obtained by calcining silica (average particle 
diameter 70 .mu.m, specific surface area 260 m.sup.2 /g, pore volume 1.65 
cm.sup.3 /g) at 300.degree. C. for 4 hours, 15 ml of a toluene solution 
(aluminum 1 mole/liter) of dimethyl aluminum monochloride and 50 ml of 
toluene were introduced into a 200 ml flask purged fully with nitrogen, 
and heated at 80.degree. C. for 2 hours. The reaction mixture was 
subjected to solid-liquid separation by filtration. The solid portion was 
transferred into 50 ml of toluene, and 6.4 ml of a toluene solution (Zr 
0.01 mole/liter) of biscyclopentadienyl zirconium chloride was added. The 
mixture was stirred at room temperature for 2 hours. Then, 31 ml of a 
toluene solution (Al 1.03 moles/liter) of aluminoxane as catalyst 
component (B) was added, and the mixture was stirred at room temperature 
for 30 minutes. Subsequently, toluene was removed from the solution at 
room temperature by means of an evaporator to give a solid catalyst 
component containing 0.14% by weight of Zr and 22% by weight of Al. The 
solid catalyst component had an average particle diameter of 83 .mu.m, and 
a specific surface area of 207 m.sup.2 /g. 
Preliminary Polymerization 
A gaseous mixture of ethylene and nitrogen (20 liters/hr and 30 liters/hr, 
respectively) was passed through the solid catalyst component prepared as 
above for 30 minutes at room temperature to pre-polymerize ethylene. 
Ethylene polymerized in an amount of 0.62 g per gram of the solid catalyst 
component. 
Main Polymerization 
One liter of hexane was introduced into a 2-liter stainless steel autoclave 
fully purged with nitrogen, and the temperature was raised to 45.degree. 
C. Then, the solid catalyst component subjected to the preliminary 
polymerization was charged into the autoclave in an amount of 0.015 
milligram-atom calculated as the zirconium atoms, and the temperature was 
raised to 60.degree. C. Subsequently, ethylene was introduced and the 
total pressure was set at 6 kg/cm.sup.2 -G. Its polymerization was 
started, and then continued at 70.degree. C. for 2 hours while maintaining 
the total pressure at 6 kg/cm.sup.2 -G by supplying ethylene alone. After 
the polymerization, the polymer slurry was separated by filtration, and 
dried overnight at 80.degree. C. under reduced pressure. There was 
obtained 85.9 g of a polymer having an MFR of 0.03 g/10 min., an Mw/Mn of 
2.65 and a bulk density of 0.36 g/cm.sup.3. No adhesion of the polymer to 
the wall of the autoclave was observed. 
Example 2 
Preparation of a zirconium catalyst 
2.3 g of calcined silica obtained by calcining silica (average particle 
diameter 70 .mu.m, specific surface area 260 m.sup.2 /g, pore volume 1.65 
cm.sup.3 /g) at 300.degree. C. for 4 hours, 4.8 ml of a toluene solution 
(Zr 0.01 mole/liter) of biscyclopentadienyl zirconium dichloride and 30 ml 
of a toluene solution (Al 1.03 mole/liter) of the aluminoxane synthesized 
in Example 1 were introduced into a 200 ml fully nitrogen-purged flask. 
The mixture was stirred at room temperature for 30 minutes. Subsequently, 
the toluene was removed from the solution at room temperature by an 
evaporator to give a solid catalyst component containing 0.11% by weight 
of Zr and 20% by weight of Al. The solid catalyst component had an average 
particle diameter of 78 .mu.m and a specific surface area of 210 m.sup.2 
/g. 
Preliminary Polymerization 
A gaseous mixture of ethylene and nitrogen (20 liters/hr and 30 liters/hr 
respectively) was passed at room temperature for 30 minutes through the 
solid catalyst component obtained as above to pre-polymerize ethylene. 
Ethylene polymerized in an amount of 0.51 g per gram of the solid catalyst 
component. 
Main Polymerization 
The same polymerization as in Example 1 was carried out to give 102.5 g of 
a polymer having an MFR of 0.05 g/10 min., an Mw/Mn of 2.73 and a bulk 
density of 0.35 g/cm.sup.3. No adhesion of the polymer to the autoclave 
wall was observed. 
Example 3 
Preparation of a Zirconium Catalyst 
A solid catalyst component containing 0.22% by weight of Zr and 21% by 
weight of Al was obtained by repeating Example 2 except that 1.9 g of 
silica, 8.0 ml of a toluene solution (Zr 0.01 mole/liter) of 
biscyclopentadienyl zirconium dicloride and 25 ml of a toluene solution 
(Al 1.03 mole/liter) of aluminoxane synthesized in Example 1 were used. 
The resulting solid catalyst component had an average particle diameter of 
78 .mu.m and a specific surface area of 220 m.sup.2 /g. 
Preliminary Polymerization 
Prepolymerization was carried out in the same way as in Example 1 to give a 
solid catalyst which catalyzed polymerization of 0.49 g of ethylene per 
gram thereof. 
Main Polymerization 
Example 1 was repeated to give 26.3 g of a polymer having an MFR of 0.02 
g/10 min., an Mw/Mn of 2.80 and a bulk density of 0.37 g/cm.sup.3. No 
adhesion of the polymer to the wall of the autoclave was observed. 
