CA1305282C - Process for polymerizing olefins - Google Patents

Abstract

ABSTRACT
This invention relates to a process for poly-merizing olefins using a catalyst composed of a tran-sition metal catalyst component,an aluminoxane component and an organoaluminum component. In the process of this invention, the catalyst exhibits excellent polymerization activity with the use of a small amount of the alumino-xane. The polymerization process gives olefin polymers having a narrow molecular weight distribution and by the copolymerization of two or more olefins, gives olefin copolymers having a narrow molecular weight distribution and a narrow composition distribution.

Description

" 13(:~Z~3Z

SPECIFICATION
PROCESS FOR POLYMERIZING OLEFINS
TEC~NOLOGICAL FIELD
This invention relates to a process for poly-merizing olefins. More specifically, it relates to a process for producing an olefin polymer of a narrow molecular weight distribution by polymerizing an olefin with a catalyst showing excellent polymerization activity using a small amount of an aluminoxane, which when applied to the copolymerization of at least two olefins, can give a copolymer having a narrow molecular weight distribution and a narrow composition distribution.
~AC~GROUND TEC~NOLOGY
lPrior Art]
For the production of an alpha-olefin polymer, particularly an ethylene polymer or an ethylene/alpha-olefin 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. Generally, ethylene/alpha-olefin copolymers obtained with titanium-type catalysts have a broad mol-ecular weight distribution and a broad composition di~-tribution and infeeior transparency, surface non-adhesiveness, and mechanical properties. Ethylene/alpha-olefin copolymers obtained with vanadium-type catalysts have a narrower molecular weight distribution and a narrower composition distribution and are considerably improved in transparency, surface non-adhesiveness, and mechanical properties, but are still insufficient for uses which require these properties. Accordingly, alpha-olefin polymers, especially ethylene/alpha-olefin 3~ copolymers, improved in these properties are required.
On the other hand, catalysts comprising a ~k 13~SZ~Z

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 poly-merizing ethylene and at least one alpha-olefin having 3 to 12 carbon atoms at a temperature of -50 C to 200 C
in the presence of a catalyst composed of a transition metal-containing catalyst represented by the following 10 formula (cyclopentadienyl)2MeRlHal wherein Rl represents cyclopentadienyl, Cl-C8 alkyl or halogen, He represents a transition metal, and Hal represents halogen, 15 with a linear aluminoxane represented by the following formula A120R24~Al~R2)-O)n wherein R2 eepre~ents methyl or ethyl, and n is a number of 4 to 20, 20 or a cyclic aluminoxane represented by the following formula ~Al~R2~- ~

wherein R2 and n are as defined above.
This patent document state~ that in order to 25 adju~t 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 ~aid-Open Patonnt Publication No. 0 95292/1984 dc w ribes an invention relating to a process i .. ... .

for producing a linear aluminoxane represented by the following formula R \ R3 ,R3 3~Al-O~Al-O~Al~ 3 wherein n is 2 to 40 and R3 is Cl-C8 alkyl, and a cyclic aluminoxane represented by the following formula l~
Al-wherein n and R3 are as defined above.
This Publication states that when an olefin is poly-merized 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 pee gram of the transition metal per hour.
Japanese Laid-Open Patent Publication No.
35005/1985 discloses a process for peoducing a catalyst for polymerization of olefins, which compri~es reacting an aluminoxane compound represented by the following formula R ~ "R4 O/ Al O~A,14 o ~ Al ~ R

wherein R4 represents Cl-C10 alkyl, and R is R4 or i~ bonded to represent -O-, with a magnesium compound, then chlorinating tbe 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 .

: .

., , . ~

i3~S2~32 for the copolymerization of ethylene with a C3-C12 alpha-olefin mixture.
Japanese ~aid-Open Patent Publication No.
35006/1985 discloses a combination of ~a) a mono-, di- or tri-cyclopentadienyl compound of at least two different transition metals or its derivative with ~b) alumoxane (aluminoxane) as a catalyst ~ystem 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 Publ ica-tion, a blend of polyethylene and an ethylene~propylenecopolymer having a number average molecular welght of 2,000, a weight avèrage molecular weight of 8,300 and a propylene component content of 7.1 mole % and con~isting 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 molo ~ and a toluene-insoluble portion having a nu~ber 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 ~nd propylene using bis~pentamcthylcyclopenta-dienyl)zirconium dichloride, bis~methylcyclopentadienyl)-; zirconium dichloride and alumoxane as a catalyst. Like-wise, 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/an) of 4.57 and a propylene component content of 20.6 ~ole ~ 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.

., .
,,"~
', " ;
~.~

"

~s~z~

35007/1985 describes a process which comprises polymeriz-ing ethylene alone or with an alpha-olefin having at least 3 carbon atoms in the presence of a catalyst system comprising metallocene and a cyclic alumoxane represented s by the following formula 4Al-O~
.5 n wherein R5 represents an alkyl group having 1 to S carbon atoms, and n is an integer of 1 to about 20, or a linear alumoxane represented by the following formula R5~Al-O)nAlR 2 wherein R5 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 distr~bution of 1.5 to 4Ø
Japanese Laid-Open Patent Publication No.
35008/1985 describes that polyethylene or a copolymer of ethylene and a C3-C10 alpha-olefin having a wide mol-eculae weight distribution i3 produced by using a cata-lyst ~ystem comprising at least two types of metallocenes and alumoxane. The Publication states that the above copolymer has a molecular weight distribution ~Mw/Mn) of 5 2 to 50.
These catalysts formed from transition metal compoundfi and aluminoxanes have much higher polymeriza-tion activity than the catalyst systems known heretofore.
On the other hand, methods using catalysts formed from solid catalyst components composed of the ~3~ 2 ~

above transition metal compounds supported on pOtOUS
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 propo~e methods using solid catalyst com-ponents supported on similar porous inorganic oxide carriers.
Furthermore, Japanese Laid-Open Patent Publications Nos. 260602/1985 and 130604/1985 propose a process for polymerizing olefins using catalysts formed from a transition metal compound and a mixed organo-aluminum compound composed of an aluminoxane and an 5 organoaluminum compound.
Japanese Laid-Open Patent Publication No.
260602/1985 discloses a proces~ for producing a poly-olefin by polymerizing an olefin using ~1) as the transition metal compound, a compound of the following formula ~Cp)MR6R R

wherein Cp i8 cyclopentadienyl, M is Tl, V, Zr or Hf, and each of R6, R7 and R8 represents Cl-C6 alkyl, cyclopentadienyl, halogen or hydrogen, and ~2) as the organoaluminum compounds, ~2)-1 an aluminoxane ~ynthesized from a trialkylaluminum and water and ~2)-2 a compound of the following formula R9AlX3-n wherein R9 is Cl-C10 alkyl, cycloalkyl or aryl, X i~ halogen, and n i~ a number of 1 to 3.

~3(~SZ~Z

This Laid-Open Patent Publication gives a working example in which ethylene is polymerized in a system comprising 3 millimoles of the aluminoxane, 3 millimoles of triethyl-aluminum and 0.003 mill$mole of bis~cyclopentadienyl)-zirconium chloride in 400 ml of toluene as a polymeriza-tion medium.
Japanese Laid-Open Patent Publication No.
130604/1985 discloses a process for producing a poly-olefin by polymerizing an olefin using a catalyst com-posed of, as main components, ~1) a transition metal compound of the follow-ing formula (Cp) 2MRlORll wherein Cp is cyclopentadienyl, M i8 Ti, Zr or Hf, and each of R10 and Rll is H, halogen, Cl-C6 alkyl or cyclopentadienyl, (2) an aluminoxane obtained by reacting a dialkyl monohalide of the formula AlR122X

wherein R12 is methyl or ethyl, and Xl i8 halogen, with water, and ~3) an organoaluminum compound represented by the following formula AlRm3X23_m wherein R13 is Cl-C10 alkyl or cycloalkyl, x2 is halogen, and m is a number of 1 to 3.
This Laid-Open Patent Publication gives examples of the amounts of the aluminoxane used per 400 ml of toluene as a polymerization medium, 4.5 millimoles (Examples 1-4 13(:~S282 and 8), 3.6 millimoles ~Example 5), 3.25 millimoles ~Example 6), 10.0 millimoles ~Example 7) and 9.0 milli-moles ~Example 9).
It is an object of this invention to provide a process for producing an alpha-olefin polymer having a narrow molecular weight distribution and a copolymer of alpha-olefins having a narrow molecular weight distribu-tion and a narrow composition distribution when appli~d to the copolymerization of at least two olefins, es-pecially a high-molecular-weight ethylene/alpha-olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution, with excellent polymerization activity using a small amount of an aluminoxane.
Another object of this invention relates to a process for producing an olefin polymer having excellent powder properties and a narrow molecular weight dis-tribution, and an olefin copolymer having a narrow mol-ecular weight distribution and a narrow composition distribution when applied to the copolymerization of at ; least two olefins, especially an ethylene polymer or an ; ethylene/alpha-olefin copolymer having excellent powder propertie~ and a narrow molecular weight di~tribution and/or a narrow composition distribution.
DI~CL08UR$ OP ~BE I m ~TION
According to this invention, these objects and advantages of this invention are firstly achieved by a proce~s for polymerizing olefins, which comprises poly-merizing or copolymerizing olefins in the presence of a cataly~t composed of ~A) a solid catalyst component comp4sed of a compound of a transition motal of Group IVB of the periodic table supported on an inorganic carrier, ~B) an aluminoxane, and ~C) an organoalu~inum compound having a hydro-carbon group other than n-alkyl groups.

,:.. .

13~S282 g The catalyst in accoedance with this invention is formed of the solid catalyst component ~A), the aluminoxane ~B) and the organoaluminum compound ~C) having a hydrocarbon group other than n-alkyl geoups.
The catalyst component ~A) is a solid catalyst component composed of a carrier and a compound of a transition metal of Group IVB of the periodic table supported on it.
The transition metal of Group IVB of the periodic table in the catalyst component ~A) is prefer-ably selected from the group consisting of titanium,zirconium and hafnium. Titanium and zirconium are more preferred, and zirconium i$ especially preferred.
The compound of a transition metal of Group IVB
of the periodic table in the catalyst component (A) preferably has a group with a conjugated ~-electron as a ligand.
Examples of the transition metal compound having a group with a conjugated ~-electron as a ligand aee compounds represented by the following formula ~I) RkR02R3RnMe ........... ~I) wherein Rl repre~ents a cycloalkadienyl group, R2, R3 and R4 are identical or different and each repre~ents a cycloalkadienyl group, an aryl group, an alkyl group, a cycloalkyl group, an aralkyl group, a halogen atom, a hydrog-n atom, or a group of the formula -ORa, -SRb or -NRC2 in which each of Ra, * and Rc represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic 8ilyl group, Me represent~ zirconiu~, titanium or hafnium, k is 1, 2, 3 or 4, 0 , m and n are each 0, 1, 2 or 3, and k~Q~m~n-4.
Example~ of the cycloalkadienyl group re-presented by Rl are a cyclopentadienyl group, a methyl-cyclopentadienyl group, an ethylcyclopentadienyl group, a .-~
: . , 130S2~Z

dimethylcyclopentadienyl group, an indenyl group and a tetrahydroindenyl group. Examples of the cycloalkadienyl group represented by R2, R3 and R4 may be the same as above.
The aryl group represented by R2, R3 and R4 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, bexyl, octyl, 2-ethyl-hexyl, 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 -ORa, -SRb and -NRC2 where Ra, Rb and Rc are alkyl, cycloalkyl, aryl and aralkyl will be clear from the above specific examples of the8e groups.
Examples of the oeganic silyl group for Ra, Rb and Rc are trimethyl~ilyl, triethyl~ilyl, phenyldimethyl-~ilyl, diphenylmethyl~ilyl and triphenyl~ilyl groups.
Example~ of zirconium compounds corresponding to formula ~I) in which Me i8 zirconium are li8ted below.
bis~Cyclopentadienyl)zirconium monochloride monohydride, bis~cyclopentadienyl)zirconium monobromide monohydride, bis~cyclopentadienyl)methylzirconium hydride, bis~cyclopentadienyl)ethylzirconium hydride, bi6~cyclopentsdienyl)cyclohexylzirconium ~ hydride, ; bi~cyclopentadienyl)phenylzirconium hydride, bis~cyclopentadienyl)benzylzirconium hydride, bis~cyclopentadienyl)neopentylzirconium hydride, - . . . .