Example 4 
Preparation of a Zirconium Catalyst 
5.8 g of calcined alumina obtained by calcining alumina (average particle 
diameter 60 .mu.m, specific surface area 290 m.sup.2 /g, pore volume 1.05 
ml/g) at 500.degree. C. for 5 hours, 17 ml of a toluene solution (Al 1 
mole/liter) of dimethylaluminum monochloride and 50 ml of toluene were 
introduced into a 200 ml flask fully purged with nitrogen, and heated at 
80.degree. C. for 2 hours. Then, the reaction mixture was subjected to 
solid-liquid separation by filtration, and the solid portion was 
transferred into 50 ml of toluene. Furthermore, 32 ml of a toluene 
solution (Zr 0.036 mole/liter) of biscyclopentadienyl zirconium chloride 
was added, and the mixture was heated at 80.degree. C. for 1 hour. The 
reaction mixture was subjected to solid-liquid separation by filtration to 
give a solid catalyst containing 0.25% by weight of Zr. The above solid 
portion had an average particle diameter of 69 .mu.m and a specific 
surface area of 240 m.sup.2 /g. 
Preliminary Polymerization 
The solid catalyst obtained as above (0.015 mg-atom as Zr), 4.9 ml of a 
toluene solution (Al 1.03 mole/liter) of the aluminoxane synthesized in 
Example 1 and 20 ml of toluene were stirred at room temperature for 30 
minutes, and then toluene was removed at room temperature by an 
evaporator. 
The resulting solid catalyst was subjected to preliminary polymerization in 
the same way as in Example 1. Ethylene polymerized in an amount of 0.32 g 
per gram of the solid catalyst. 
Main Polymerization 
Sodium chloride (special reagent grade, Wako Pure Chemicals, Co., Ltd.; 250 
g) was introduced into a 2-liter stainless steel autoclave fully purged 
with nitrogen, and dried at 90.degree. C. under reduced presure for 1 
hour. Thereafter, the inside of the autoclave was purged with ethylene, 
and the temperature was raised to 75.degree. C. Subsequently, all the 
catalyst subjected to preliminary polymerization was charged into the 
autoclave, and ethyene was introduced. The total pressure was adjusted to 
8 kg/cm.sup.2 -G, and the polymerization of ethylene was started. 
Thereafter, the polymerization was carried out at 80.degree. C. for 1 hour 
while maintaining the total pressure at 8 kg/cm.sup.2 -G by supplying 
ethylene alone. After the polymerization, sodium chloride was removed by 
washing with water, and the remaining polymer was washed with hexane and 
then dried overnight at 80.degree. C. under reduced pressure. There was 
obtained 32.2 g of a polymer having an MFR of 0.10 g/10 min., an Mw/Mn of 
2.79 and a bulk density of 0.40 g/cm.sup.3. No adhesion of the polymer to 
the wall of the autoclave was observed. 
Example 5 
Main Polymerization 
Ethylene and 1-hexene were copolymerized under a total pressure of 7 
kg/cm.sup.2 -G using 900 ml of hexane and 100 ml of 1-hexene. Otherwise, 
Example 1 was repeated to give 110 g of a polymer having an MFR of 0.12 
g/10 min., an Mw/Mn of 2.80, a bulk density of 0.34 g/cm.sup.3, a density 
of 0.915 g/cm.sup.3 and a weight fraction of a portion soluble in decane 
at room temperature of 0.25% by weight. Hardly any adhesion of the polymer 
to the wall of the autoclave was observed. 
Comparative Example 1 
The catalyst preparation and polymerization were carried out in the same 
way as in Example 2 except that the preliminary polymerization was not 
carried out. There was obtained 95.9 g of a polymer having an MFR of 0.002 
g/10 min., an Mw/Mn of 2.91 and a bulk density of 0.07 g/cm.sup.3. 
Considerable adhesion of the polymer to the wall of the autoclave was 
observed. 
Example 6 
Preparation of a Zirconium Catalyst 
2.3 g of calcined silica obtained by calcining silica (average particle 
diameter 70 .mu.m, specific surface area 260 m.sup.2 /g, pore volume 1.65 
cm.sup.3 /g) at 300.degree. C. for 4 hours, 15 ml of a toluene solution 
(Al 1 mole/liter) of dimethylaluminum monochloride, and 50 ml of toluene 
were introduced into a 200 ml fully nitrogen-purged flask, and heated at 
80.degree. C. for 2 hours. Subsequently, the reaction mixture was 
subjected to solid-liquid separation by filtration, and the solid portion 
was transferred into 50 ml of toluene. Then, 6.4 ml of a toluene solution 
(0.01 mole-Zr/liter of solution) of bis(cyclopentadienyl)zirconium 
dichloride was added. The mixture was stirred at room temperature for 2 
hours and then subjected to solid-liquid separation by filtration. The 
solid portion was suspended in 100 ml of n-decane. While the suspension 
was stirred, 31 ml of a toluene solution (2.3 moles-Al/liter of solution) 
of aluminoxane was added. The mixture was warmed to 35.degree. C., and the 
pressure of the inside of the reactor was reduced to 4 torr to evaporate 
the toluene. The reaction suspension was filtered at -20.degree. C. The 
solid portion was collected and suspended in 50 ml of n-decane. The 
resulting solid catalyst had an average particle diameter of 78 .mu.m and 
a specific surface area of 226 m.sup.2 /g. 
Preliminary Polymerization 
A 400 ml reactor equipped with a stirrer was charged with 100 ml of 
purified n-decane and 0.1 mg-atom, as Zr, of the above solid catalyst in 
an atmosphere of nitrogen, and then ethylene was fed into the reactor for 
1 hour at a rate of 4N l/hour. During this time, the temperature was 
maintained at 20.degree. C. After the feeding of ethylene, the inside of 
the reactor was purged with nitrogen, and the reaction mixture was washed 
once with purified hexane, and suspended in hexane. The catalyst was thus 
stored in a catalyst bottle. 