13~528Z

bis~methylcyclopentadienyl)zirconium mono-chloride monohydride, bis(indenyl)zirconium monochloride monohydride, bis(cyclopentadienyl)zirconium dichloride, S bis(cyclopentadienyl)zirconium dibromide, bis(cyclopentadienyl)methylzirconium mono-chloride, bis(cyclopentadienyl)ethylzirconium mono-chloride, bis(cyclopentadienyl)cyclohexylzirconium mono-chloride, bis(cyclopentadienyl)phenylzirconium mono-chloride, bis(cyclopentadienyl)benzylzirconium mono-chloride, bis(methylcyclopentadienyl)zirconium di-chloride, bi~(indenyl)zirconium dichloride, bis~indenyl)zirconium dibromide, bis~cyclopentadienyl)diphenylzirconium, bis(cyclopentadienyl)dibenzylzirconium, bis(cyclopentadienyl)methoxyzirconium chloride, bi~(cyclopentadienyl)ethoxyzirconium chloride, bis(cyclopentadienyl)butoxyzirconium chloride, bis~cyclopenadienyl)2-ethylhexoxyzirconium chlorido, bi~(cyclopentadienyl)methylzirconium ethoxide, bi~cyclopentadienyl)methylzirconium butoxide, bis(cyclopentadienyl)ethylzirconium ethoxide, bis(cyclopentadienyl)phenylzirconium ethoxide, bi~(cyclopentadienyl)benzylzirconium ethoxide, bis~methylcyclopentadienyl)ethoxyzirconium chloride, bis(indenyl)ethoxyzirconium chloride, ; 35 bi~cyclopentadienyl)ethoxyzirconium, bis~cyclopentadienyl)butoxyzirconium, . . . . . . ~

-13~SZ8Z

bis(cyclopentadienyl)2-ethylhexoxyzirconium, bis~cyclopentadienyl)phenoxyzirconium chloride, bis~cyclopentadienyl)cyclohexoxyzirconium chloride, bis(cyclopentadienyl)phenylmethoxyzirconium chloride, bis(cyclopentadienyl)methylzirconium phenyl-methoxide, bis~cyclopentadienyl)trimethylsiloxyzirconium 10 chloeide, bis~cyclopentadienyl)triphenylsiloxyzirconium chloride, bis~cyclopentadienyl)thiophenylzirconium chloride, bis~cyclopentadienyl)thioethylzirconium chloride, bis(cyclopentadienyl)bis~dimethylamide)-zirconium, bis~cyclopentadienyl)diethylamidezirconium 20 chloride, ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis~4,5,6,7-tetrahydro-1-indenyl)-ethoxyzieconium chloride, ethylenebistindenyl)dimethylzirconium, ethylenebi~(indenyl)diethylzieconium, ethylenebi~indenyl)dibenzylzlrconium, ethylenebi~(indenyl)methylzirconium mono-bromide, ethylenebistindenyl)ethylzirconium mono-chloride~
ethylenebis~indenyl)benzylzirconium mono-: chloride, ethylenebi~indenyl)methylzirconium mono-chloride, ethylenebis~indenyl)zirconium dichloride, ethylenebi~(indenyl)zirconium dibromide, , .:
., ...., ~ .

1;3~ 2 ethylenebis~4,5,6,7-tetrahydro-1-indenyl)di-methylzirconium, 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 di-Chloride, ethylenebis~5-methyl-1-indenyl)zirconium di-chloride, ethylenebis~6-methyl-1-indenyl)zirconium di-chloride, ethylenebis~7-methyl-1-indenyl)zirconium di-chloride, ethylenebis~5-methoxy-1-indenyl)zirconium dichloride, ethylenebis~2,3-dimethyl-1-indenyl)zirconium 0 dichloride, ethylenebisl4,7-dimethyl-1-indenyl)zirconium dichloride, ethylenebis~4,7-dimethoxy-1-indenyl)zirconlum dichloride, 2S ethylenebis~indenyl)zirconium dimethoxide, ethylenebis~indenyl)zirconium diethoxide, ethylenebi~indenyl)methoxyzirconium chloeide, ethylenebis~indenyl)ethoxyzirconium chloride, ethylenebistindenyl)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)- 5 methoxyzirconium chloride, ethylenebis~4,5,6,7-tetrahydro-1-indenyl)-ethoxyzirconium chloride, and 13~ 5 ~ ~ ~

ethylenebis~4,5,6,7-tetrahydro-1-indenyl)methyl-zirconium 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, bislcyclopentadienyl)methyltitanium ethoxide, lS 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)-5 titanium dlchlor~de.
Example~ of hafnium compounds corresponding to formula ~I) in which Me is hafnium are listed below.
bis~Cyclopentadienyl)hafnium monochloride monohydride, bi~cyclopentadienyl)ethylhafnium hydride, bis~cyclopentadionyl)phenylhafnium chloride, bi6~cyclopentadlenyl)hafnium dichloride, bis~cyclopentadienyl)dibenzylhafnium, bis~cyclopentadienyl)ethoxyhafnium chloride, bis~cyclopentadienyl)butoxyhafnium chloride, bis~cyclopentadienyl)~ethylhafnium ethoxide, 13~3S28Z

bis(cyclopentadienyl)phenoxyhafnium chloride, bistcyclopentadienyl)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 transi-tion metal compound may be treated with an organic metal compound or a halogen-containing ~ilicon compound prior to deposition. 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 organo-aluminum compound is preferred.
Examples of the organoaluminum compound includetrialkylaluminums such as trimethylaluminum, triethyl-aluminum and tributylaluminum; alkenylaluminums such as isoprenylaluminum; dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide and dibutyl aluminum butoxide~ alkyl aluminum sesqui-alkoxides such as methyl aluminum sesquimethoxide and ethyl aluminum sesquiethoxides partially alkoxylated alkylaluminums having an average composition of the formula Rl 5Al~OR2)o 5~ dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride and dimethyl aluminum bromide~ alkyl aluminum sesquihalides ~uch as methyl aluminum sesquichloride and ethyl aluminum ~esquichloride; partially halogenated alkylaluminums, for example alkyl aluminum dihalides such as methyl aluminum dichloride and ethyl aluminum dichloride.
$he 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.

~. :

.
.
.
:

13~528Z

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.
An organoaluminum compound is preferred as the organic metal compound (C).
As the halogen-containing silicon compound as a treating agent, compounds of the following formula (IV~
SiYdRe~OR )4-d-e (IV) wherein Y is a chlorine or bromine atom, R5 and lS R6, 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 atom, d is a number of 1 to 4 and e is a number of 0 to 4, provided that the sum of d and _ is a number of 1 to 4, ~re pref-r~bly used.
Examples of such compounds include ~ilicon tetrachlorlde, 8ilicon tetrabromide, silicon teichloride, methyl8ilicon trichloride, ethyl~ilicon trichloride, Z5 propylsilicon trichloride, phenyl8ilicon trichloride, cyclohexyl8ilicon trichloride, silicon tribromidé, ethyl-silicon tribromide, dimethyl~ilicon dichloride, methyl-silicon dichloride, phenylsilicon dichloride, methoxy-silicon trlchlorlde, ethoxysilicon trichloride, propoxy-8ilicon trichlorlde, phenoxysilicon trichloride, ethoxy-silicon tribromlde, methoxysillcon dlchlorlde, di-methoxysilicon dichloride, and silanol trichloride.
The~e compounds may be used singly or ln combination.
A~ong them, silicon tetrachloride, silicon trichloeide ' .

.~ .
:.
, ,. ..

', ' ',.

.

~3~S ~Z

and methylsilicon trichloride are preferred.
The mixing ratio of the organometallic compound to the inorganic carrier in the above treatment, as the ratio of the amount of the organometallic compound in millimoles/the amount of the carrier in grams, is from o.s to 50, preferably from 1 to 30, more preferably from 1.5 to 20.
The treatment of the inorganic carrier with the organometallic compound in the preparation of the cata-lyst component ~A) can be carried out by dispersing thecarrier in an inert solvent, adding at least one of the above-described organometallic compounds, and treating the carrier at a temperature of 0 to 120 C, preferably 10 to 100 C, more preferably 20 to 90 C, for a period Of 10 minutes to 10 hours, preferably 20 minutes to 5 houcg, more preferably 30 minutes to 3 hours, under reduced or elevated pressure.
Examples of the inert solvent are aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane and i~ooctane and alicyclic hydrocarbons such as cyclohexane.
In the above-treatment, the mixing ratio of the inorganic carrier to the halogen-containing silicon compound, i~ ~uch that the halogen-containing silicon 2S compound 1~ used in an amount of 0.001 to 10 moles, preferably 0.01 to 50 moles, more preferably 0.05 to 1 mole, per gram of the carrier compound. Preferably, after the above treatment, the liquid portion containing the exco~s of the halogen-containing silane compound, etc. is removed from the reaction mixture by such a method a~ filtration or decantation.
The treat~ent of the inorganic carrier with the halogen-containing silicon compound in preparing the cataly~t componont ~A) may be carried out at a tempera-ture of -50 to 200 C, preferably 0 to 100 C, more preferably 20 to 70 &, for a period of 10 minutes to .

~ . , .
.
- , .
' , ' ~,' . .'' , : ', . ' . .

~3~S~2 10 hours, preferably 20 minutes to S hours, under atmos-pheric, reduced or elevated pressure.
An inert solvent may be used in the above treatment. Examples of the inert solvent 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.
In th~ deposition of the Group IVB transition metal compound on the inorganic carrier in the prepara-tion of the catalyst component ~A), an inert solvent needs not to be used when the transition metal compound is a liquid substance. If the transition metal compound lS is a solid substance at ordinary temperature, it is preferred generally to use an inert solvent capable of dis~olving the transition metal compound.
The inert solvent used at this time may be the same inert solvent as that used in treating the inorganic carrier with the halogen-containing silicon compound.
Aromatic bydrocarbons such as benzene and toluene and halogenated hydrocarbons ~uch as chlorobenzene are es-pecially preferred.
The amount of the transition metal compound u~ed in the above ~upporting reaction i~ preferably 0.001 to 500 millimoles, more preferably 0.01 to 100 milli-moles, especially preferably 0.1 to 50 millimoles, per gram of the inorganic carrier.
The amount of the inert solvent used in the above supporting reaction is preferably 0.5 to 1000 ml, more preferably 1 to 100 ml, especially preferably 2 to 50 ml, per gram of the inorganic carrier treated with the halogen-containing silane compound.
The above ~upporting reaction can be carried out by contacting and mixlng the inorganic ca~rier and the tran~ition metal compound at a temperature of 0 to . ~ .

13q. ~52~'~

200 C, preferably 0 to 100 C, especially preferably 20 to 80 C, for a period of 1 minute to 10 hours, 5 minutes to 5 hours, 10 minutes to 3 hours.
After the supporting reaction by the above method, it is preferred to remove the liquid portion of the reaction mixture by such a method as filtration or decantation and wash the residue several times with an inert solvent.
In the catalyst of this invention, the solid catalyst component ~A) is obtained by supporting the compound of a transition metal of Group IVB of the periodic table on the carrier.
The inorganic carrier is advantageously a granular or fine particulate solid having a particle diameter of, for example, 10 to 300 micrometers, pre-ferably 20 to 200 micrometers. Preferably, it is a porous oxide. Specific examples include SiO2, A12O3, MgO, ZrO2, TiO2, 82O3, CaO, ZnO, BaO, ThO2 and mixtures of these such as SiO2-MgO, SiO2-A12O3, SiO2-TiO2, SiO2-V2O5~ SiO2-Cr2O3 and SiO2-TiO2-MgO. Carriers con-taining at least one component selected from the group consi~t~ng of SiO2 and A12O3 as a main component are preferred.
The inorganic oxides may contain small amounts of carbonates, sulfates, nitrates or oxide components such as Na2CO3, K2CO3~ CaCO3~ MgC03~ Na2SO4~ 2 4 3 BaSO4, KNO3, Mg~NO3)2, Al~NO3)3, Na2O, R2O and Li2O.
The porous inoeganic carrier have diferent properties depending upon its type and the method of production. Carriers preferably used in this invention have a specific surface area of 50 to 1000 m2/g, pre-ferably 100 to 700 m2/g and a pore volume of 0.3 to 2.5 cm2/g. The above carrier is used after it is calcined at a temperature of usually 150 to 1000 C, preferably 200 to 800 C.
In the catalyst component ~A) in this ~'' ~' ,' . -.
.

13QSZ~

invention, the compound of the transition metal of Group IVB of the periodic table is supported in an amount of 3 x 10 3 to 3 milligram-atoms, preferably 5 x 10 3 to 2 milligram-atoms, more preferably 1 x 10 2 to 1 milligram-atom, as the transition metal atom, per gram of theinorganic carrier treated with the organometallic com-pound.
The catalyst component (A) contains the tran-sition metal compound in an amount of usually 0.005 millimole to 5 millimoles, preferably 0.01 millimole to 1 millimole, especially preferably 0.03 millimole to 0.3 millimole, per gram of the inorganic carrier treated with the halogen-containing silicon compound.
The catalyst component (B) is an aluminoxane.
The aluminoxane used as the catalyst component is, for example, an organoaluminum compound of the following formula (II) R R X

wherein R is a hydrocarbon group, X i8 a halogen atom, and _ and _, lndependently from each other, represent a number of 0 to 80 with the proviso that a and b are not simultaneously zero (in this formula, the degree of polymeri-zation i8 a+b~2), or the following formula (III) 0-Al ~ 0-Al ~ (III) R X