Main Polymerization 
Sodium chloride as a dispersant was added in an amount of 250 g/cm.sup.3 to 
a 2-liter autoclave purged fully with nitrogen, and while the autoclave 
was heated at 90.degree. C., pressure reduction treatment was carried out 
for 2 hours using a vacuum pump so that the pressure of the inside of the 
autoclave was below 50 mmHg. Then, the temperature of the autoclave was 
lowered to 75.degree. C., and the inside of the autoclave was purged with 
ethylene. The solid catalyst component subjected to prepolymerization was 
added in an amount of 0.007 millimole as Zr, and the autoclave was sealed 
up. Hydrogen (50N ml) was added, and ethylene was introduced so that the 
inside pressure of the autoclave reached 8.0 kg/cm.sup.2 -G. The stirring 
speed was raised to 300 rpm, and the polymerization was carried out at 
80.degree. C. for 1 hour. 
After the polymerization, all the polymer and sodium chloride in the 
autoclave were taken out and fed into about 1 liter of water. By stirring 
for about 5 minutes, almost all sodium chloride dissolved in water and 
only the polymer came afloat on the water surface. The floating polymer 
was recovered, washed thoroughly with methanol, and dried overnight at 
80.degree. C. under reduced pressure. The amount of the polymer yielded 
was 106.2 g/cm.sup.3. It had an MFR of 2.1 dg/min. and an apparent bulk 
density of 0.46 g/ml. The amount of a fine powdery polymer having a 
particle size of less than 105 .mu.m was 0.1% by weight of the total 
amount of the polymerization product. On the other hand, no coarse polymer 
having a size of more than 1120 .mu.m was seen to form. The Mw/Mn, 
determined by GPC measurement, was 3.0. 
Comparative Example 2 
Catalyst preparation and polymerization were carried out in the same way as 
in Example 6 except that no preliminary polymerization as in Example 6 was 
carried out. There was obtained 63.3 g of a polymer having an MFR of 3.6 
dg/min. and an apparent density of 0.28 g/ml. The amount of a fine powdery 
polymer having a size of less than 105 .mu.m was 7.6% by weight based on 
the total amount of the polymerization product. 
Example 7 
Preparation of a Zirconium Catalyst 
67 ml of a toluene solution containing 100 millimoles, as the Al atoms, of 
the aluminoxane and 2 g of a polyethylene powder having an average 
particle diameter of 35 .mu.m (MIPERON.RTM., a trademark for a product of 
Mitsui Petrochemical Industries, Ltd.) were charged into a 300 ml 
pressure-reducible reactor equipped with a stirrer, and with stirring at 
room temperature, 100 ml of purified n-decane was added over the course of 
about 0.5 hour, whereupon the aluminoxane was precipitated. Then, the 
temperature of the inside of the reactor was raised to 35.degree. C. over 
the course of about 3 hours while the pressure of the inside of the 
reactor was reduced to 4 torr by means of a vacuum pump. Consequently, the 
toluene in the reactor was removed, and the aluminoxane was further 
precipitated. The reaction solution was filtered by a filter, and the 
liquid portion was removed. The solid portion was suspended in n-decane, 
and 5 ml of a toluene solution containing 0.2 millimole of 
bis(cyclopentadienyl)zirconium chloride was added. They were mixed at room 
temperature for about 1 hour, and the liquid portion was removed by a 
filter. Thus, a solid catalyst for olefin polymerization was formed. 
The Zr content of the resulting solid catalyst was 9 millimoles per 100 g 
of the polyethylene used as a carrier, and its Al content was 2.0 moles 
per 100 g of the polyethylene carrier. The average catalyst particle 
diameter of the catalyst determiend by microscopic observation was about 
40 .mu.m, and it had a specific surface area of 143 m.sup.2 /g. 
Prepolymerization and vapor-phase polymerization of ethylene were carried 
out by the same operations as in Example 6. There was obtained 128.2 g of 
a polymer having an MFR of 1.6 dg/min. and an apparent bulk density of 
0.46 g/ml. The amount of a fine powdery polymer having a particle diameter 
of less than 105 .mu.m was 0.1% by weight based on the total amount of the 
polymerization product. The Mw/Mn determined by GPC measurement was 2.6. 
Example 8 
A solid catalyst was prepared in the same way as in Example 7 except that 2 
liters of spherical polystyrene particles having a particle diameter of 
about 30 .mu.m (#200 to #400, a product of Eastman Kodak Co.) was used 
instead of the polyethylene carrier. Preliminary polymerization and 
vapor-phase polymerizaton of ethylene were carried out as in Example 7. 
The resulting solid catalyst had an average particle diameter of 35 .mu.m 
and a specific surface area of 143 m.sup.2 /g. As a result, there was 
obtained 110.6 g of a polymer having an MFR of 3.6 dg/min. and an apparent 
bulk density of 0.44 g/ml. The amount of a fine powdery polymer having a 
particle diameter of less than 105 .mu.m was 0.2% by weight based on the 
total amount of the polymerization product. 