wherein R, X, a and b are as defined here-inabove with regard to formula (II) ~in this ... . .

``` 131~Z~Z

formula, the degree of polymerization is a+b).
In formulae ~II) and (III), R represents a hydrocarbon group such as an alkyl, cycloalkyl, aryl or aralkyl group. Preferred as the alkyl group are lower alkyl groups such as a methyl, ethyl, propyl or butyl group. Cyclopentyl and cyclohexyl groups are preferred examples of the cycloalkyl group. Preferred aryl groups are, for example, phenyl and tolyl groups. Preferably, the aralkyl group is, for example, a benzyl or neophile group. Of these, the alkyl groups are especially pre-ferred.
x is a halogen atom such as fluorine, chloeine, bromine and iodine. Chlorine i8 especially preferred.
a and b, independently from each other, are numberg of 0 to 80, with the proviso that a and b are not simultaneously zero.
When b is 0, formula ~II) may be written as the following formula (II)-l ~Al-0~0-Al ~ Al~ ~II~-l R R R

wherein R and a are a~ defined above, and formula ~III) may be written as the following formula ~III)-l ~ ~III)-l wherein R and a are as defined above.
In formula ~II)-l, a i~ preferably 2 to 50, more preferably 4 to 30. Furthermore, in formula ~III)-l, _ is preferably 4 to 52, more preferably 6 to 32.
a i8 preferably 0 to 40, more preferably 3 to 30, and b i8 preferably 1 to 40, more preferably 3 to 30.
The value of a~b i8 preferably 4 to 50, more preferably 8 to 30.

", , ' " ' - 13C~2~2 In formulae (II) and ~III), the two units -0-Al- and -0-Al- may be bonded in blocks or at randon~.
R R
When a is 0 in formulae (II) and ~III), it is desirable to use an organoaluminum compound of the fol-lowing formula (~) AlRfZ3_f (V) wherein R7 is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, Z is a halogen atom, and f is a number of 1 to 3, together with the halogenated aluminoxane. Examples of such an organoaluminum compound include trimethyl-aluminum, triethylaluminum, tributylaluminum trihexyl-aluminum, diethylaluminum chloride and ethylaluminum sesquichloride.
Preferably, the halogenated aluminoxane and the organoaluminum compound are used at this time such that the amount of the organoaluminum compound is 0.1 to 10 moles, preferably 0.3 to 3.0 moles, especially preferably 0.5 to 2.0 mole, per mole of Al atom in the halogenated aluminoxane.
The aluminoxane or the halogenated aluminoxane desccibed above can be produced, for example, by the following methods.
~1) A method which comprises suspending a compound containing water of adsoeption oe a salt con-taining water of crystallization, such as magnesium chloeide hydeate, nickel sulfate hydeate or cerous chloeide hydeate in a medium such as benzene, toluene, ethyl ether or teteahydeofuran, and reacting it with a teialkylaluminum and/or a dialkylaluminum monohalide.
(2) A method which compeises reacting a trialkylaluminum and/or a dialkylaluminum monohalide ~3 ~

directly with water in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
It is preferred to adopt the method (1).
Incidentally, the aluminoxane may contain a small amount of an organometallic compound.
Then catalyst component (C) is an organo-aluminum compound having a hydrocarbon group other than n-alkyl groups. Such a hydrocarbon group may be, for example, an alkyl group having a branched chain such as an iso-alkyl group, a cycloalkyl group and an aryl group.
Examples of the above organoaluminum compound a~e tri-alkylaluminums such as triisopropylaluminum, triiso-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum; triarylaluminums such as tri-phenylaluminum and tritolylaluminum; dialkylaluminum hydrides such as diisobutylaluminum hydride; and alkyl-aluminum alkoxides such as i~obutylaluminum methoxide, isobutylaluminum ethoxide and isobutylaluminum iso-propoxide. Of these organoaluminum compounds, organo-aluminum compound~ having a branched alkyl group are preferred, and the trialkylaluminums are especially preferred. Furthermore, isoprenylaluminums having the general formula ~i-C4Cg)xAly~C5Hlo)z wherein x, y and z aee po~itivc numbers and z>2x are also preferably used.
There can al~o be used compounds which will yield the above organoaluminum compounds in the polymerization ~y~tem, for example a combination of an aluminum halide and an alkyllithium or a combination of an aluminum halide and an alkylmagnesium, may also be used.
In the proces~ of thi~ invention, the poly-~;35 merization of olefins may be carried out by a liquid-phace polymerization method ~e.g., slurry polymerization ~, :

: ' .

3~!S Z ~Z

or solution polymerization) or a gas-phase polymerization method. Prior to the olefin polymerization, prepolymeri-zation may be carried out using a small amount of an olefin.
The prepolymerization is carried out (1) in the absence of solvent, or 12) in an inert hydrocarbon medium. Of these, the method (1) is preferred. Desir-ably, at this time, the catalyst components lA~ and (B) are mixed in an inert hydrocarbon medium, and the solvent is removed by using an evaporator at room temperature or an elevated temperature under atmospheric or reduced pressure. The mole ratio of the transition metal atom in catalyst component tA) to the aluminum atom in catalyst component lB) in the prepolymerization treatment (Al/the transition metal atom) i8 from 20 to 5000, preferably from 25 to 2000, more preferably from 30 to 1000. The prepolymerization temperature is from -20 C to 70 C, preferably -10 C to 60 C, more preferably 0 C to so C
The treatment may be carried out either batch-wise or continuously under reduced, atmospheric or elevated pressure. The prepolymerization may be carried out in the pre~ence of a molecular weight controlling agent such a~ hydrogen, but it i8 preferred to limit its amount at least to one sufficient to produce a prepolymer having an intrinsic visco~ity 1~1, measured in decalin at 135 C, of at lea~t 0.2 dl/g, preferably 0.5 to 20 dl/g.
The amount of the transition metal compound ~A) at the time of performing the process of this invention by the slurry polymerization technique or the gas-phase polymerization technique i~, in terms of the concentra-tion of the tran~ition metal atom in the polymerization reaction system, 10 8 to 10 2 gram-atom/liter, preferably 10-7 to 10-3 gram-atom/liter.
3s In the process of this invention, the amount of the aluminoxane (B), calculated as the aluminum atom in -` 13(~52&2 the reaction system, is not more than 3 milligram-atoms/
liter, preferably 0.1 to 2.5 milligram-atoms/liter, es-pecially preferably 0.2 to 2 milligram-atoms/liter. The proportion of the aluminum atoms of the aluminoxane component ~B) based on the total amount of the aluminum atoms in the aluminoxane component ~B) and the organo-aluminum compound component ~C) is usually 20 to 80 %, preferably 25 to 75 mole %, and especially preferably 30 to 70 %. Corresponding to this amount, the proportion of the aluminum atom in the organoaluminum compound com-ponent ~C) is usually 20 to 80 %, preferably 25 to 75 %, e~pecially preferably 30 to 70 %. In the process of this invention, the ratio of the total amount of aluminum atoms ln the aluminoxane component ~B) and the organo-aluminum compound component ~C) to the transition metalatom in the reaction system is usually from 20 to 10000, preferably from 50 to S000, especially preferably from 100 to 2000.
According to the above catalyst in accordance with this invention, olefins can be polymerized or co-polymerized advantageously.
~ Investigations of the present inventors have ; ~hown that when a compound of a transition metal of group IV of the periodic table and containing a ligand having a 2S con~ugatod ~eloctron and a ligand containing hetero atom capable of being bonded to the transition metal and ~-lected from the group consisting of oxygen, sulfur, nitrogen and pho~phorus is u~ed as the transition metal compound in the catalyst ~ystem, the re~ulting compound show~ the same excellent activity as the catalyst system composed of the components ~A), (B) and ~C) even if it is ; not ~upported on the inorganic carrier.
Accordingly, the pre~ent invention ~econdly provide~ a proce~ for producing olefin~, which comprises polymerizing or copolymerizing the olefins in the pre-sence of a catalyst compo~ed of , . .
'.:
" .

13~a5~2 (A)' a compound of a transition metal of Group IV of the periodic table containing a ligand having a conjugated ~-electron and a ligand containing a hetero atom capable of being bonded to the transition metal and selected from the group consisting of oxygen, ~ulfur, nitrogen and phosphorus, (B) an aluminoxane, and (c) an organoaluminum compound having a hydro-carbon group other than n-alkyl groups.
For example, the transition metal compound (A)' may preferably be a compound of the following formula ~I)' RllRl2Rl3Rl4Me wherein Rll i8 cycloalkadienyl, R12 is selected from the class consisting of -ORa, -SRb, -NRC2 and -PRd2, R13 and R14, independently from each other, represent cycloalkadienyl, aryl, aralkyl, halogen or hydrogen, Ra, Rb and Rc repre~ent alkyl, cycloalkyl, aryl, aralkyl or organic ~ilyl, Me is zirconium, titanium, or hafnium, k and R are 1, 2 or 3, m and n are 0, 1 or 2 and k+Q+m+n~4, Example~ of the compounds of formula (I)' include zirconium compound~ ~uch as bi~(cyclopentadienyl)methoxyzirconium chloride, bi~(cyclopentadienyl)ethoxyzirconium chloride, bi~(cyclopentadienyl)butoxyzirconium chloride, bi~(cyclopentadienyl)2-ethylhexoxyzirconium chloride, bi~(cyclopentadienyl)methylzirconium ethoxide, bi~(cyclopentadienyl)methylzirconium butoxide, bi~(cyclopentadienyl)ethylzirconium ethoxide, bi~cyclopentadienyl)phenylzirconium ethoxide, bi~cyclopentadienyl)benzylzirconium ethoxide, bi~methylcyclopentadienyl)ethoxyzirconium chloride, ... .

-- 13~52&2 bis~indenyl)ethoxyzirconium chloride, bis~cyclopentadienyl)ethoxyzirconium, bis~cyclopentadienyl)butoxyzirconium, bis~cyclopentadienyl)2-ethylhexoxyzirconium, bis(cyclopentadienyl)phenoxyzirconium chioride, bis(cyclopentadienyl)cyclohexoxyzirconium chloride, bis(cyclopentadienyl)phenylmethoxyzirconium chloride, bis(cyclopentadienyl)methylzirconium phenyl-methoxide, bis(cyclopentadienyl)trimethylsiloxyzirconium chloride, bis~cyclopentadienyl)triphenylsiloxyzirconium 15 chloride~
bis~cyclopentadienyl)thiophenylzirconium chloride, bis~cyclopentadienyl)bi~(dimethylamide)-zirconium, 20 bis~cyclopentadienyl)diethylamidezirconium chlolride, ethylenebis~indenyl)ethoxyzirconium chloride, and ethylenebis~4,5,6,7-tetrahydro-1-indenyl)-ethoxyzirconium chloridet titanlum compounds such as bis~cyclopentadienyl)ethoxytitanium chloride, bis~cyclopentadienyl)butoxytitanium chloride, bis~cyclopentadienyl)methyltitanium ethoxide, bis~cyclopentadienyl)phenoxytitanium chloride, bis~cyclopentadienyl)trimethylsiloxytitanium chloride, bis~cyclopentadienyl)thiophenyltitanium chloride, ~ : 35 bis~cyclopentadienyl)bis~dimethylamide)titanium I~ and i;
I

~3C~2 bis(cyclopentadienyl)ethoxytitanium; and hafnium compounds such as bis~cyclopentadienyl)ethoxyhafnium chloride, bis~cyclopentadienyl)butoxyhafnium chloride, bis(cyclopentadienyl)methylbafnium ethoxide, bis~cyclopentadienyl)phenoxyhafni~m chloride, bis~cyclopentadienyl)thiophenylhafnium chloride, and bis~cyclopentadienyl)bis~diethylamide)hafnium.
It should be understood that in the process of this invention using the above catalyst system composed of the catalyst components (A)', (B) and ~C), the pre-ferred concentrations and proportions of these catalyst components tA)', (B) and ~C) are the same as described hereinabove with the aforesaid catalyst system.
Investigations of the present inventors have also shown that by limiting the amount of the aluminoxane used to not more than 3 milligram-atoms/liter as Al atom in the catalyst system composed of the components ~A), ~B) and ~C) and the catalyst system composed of ~A)', ~B) and ~C), excellent catalytic activity can be exhibited.
On the basis of this fact, it has been found that when the amount of the aluminoxane used is limited to not more than 3 milligram-atoms/liter as Al atom in the reaction system, the use of any of the compounds of formula ~I) as the group IVB transition metal compounds without being supported on the inorgnaic carrier can exhibit the same excellent activity.
Accordingly, the present invention thirdly provides a process for polymerizing or copolymerizing olefins in the pre~ence of a catalyst composed of ~ A)~ a compound of a transition metal of Group IVB of the periodic table, ~B) an aluminoxane in a concentration of not more than 3 milligram~/liter as aluminum atom in the reaction sy~tem, and .S~Z

(C) an organoaluminum compounds having a hydrocarbon group other than n-alkyl groups.