Example 9 
Preparation of a Solid Catalyst Component (Zirconium Catalyst) 
5.2 g of calcined silica obtained by calcining silica (average particle 
diameter 70 .mu.m, specific surface area 260 m.sup.2 /g pore volume 1.65 
cm.sup.3 /g) at 700.degree. C. for 5 hours, 26 ml of a toluene solution 
(Al 1 mole/liter) of diethylaluminum monochloride and 50 ml of toluene 
were introduced into a 200 ml flask fully purged with nitrogen, and heated 
at 80.degree. C. for 2 hours. The reaction mixture was then subjected to 
solid-liquid separation by filtration to obtain a catalyst component. The 
catalyst component was transferred into 50 ml of toluene, and 43 ml of a 
toluene solution (Zr 0.04 mole/liter) of bis(cyclopentadienyl)zirconium 
chloride as another catalyst component was added, and the mixture was 
heated at 80.degree. C. for 1 hour. The reaction mixture was subjected to 
solid-liquid separation by filtration to obtain a solid catalyst component 
(A') having 0.012 mg-atom and 1.12 mg-atom of Al supported per gram of 
silica. The solid catalyst component (A') in an amount of 0.015 mg-atom, 
as Zr, was added to 4.9 ml of a toluene solution (Al 1.03 moles/liter) of 
aluminoxane as catalyst component (B) and 20 ml of toluene, and the 
mixture was stirred at room temperature for 30 minutes. Then, the toluene 
was removed from the mixture by an evaporator to give a solid catalyst 
component containing 0.08% by weight of Zr and 10% by weight of Al. 
Polymerization 
250 g of sodium chloride (special reagent grade, Wako Pure Chemical Co., 
Ltd.) was introduced into a 2-liter stainless steel autoclave fully purged 
with nitrogen, and dried at 90.degree. C. for 1 hour under reduced 
presure. Thereafter, the inside of the autoclave was purged with ethylene, 
and the temperature was adjusted to 75.degree. C. Subsequently, all the 
catalyst prepared as above was introduced. Ethylene was introduced, and 
under a total pressure of 8 kg/cm.sup.2 -G, its polymerization was 
started. Thereafter, only ethylene was supplied, and the polymerization 
was carried out at 80.degree. C. for 1 hour while the total pressure was 
maintained at 8 kg/cm.sup.2 -G. After the polymerization, sodium chloride 
was removed by washing with water. The remaining polymer was washed with 
hexane, and dried overnight at 80.degree. C. under reduced pressure. There 
was obtained 72 g of a polymer having an MFR of 0.07 g/10 min., an Mw/Mn 
of 2.64 and a bulk density of 0.36 g/cm.sup.3. No adhesion of the polymer 
to the wall of the autoclave was observed. 
Example 10 
Preparation of a Solid Catalyst Component (Zirconium Catalyst) 
5.8 g of calcined alumina obtained by calcining alumina (average particle 
diameter 60 .mu.m, specific surface area 270 m.sup.2 /g, pore volume 1.05 
cm.sup.3 /g) at 500.degree. C. for 5 hours, 17 ml of a toluene solution 
(Al 1 mole/liter) of dimethylaluminum monochloride and 50 ml of toluene 
were added to a 200 ml flask purged fully with nitrogen, and the mixture 
was heated at 80.degree. C. for 2 hours. The reaction mixture was then 
subjected to solid-liquid separation by filtration. The solid portion was 
transferred into 50 ml of toluene, and 32 ml of a toluene solution (Zr 
0.036 mole/liter) of bis(cyclopentadienyl)zirconium chloride was added. 
The mixture was heated at 80.degree. C. for 1 hour. The reaction mixture 
was subjected to solid-liquid separation by filtration to obtain a solid 
component containing 0.25% by weight of Zr. This solid component was 
reacted with aluminoxane in the same way as in Example 9 to give a solid 
catalyst component containing 0.16% by weight of Zr. 
Polymerization 
The same polymerization as in Example 9 was carried out using 0.015 
mg-atom, as Zr atom, of the above solid catalyst. There was obtained 42 g 
of a polymer having an MFR of 0.09 g/10 min., an Mw/Mn of 2.77 and a bulk 
density of 0.35 g/cm.sup.3. No adhesion of the polymer to the wall of the 
autoclave was observed. 
Example 11 
Preparation of a Solid Catalyst Component (Zirconium Catalyst) 
2.3 g of calcined silica obtained by calcining silica (average particle 
diameter 70 .mu.m, specific surface area 260 m.sup.2 /g, pore volume 1.65 
cm.sup.3 /g) at 300.degree. C. for 4 hours, 15 ml of a toluene solution 
(Al 1 mole/liter) of dimethylaluminum monochloride and 50 ml of toluene 
were introduced into a 200 ml flask purged with nitrogen, and heated at 
80.degree. C. for 2 hours. The reaction mixture was subjected to 
solid-liquid separation by filtration. The solid portion was transferred 
into 50 ml of toluene, and 6.4 ml of a toluene solution (Zr 0.01 
mole/liter) of bis(cyclopentadienyl)zirconium chloride was added. The 
mixture was stirred at room temperature for 2 hours. Then, 31 ml of a 
toluene solution (Al 1.03 mole/liter) of the aluminoxane synthesized in 
Example 9 was added, and the mixture was stirred at room temperature for 
30 minutes. The reaction mixture was worked up as in Example 9 to give a 
solid titanium component containing 0.14% by weight of Zr and 22% by 
weight of Al. 
Polymerization 
The same polymerization as in Example 9 was carried out using 0.015 
mg-atom, as Zr, of the above solid catalyst. There was obtained 70 g of a 
polymer having an MFR of 0.12 g/10 min., an Mw/Mn of 2.67, and a bulk 
density of 0.38 g/cm.sup.3. No adhesion of the polymer to the wall of the 
autoclave was noted. 
Comparative Example 3 
Catalyst preparation and polymerization were carried out in the same way as 
in Example 9 except that silica was not treated with dimethylaluminum 
monochloride. There was obtained 21 g of a polymer having an MFR of 0.02 
g/10 min., an Mw/Mn of 2.89 and a bulk density of 0.15 g/cm.sup.3. 
The solid catalyst component used in the polymerization contained 0.35% by 
weight of Zr and 35% by weight of Al. 
Example 12 
Preparation of a Solid Catalyst Component (Zirconium Catalyst) 
Example 9 was repeated except that 6 millimoles of triethyl aluminum 
instead of dimethyl aluminum monochloride was added to 1 g of silica 
calcined at 800.degree. C. for 12 hours and reacted at 50.degree. C. for 2 
hours, and that 0.042 millimole of biscyclopentadienyl zirconium 
dichloride per gram of silica was added and reacted at room temperature 
for 2 hours. There was obtained a solid catalyst component having 
6.7.times.10.sup.-3 milligram-atom of zirconium supported per gram of 
silica. 
Polymerization 
Polymerization was carried out in the same way as in Example 9 except that 
15 milligram-atom, as aluminum atom, of aluminoxane, and 0.015 
milligram-atom, as zirconium atom, of the solid catalyst component 
prepared above were introduced, and furthermore, 50 ml of hydrogen was 
added. There was obtained 69 g of a polymer having an MFR of 24 g/10 min., 
an Mw/Mn of 2.70 and a bulk density of 0.31 g/cm.sup.3. 
Adhesion of the polymer to the autoclave wall was hardly observed. 
Example 13 
Preparation of a Solid Catalyst Component (Zr Catalyst) 
Example 12 was repeated except that diethyl aluminum monochloride was used 
instead of triethyl aluminum. A solid catalyst component having 
5.7.times.10.sup.-3 milligram-atom of zirconium supported on it per gram 
of silica was obtained. 
Polymerization 
Polymerization was carried out as in Example 12 to give 71 g of a polymer 
having an MFR of 9.5 g/10 min., an Mw/Mn of 2.59 and a bulk density of 
0.34 g/cm.sup.3. Adhesion of the polymer to the autoclave wall was hardly 
observed. 
Example 14 
Polymerization 
Example 9 was repeated except that 10 ml of hexene-1 was added, and the 
polymerization was carried out at 70.degree. C. for 0.5 hour. There was 
obtained 42 g of a polymer having an MRF of 2.05 g/10 min., an Mw/Mn of 
2.84, a bulk density of 0.31 g/cm.sup.3, a density of 0.926 g/cm.sup.3 and 
a weight fraction of a decane-soluble portion of 0.15% by weight. 
Adhesion of the polymer to the autoclave wall was hardly observed. 
Example 15 
Preparation of a Solid Catalyst Component [A] 
In a 400 ml glass flask equipped with a stirrer and fully purged with 
nitrogen, a mixed suspension composed of 3 g of silica (#952 made by 
Davison Co.) calcined for 12 hours at 300.degree. C. and 50 ml of 
trichlorosilane was reacted at 50.degree. C. for 2 hours with stirring. 
After the reaction, the liquid portion was removed from the reaction 
mixture by using a filter, and the remaining solid portion was suspended 
in 50 ml of toluene. To the suspension was added 300 ml of toluene 
containing 15 millimoles of bis(cyclopentadienyl)zirconium dichloride at 
25.degree. C. The mixture was reacted at 50.degree. C. for 2 hours with 
stirring. After the reaction, the liquid portion was removed from the 
suspension by using a filter. The remaining solid portion was washed twice 
with toluene to give a solid catalyst component (A). The amount of 
zirconium supported on the catalyst component (A) was 1.4% by weight. 
Polymerization 
Sodium chloride (250 g) as a dispersant was added to a 2-liter autoclave 
fully purged with nitrogen. While the autoclave was heated to 90.degree. 
C., the inside of the autoclave was subjected to a pressure reduction 
treatment for 2 hours using a vacuum pump so that the inside pressure of 
the autoclave became 50 mmHg or below. The temperature of the autoclave 
was then lowered to 75.degree. C., and the inside of the autoclave was 
replaced by ethylene. Then, 0.13 millimole of aluminoxane was added, and 
the mixture was stirred for 2 minutes at a rotating speed of 50 rpm. 
Thereafter, 0.87 millimole of aluminoxane and 0.015 millimole, as 
zirconium atom, of the solid catalyst component were added, and the 
autoclave was sealed up. Hydrogen (20N ml) was added and the autoclave was 
pressurized with ethylene so that the pressure of the inside of the 
autoclave reached 8 kg/cm.sup.2 -G. The stirring speed was increased to 
300 rpm, and the polymerization was carried out at 80.degree. C. for 1 
hour. 
After the polymerization, all the polymer and sodium chloride in the 
autoclave were taken out and put in about 1 liter of water. The mixture 
was stirred for about 5 minutes to dissolve almost all sodium chloride in 
water. As a result, only the polymer came afloat on the water surface. The 
floating polymer was recovered, fully washed with methanol, and dried 
overnight at 80.degree. C. under reduced pressure. The amount of the 
polymer yielded was 48.3 g, and the polymer had an MFR of 13 and an 
apparent bulk density of 0.42 g/ml. A fine powdery polymer having a size 
of not more than 105 micrometers and a coarse polymer having a size of at 
least 1120 micrometers were not observed. The polymer had an Mw/Mn of 2.7. 
Examples 16 to 19 
Ethylene was polymerized in the same way as in Example 15 except that each 
of the silane compounds indicated in Table 1 was used instead of the 
trichlorosilane used in preparing the solid catalyst component in Example 
15. The results are shown in Table 1. 
Example 20 
A solid catalyst component was prepared, and ethylene was polymerized, as 
in Example 15 except that the amount of trichlorosilane used to treat 
silica was changed from 50 ml to 10 ml in the preparation of the solid 
catalyst component in Example 15. The results are shown in Table 2. 
Example 21 
A solid catalyst component was prepared, and ethylene was polymerized, as 
in Example 20 except that the amount of bis(cyclopentadienyl)zirconium 
dichloride used in the preparation of the solid catalyst component in 
Example 20 was changed from 15 millimoles to 3 millimoles, and the amount 
of toluene at this time was changed from 300 ml to 60 ml. The results are 
shown in Table 2. 