The same compounds as represented by formula ~I) can be used as the transition metal compound (A)~.
The alumionoxane ~B) and the organoaluminum compound (C) may be the same as de~cribed above.
In the process of this invention, the catalyst components (A)~, ~B) and (C) may be separately fed into the reaction system. Or it is possible to add a pre-mixture of any two of the above compounds and the re-maining one catalyst component sepaeately into the re-action system. Alternatively, all the catalyst com-ponents may be pre-mixed and then fed into the reaction system. When two catalyst components aee to be mixed in advance, the catalyst components to be mixed are pre-ferably the catalyst components (A) and ~B).
In the premixing of the catalyst components ~A) and ~B), the concentration of the transition metal atom is ùsually 2.5 x 10-4 to 1.5 x 10~1 gram-atom/liter, preferably 5.0 x 10 4 to 1.0 x 10 1 gram-atom/liter. The concentration of the aluminoxane i8 usually 0.05 to 5 gram-atoms~liter, preferably 0.1 to 3 gram-atoms/liter, a8 Al atom. The temperature in the premixing is usually -50 C to 100 C, and the mixing time is usually 0.1 minute to 50 hours.
It should be understood that the preferred concentrations and mixing ratios of the components ~A)~, - ~B) and ~C) in the polymerization system are the same as in the above catalyst system.
All the catalysts de6cribed above can be used advantageously in the homopolymerization or copoly-merization of olefins. They are especially effective for the production of an ethylene polymer and ethylene/alpha-olefin copolymers. Examples of the olefin~ that can be utilized are ethylene and alpha-olefins having 3 to 20 carbon atoms, such as propylene, l-butene, l-hexene, .
_. .... .

~3r~

4-methyl-1-pentene, l-octene, l-decene, l-dodecene, l-tetradecene, l-hexadecene, l-octadecene and l-eicocene.
The polymerization of olefins by the process of this invention is usually carried out in a gas-phase or in a liquid phase, for example in slurry. In the slurry polymerization, an inert hydrocarbon may be used as a solvent. It is also possible to use an olefin itself as the solvent.
Specific examples of the hydrocarbon solvent are 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 hydrocarbon media, the aliphatic hydro-carbons, alicyclic hydrocarbons and petroleum fractions are preferred.
When slurry polymerization is carried out in the process of this invention, the polymerization tem-perature iB usually -50 to 120 C, preferably 0 to 100 C.
When slurry polymerization or gas-phase poly-merization is carried out by the process of this invention, the proportion of the transition metal compound is usually 10 8 to 10 2 gram-atom/liter, pre-ferably 10 7 to 10 3 gram-atom/liter as the transition metal atom in the polymerization ~ystem.
In the present polymerization reaction, the aluminoxane may, or may not, be used additionally. To obtain a polymer having excellent powder properties, it i9 preferred not to use the aluminoxane additionally.
The polymerization pressure is usually atmos-pheric pressure to 100 kg/cm2, preferably 2 to 50 kg/cm2.
The polymerization may be carried out batchwi8e, semi-continuously or continuously.

, . . .

13~t5~8 The polymerization may be carried out in two or more stages having different reaction conditions.
When the slurry polymerization method or the gas-phase polymerization method is used to polymerize olefins, particularly polymerie ethylene or ethylene with an alpha-olefin in this invention, there is no polymer adhesion to the reactor and the resulting polymer has excellent powder properties and a narrow molecular weight distribution. When the invention is applied to the copolymerization of at least two olefins, an olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution can be obtained.
lEXAMPLES~
~he prccess of this invention will now be specifically illustrated by the following examples. The Mw/Mn value was measured by the following procedure in accordance with Takeuchi, "Gel Permeation Chromatography~, published by Maruzen Co., Ltd.
(1) By using standard polystyrene of a known molecular weight ~monodisperse polystyrene produced by Toyo Soda Co., Ltd.), the molecular weight M and its GPC
~gel permeation chromatograph) count are measured. A
calibration curve of the molecular weight M versus EV
~elution volume) is prepared. The concentration at this time is adjusted to 0.02 % by weight.
~ 2) The GPC chromatogram of the sample i8 taken by GPC, and the number average molecular weight Mn and the weight average molecular weight Mw of the sample are calculated as polyethylene by the procedure ~1) above, and the Mw/Mn value is determined. The sample preparation conditions and the GPC measurement conditions at this time are as follows:-Sample preparation:
~a) Take the sample together with o-dichloro-benzene ~olvent in an Erlenmeyer flask 80 that its con-centration i8 0.1 % by weight.

~, . . .

-- 13~S28Z

~b) Heat the flask to 140 C and stir the contents for about 30 minutes to dissolve the sample.
(c) Subject the filtrate from it to GPC.
GPC measurement conditions:
(a) Device: l50C-ALC/GPC made by Waters Co.
(b) Column: GMH type made by Toyo Soda Co., Ltd.
Ic) Amount of the ~ample: 400 microliters ~ d) Temperature: 140 &
10 (e) Flow rate: 1 ml/min.
The amount of an n-decane-soluble poetion in the copolymer (as the amount of the soluble portion is smaller, the narrow i8 the composition distribution) was measured by adding about 3 9 of the copolymer to 450 ml 15 f n-decane, dissolving the copolymer at 145 C, cooling the solution to 23 &, removing the n-decane-insoluble portion by filtration, and recovering the n-decane-soluble portion from the filtrate.
The B value of the ethylenic copolymer of this 20 invention is defined a~ follows:
POE
2Po-PE
, wherein PE represents the molar fraction of the ethylene component in the copolymer, P0 represents the molar fraction of the alpha-olefin component, and POE represents the molar fraction of the alpha-olefin/ethylene sequence in the total dyad sequence.
The B value i~ an index showing the state of distribution of the individual ~onomer component~ in the 30 copolymer and i8 calculated by determining Pe~ P0 and POE