Example 22 
Ethylene was polymerized as in Example 15 except that chlorinated 
aluminoxane was used instead of the aluminoxane used at the time of 
polymerization in Example 15. The results are shown in Table 2. The 
chlorinated aluminoxane was prepared by the following method. 
Aluminoxane-III 
This compound was synthesized as in the synthesis of aluminoxane-I except 
that in the synthesis of aluminoxane-I, the amount of trimethyl aluminum 
was changed from 50 ml to 24.7 ml and 25.3 ml of dimethyl aluminum 
chloride was simultaneously added dropwise. The aluminoxane had an average 
degree of polymerization of 12. 
Example 23 
Polymerization was carried out in the same way as in Example 15 except that 
in Example 15, a gaseous mixture of butene-1 and ethylene containing 9.5 
mole % of butene-1 was used instead of ethylene alone, and the 
polymerization temperature was changed from 80.degree. C. to 70.degree. C. 
The results are shown in Table 3. 
Comparative Example 4 
An MgCl.sub.2 -supported Ti catalyst component prepared in accordance with 
the method of Example 1 of Japanese Laid-Open Patent Publication No. 
811/1981 was used. Polymerization was carried out in the same way as in 
Example 15 except that aluminoxane described under the heading 
Polymerization in Example 15 was replaced by triethyl aluminum, and the 
same gaseous mixture of butene-1 and ethylene containing 9.5 mole % of 
butene-1 as used in Example 23 was used, and the polymerization 
temperature was changed from 80.degree. C. to 70.degree. C. The results 
are shown in Table 3. 
TABLE 1 
__________________________________________________________________________ 
Particle size 
distribution (wt. %) 
Amount of 
Polymerization 
Bulk 
105 .mu.m 
1120 .mu.m 
Si Zr supported 
activity 
density 
and and 
Example 
Compound 
(wt. %) 
(g-PE/mM-Ti) 
(g/ml) 
below 
above 
__________________________________________________________________________ 
15 HSiCl.sub.3 
1.2 3,200 0.42 
0 0 
16 SiCl.sub.4 
1.3 3,100 0.42 
0.1 0 
17 HMeSiCl.sub.2 
0.9 2,700 0.40 
0.1 0 
18 HPhSiCl.sub.2 
0.7 2,000 0.39 
0.1 0.1 
19 MeSiCl.sub.2 
1.4 2,600 0.39 
0 0 
__________________________________________________________________________ 
TABLE 2 
______________________________________ 
Particle size 
Amount distribution (wt. %) 
of Zr Polymerization 
Bulk 105 .mu.m 
1120 .mu.m 
supported 
activity density 
and and 
Example 
(wt. %) (g-PE/mM-Ti) 
(g/ml) 
below above 
______________________________________ 
20 1.0 3,000 0.42 0 0 
21 3.0 4,300 0.41 0.1 0 
22 -- 2,100 0.41 0.2 0 
______________________________________ 
TABLE 3 
__________________________________________________________________________ 
Amount of the 
Polymerization 
Bulk decane-soluble 
activity 
MFR density 
Density 
component 
Run (g-PE/mM-Metal) 
(dg/min) 
(g/ml) 
(g/ml) 
(wt. %) 
Mw/Mn 
__________________________________________________________________________ 
Example 23 
3,300 11.0 0.38 
0.919 
3.0 2.7 
Comparative 
5,200 3.0 0.30 
0.918 
6.4 4.7 
Example 4 
__________________________________________________________________________ 
Example 24 
Synthesis of Aluminoxane 
Aluminoxane-I: 
Al.sub.2 (SO.sub.4).sub.3.14H.sub.2 O (37 g) and 125 ml of toluene were put 
in a 400 ml glass flask equipped with a stirrer and purged fully with 
nitrogen, and cooled to 0.degree. C. Then, 125 ml of toluene containing 50 
ml of trimethyl aluminum was added dropwise over 1 hour. The mixture was 
heated to 40.degree. C. over 2 hours and the reaction was continued at 
this temperature for 10 hours. After the reaction, the reaction mixture 
was subjected to solid-liquid separation by filtration. Low-boiling 
materials were removed from the separated liquid by means of an 
evaporator. Toluene was added to the remaining viscous liquid and the 
toluene solution was collected. The resulting aluminoxane had a molecular 
weight, determined from its freezing point depression in benzene, of 885 
and an average degree of polymerization of 15. 
Aluminoxane-II: 
The synthesis of aluminoxane-I was repeated except that the reaction time 
at 40.degree. C. was changed from 10 hours to 2 hours. The resulting 
aluminoxane had a degree of polymerization of 6. 
Preparation of a Solid Catalyst Component (Zr Catalyst) 
In a 400 ml glass flask equipped with a stirrer and purged fully with 
nitrogen, a solution of 2 millimoles of aluminoxane (I) in 50 ml of 
toluene was added at room temperature to a suspension composed of 5 g of 
silica (#952 produced by Davison Co.) calcined at 800.degree. C. for 12 
hours and 100 ml of toluene. The mixture was heated to 50.degree. C. and 
reacted at 50.degree. C. for 2 hours. After the reaction, the liquid 
portion was removed from the reaction mixture by using a filter. The 
remaining solid portion was suspended in 100 ml of toluene. To the 
suspension was added 9.4 ml of toluene containing 0.38 millimole of 
bis(cyclopentadienyl)zirconium dichloride at 25.degree. C., and the 
mixture was reacted at 25.degree. C. for 2 hours. After the reaction, the 
liquid portion was removed from the suspension by using a filter. The 
remaining solid portion was washed twice with toluene to give a solid 
catalyst component. The catalyst component had 0.6% by weight of zirconium 
supported on it. 
Polymerization 
Sodium chloride (250 g) as a dispersing agent was added to a 2-liter 
autoclave purged fully with nitrogen, and while the autoclave was heated 
at 90.degree. C., it was subjected to a pressure reduction treatment for 2 
hours by means of a vacuum pump so that the inside pressure of the 
autoclave became 50 mmHg or below. The temperature of the autocalve was 
then lowered to 75.degree. C., and the inside of the autoclave was 
replaced by ethylene. 0.13 millimole of aluminoxane (aluminoxane-II) was 
then added, and the mixture was stirred at a speed of 50 rpm for 2 
minutes. Thereafter, 0.87 millimole of aluminoxane (aluminoxane-I) and 
0.015 millimole, as zirconium atom, of the solid catalyst component were 
added. The autoclave was sealed up. Hydrogen (20N ml) was added and the 
inside of the autoclave was pressurized with ethylene so that the inside 
pressure became 8 kg/cm.sup.2 -G. The stirring speed was increased to 300 
rpm, and the polymerization was carried out at 80.degree. C. for 1 hour. 
After the polymerization, all the polymer and sodium chloride in the 
autoclave were taken out, and put in about 1 liter of water. The mixture 
was stirred for about 5 minutes to dissolve almost all the sodium 
chloride. Only the polymer came afloat on the water surface. The floating 
polymer was recovered, washed fully with methanol, and dried overnight at 
80.degree. C. under reduced pressure. The amount of the polymer yielded 
was 82.1 g. The polymer had an MFR of 7.9 and an apparent bulk density of 
0.43 g/ml. The amount of a fine powdery polymer having a size of not more 
than 105 micrometers was 0.1% by weight of the entire polymerization 
product. A coarse polymer having a size of at least 1120 micrometers was 
not observed. The Mw/Mn of the polymer was 2.7. The results are shown in 
Table 4. 
Example 25 
A solid catalyst component was prepared, and ethylene was polymerized, in 
the same way as in Example 24 except that in the preparation of the solid 
catalyst component in Example 24, the amount of aluminoxane used to treat 
silica was changed from 2 millimoles to 10 millimoles. The results are 
shown in Table 4. 
Examples 26 and 27 
A solid catalyst component (A) was prepared, and ethylene was polymerized, 
in the same way as in Example 24 except that in the preparation of the 
solid catalyst component in Example 24, the temperature at which the 
reaction of supporting cyclopentadienyl zirconium dichloride was carried 
out in the preparation of the solid catalyst component in Example 24 was 
changed to 50.degree. and 80.degree. C. respectively from 25.degree. C. 
The results are shown in Table 4. 
Example 28 
A solid catalyst component was prepared, and ethylene was polymerized, in 
the same way as in Example 24 except that in the preparation of the solid 
catalyst component in Example 24, aluminoxane-II was used instead of the 
aluminoxane-I. The results are shown in Table 4. 
Example 29 
Ethylene was polymerized in the same way as in Example 24 except that 
aluminoxane-II was used instead of the aluminoxane-I at the time of 
polymerization in Example 24. The results are shown in Table 4. 
Example 30 
Polymerization was carried out in the same way as in Example 24 except that 
a gaseous mixture of butene-1 and ethylene containing 9.5 mole % of 
butene-1 was used instead of ethylene, and the polymerization temperature 
was changed from 80.degree. C. to 70.degree. C. The results are shown in 
Table 5. 
TABLE 4 
______________________________________ 
Polymeri- Particle size 
zation distribution (wt. %) 
activity Apparent 
105 .mu.m 
1120 .mu.m 
(g-PE/ MFR bulk density 
and and 
Example 
mM-Zr) (dg/min) (g/ml) below above 
______________________________________ 
24 5,500 7.9 0.43 0.1 0 
25 4,800 12 0.43 0.1 0 
26 5,400 13 0.42 0.1 0.1 
27 5,000 17 0.43 0.1 0 
28 4,900 6.1 0.43 0 0 
29 3,800 8.3 0.42 0.1 0 
______________________________________ 
TABLE 5 
__________________________________________________________________________ 
Polymerization 
Apparent Amount of the 
activity 
MFR bulk density 
Density 
decane-soluble 
Example 
(g-PE/mM-Metal) 
(dg/min) 
(g/ml) 
(g/ml) 
portion (wt. %) 
Mw/Mn 
__________________________________________________________________________ 
30 4,900 21 0.39 0.916 
2.6 2.6 
__________________________________________________________________________ 
Example 31 
Synthesis of Aluminoxane 
Halogenated Aluminoxane-I: 
This compound was synthesized by the same method as in the synthesis of 
aluminoxane-I except that in the synthesis of aluminoxane-I, 46 ml of 
dimethyl aluminum chloride was used instead of 50 ml of trimethyl 
aluminum. The resulting halogenated aluminoxane had an average degree of 
polymerization of 11. 
Halogenated Aluminoxane-II: 
This compound was synthesized in the same way as in the synthesis of 
aluminoxane-I except that in the synthesis of aluminoxane-I, the amount of 
trimethyl aluminum added was changed from 50 ml to 24.7 ml and 25.3 ml of 
dimethyl aluminum chloride was added dropwise at the same time. This 
halogenated aluminoxane had a degree of polymerization of 12. 
Preparation of a Solid Catalyst Component (Zr Catalyst) 
In a 400 ml glass flask equipped with a stirrer and purged fully with 
nitrogen, 50 ml of toluene solution containing 2 millimoles of halogenated 
aluminoxane-I was added to a suspension composed of 5 g of silica (#952 
produced by Davison Co.) calcined at 800.degree. C. for 12 hours and 100 
ml of toluene. The mixture was heated to 50.degree. C. and reacted at 
50.degree. C. for 2 hours. After the reaction, the liquid portion was 
removed from the reaction mixture by using a filter. The remaining solid 
portion was suspended in 100 ml of toluene. To the suspension was added 
9.4 ml of toluene containing 0.38 millimole of 
bis(cyclopentadienyl)zirconium dichloride at 25.degree. C., and the 
reaction was carried out at 25.degree. C. for 2 hours. After the reaction, 
the liquid portion was removed from the suspension by using a filter. The 
remaining solid portion was washed twice with toluene to give a solid 
catalyst component having 0.7% by weight of zirconium supported on it. 
Polymerization 
Sodium chloride (250 g) as a dispersing agent was added to a 2-liter 
autoclave purged fully with nitrogen, and while the autoclave was heated 
at 90.degree. C., it was subjected to a pressure reduction treatment for 2 
hours by means of a vacuum pump so that the inside pressure of the 
autoclave became 50 mmHg or below. The temperature of the autoclave was 
then lowered to 75.degree. C., and the inside of the autoclave was 
replaced by ethylene. 0.13 millimole of aluminoxane (aluminoxane-I) was 
then added, and the mixture was stirred at a speed of 50 rpm for 2 
minutes. Thereafter, 0.87 millimole of aluminoxane (aluminoxane-I) and 
0.015 millimole, as zirconium atom, of the solid catalyst component were 
added. The autoclave was sealed up. Hydrogen (20N ml) was added and the 
inside of the autoclave was pressurized with ethylene so that the inside 
pressure became 8 kg/cm.sup.2 -G. The stirring speed was increased to 300 
rpm, and the polymerization was carried out at 80.degree. C. for 1 hour. 
After the polymerization, all the polymer and sodium chloride in the 
autoclave were taken out, and put in about 1 liter of water. The mixture 
was stirred for about 5 minutes to dissolve almost all the sodium 
chloride. Only the polymer came afloat on the water surface. The floating 
polymer was recovered, washed fully with methanol, and dried overnight at 
80.degree. C. under reduced pressure. The amount of the polymer yielded 
was 93.1 g. The polymer had an MFR of 11.3 and an apparent bulk density of 
0.43 g/ml. The amount of a fine powdery polymer having a size of not more 
than 105 micrometers was 0.1% by weight of the entire polymerization 
product. A coarse polymer having a size of at least 1120 micrometers was 
not observed. The Mw/Mn of the polymer was 2.9. The results are shown in 
Table 6. 
Example 32 
A solid catalyst component was prepared, and ethylene was polymerized, in 
the same way as in Example 31 except that in the preparation of the solid 
catalyst component in Example 31, the amount of the halogenated 
aluminoxane-I used to treat silica was changed from 2 millimoles to 10 
millimoles. The results are shown in Table 6. 
Example 33 
A solid catalyst component (A) was prepared, and ethylene was polymerized, 
in the same way as in Example 31 except that in the preparation of the 
solid catalyst component in Example 31, the temperature employed in the 
supporting reaction of bis(cyclopentadienyl)zirconium dichloride was 
changed to 50.degree. C. from 25.degree. C. The solid catalyst component 
contained 0.7% by weight of Zr supported on it. The results are shown in 
Table 6. 
Example 34 
A catalyst component was prepared, and ethylene was polymerized, in the 
same way as in Example 31 except that in the preparation of the solid 
catalyst component in Example 31, the amount of 
bis(cyclopentadienyl)zirconium dichloride was changed from 0.38 millimole 
to 0.75 millimole, and the amount of the toluene solution of the above 
zirconium compound was changed from 9.4 ml to 18.8 ml. The amount of Zr 
supported on the solid catalyst component was 1.2% by weight. The results 
are shown in Table 6. 
Example 35 
A solid catalyst component was prepared, and ethylene was polymerized, in 
the same way as in Example 31 except that in the preparation of the solid 
catalyst component in Example 31, halogenated aluminoxane-II was used 
instead of the halogenated aluminoxane-I. The results are shown in Table 
6. 
Example 36 
Ethylene was polymerized in the same way as in Example 31 except that 
halogenated aluminoxane-II was used instead of the aluminoxane-I at the 
time of polymerization. The results are shown in Table 6. 
Example 37 
Polymerization was carried out in the same way as in Example 31 except that 
a gaseous mixture of 1-butene and ethylene having a butene-1 content of 
9.5 mole % was used instead of ethylene alone, and the polymerization 
temperature was changed from 80.degree. C. to 70.degree. C. The results 
are shown in Table 7. 
TABLE 6 
______________________________________ 
Polymeri- Particle size 
zation distribution (wt. %) 
activity Apparent 
105 .mu.m 
1120 .mu.m 
(g-PE/ MFR bulk density 
and and 
Example 
mM-Zr) (dg/min) (g/ml) below above 
______________________________________ 
31 6,200 11 0.43 0.1 0 
32 5,700 17 0.42 0.1 0 
33 5,900 10 0.43 0 0 
34 4,300 16 0.43 0 0 
35 5,200 5 0.43 0 0 
36 3,800 6 0.43 0.1 0 
______________________________________ 
TABLE 7 
__________________________________________________________________________ 
Apparent Amount of the 
Polymerization 
Bulk decane-soluble 
activity 
MFR density 
Density 
component 
Example 
(g-PE/mM-Metal) 
(dg/min) 
(g/ml) 
(g/ml) 
(wt. %) 
Mw/Mn 
__________________________________________________________________________ 
37 5,100 18 0.37 0.918 
2.8 2.9 
__________________________________________________________________________