in the above definition in accordance with the papers of G. J. Ray IMacromolecule8, 10, 773 ~1977)1, J. C. Randall IMacromolecule~, 15, 353 ~1982), J. Polymee Science, Polymer Physics Ed., 11, 275 ~1973)1, and R. Kimura :

.
.

. ' , ~
--- 13~5282 tPolymer, 25, 441 ~1984)1. As the B value is larger, the amount of block-like sequences is smaller and the dis-tribution of ethylene and the alpha-olefin i8 more uniform. Thus, the copolymer has a narrower composition distribution.
The composition distribution B value is deter-mined as follows: About 200 mg of the copolymer is uniformly dissolved in 1 ml of hexachlorobutadiene in a sample tube having a diameter of 10 mm, and a 13C-NMR
spectrum of the sample is taken usually at a temperature of 120 C under the following conditions.
Measuring frequency: 25.05 MHz Spectral width: 1500 Hz Filter width: 1500 Hz Pul~e repeating time: 4.2 sec Pulse width: 7 microseconds Number of integration~: 2000 to 5000 Prom the spectrum, PE, PO and POE are determined, and the B value i8 calculated from them.

Preparation of aluminoxane A 400 ml flask purged fully with nitrogen was charged with 37 g of A12(SO4)3.14H20 and 125 ml of toluene. The flask was cooled to 0 C, and 500 milli-moles of tr~methyl aluminum diluted with 125 ml of toluene wa8 added dropwise. The mixture was heated to 40 C, and the reaction was continued at this temperature for 10 hours. After the reaction, the reaction mixture was ~ubjected to ~olid-liquid separation by filtration.
Toluene was removed from the filtrate to give 13 g of aluminoxane a~ a white solid. It has a molecular weight, determined by freezing point deprossion in benzene, of 930. It~ m value in the catalyst component lBl was 14.
; Polymerization Toluene ~500 ml) was introduced into a l-liter glass autoclave fully purged with nitrogen, and a gaseous , .

~3(~5;~:~Z

mixture of ethylene and propylene (120 liters/hr, and 80 liters/hr, respectively) was passed through the flask and left to stand at 20 C for 10 minutes. Then, 0.5 milli-mole of triisobutyl aluminum was added. Five minutes later, 0.25 milligram-atom, as aluminum atom, of the aluminoxane and subsequently 2.5 x 10 3 millimole of bis~cyclopentadienyl)zirconium dichloride were added, and the polymerization was staeted. The gaseous mixture of ethylene and propylene was continuously fed, and poly-merized at 20 C under atmospheric pressure for 1 hour.After the polymerization, a small amount of methanol was added to stop the polymerization. The polymer solution was poured into a large excess of methanol to precipitate the polymee. The precipitated polymer was dried at 130 C under reduced pressure for 12 hour~. There was consequently obtained 19.1 9 of a polymer having an MFR
of 0.31 g/min., an ethylene content, measured by C-NMR, of 84.1 mole %, an Mw/Mn of 2.39 and a B value of 1.13.

Example 1 was repeated except that in the polymerizat$on of ~xample 1, trii~obutyl aluminum was not u~ed. Hardly any polymer was obtained.
~XAMPL~S 2-9 AND COMPARATIVE EXAMPLES 2-6 Polymerization was carried out undee the con-dition~ de w ribed in Table 1 by the same operation as in ~xample 1. The re~ult~ are ~hown in Table 2.

PolYmerization A 2-liter ~tainle~s ~teel autoclave fully purged with nitrogen was charged with 250 ml of hexane and 750 ml of 4-methyl-1-pentene, and heated to 35 C.
Then, 0.25 millimole of trii~obutyl aluminum, 0.5 milli-gram-atom, calculated a8 aluminum atom, of the alumino-xane ~yntho~ized in ~xample 1, and 1 x 10 3 millimole of 3s bi~(cyclopentadienyl)zirconium dichloride were introduced into the autoclave. Ethylene wa~ sub~equently introduced .

, ,, . . : , .
, - , . .. ~, ~

131 ~SZ82 and the polymerization was started. Ethylene was con-tinuously fed so as to maintain the total pressure at 8 kg/cm2-G; and polymerized at 45 C for 1 hour. The subsequent operation was carried out in the same way as in Example 1 to give 33.1 9 of a polymer having an MFR of 0.55 g/10 min., a density of 0.901 g/cm3, an Mw/Mn of 2.92 and a decane-soluble weight fraction at room tem-perature of 1.8 % by weight.

Polymerization was carried out under the con-ditions described in Table 3 by the same operation as in Example 10. The results are shown in Table 4.

. ~ ` .

. .

13~528Z

. .
o ~ o C

~ 1:~ ~ tt~ 5~
_ ~1 S c~l, , t ~ ~
eeee~e~e~c~
~1 ~-~' ''i'Z"

~ ~ ~ To ~o ~o To ~ ~
P~ X ~ X X X ~
,~ ~
7~ . . . . . ~*

~ 31~SZ~2 ~ .
~ ooooooooo o ooo 1 1 q' ~ ~ o ~ ~D I CO I ~ ~ ~D
o _~ ~ U~ o ~ ~ U~
r ~ ~ o ~ ~r 8 ~ #
_ ,~'~ ~ o b ~ ~ ~J U~ U~
_ ~ ~0~ 10 .~ b ~_ ~ C Ll ~- O O O O O O
~ ~ . . . . .

LL~

131~5~2 Table 2 MFR Ethylene iwv~n B value _ tg/10 mun.) ClnmoelnS) ldlJg) Example 10.31 84.1 2.39 1.13 n 20.59 83.4 1.951.13 _ n 30.20 85.2 2.321.12 _ ~ 40.30 82.3 2.281.15 _ n 50.26 80.5 2.031.19 n 6 - 61.0 1.98 _ 0.21 n 7 _ 0 2.03 _ 0.08 n 80.67 85.5 2.361.12 n 93.88 80.1 2.051.18 Calp.
Example 1 _ _ _ _ ~ 2 0.64 83.8 2.37 1.13 n 3 _ _ _ _ n 4 _ 85.4 _ 1.112.14 ~ 5 _ 85.8 _ 1.112.20 n 6 - 86.2 _ 1.102.09 * Measured in decalin at 135qC

_ ~ o o o C o 11 ~ L 5~ ~ ~

. Y
~ oo _ ~ O , ,~ u~, In ~ To To _ ~ ~
~ ~ ~ "

il ~ a ~ ~
~ ~ C

13~5Z82 Table 4 MFR Density _ n-decane-soluble (9/lO mun.) (g/cm3) portion at room temperature E:cample 10 0.55 0.901 2.92 1.8 11 0.46 0.898 2.88 2.1 n 12 0-.59 0.904 2.98 2.0 13 1.03 0.902 3.02 2.3 Exalple 7 0.82 0.910 ~.90 0.72 A l-liter continuous polymerization reactor was continuously fed with 500 ml/hr of toluene, 0.5 milligram-atom/hr, calculated as aluminum atom, o~ the aluminoxane ~ynthesized in Example 1, and 5 x 10 3 millimole/hr of bis~cyclopentadienyl)zirconium di-chloride, and simultaneously, 150 liters/hr of ethylene, 100 liters~hr of propylene and 1~2 g/hr of S-ethylidene-2-norbornene lENB) were continuously fed into the~ee-actor, and polymerized at 20 C under atmospheric pres~ure with a residence time of 1 hour and a polymer concentration of 15 g/liter. The resulting polymeriza-tion product was worked up as in Example 1 to give an ethylene/propylene/EMB copolymer having an MFR of 2.25 g/10 min., an ethylene content, measured by 13C-NMR, of 86.9 mole ~, an Mw/Mn of 2.45, and an iodine value of 11 .

Example 1 was repeated except that in the polymerization of Example 1, tr~isobutyl aluminum was not used, the amount of the aluminoxane was changed to ~ . :: , , .

13(~5~b~Z

2.5 milligram-atoms calculated as aluminum atom, and the polymerization was carried out for 30 minutes. There was obtained 22.8 g of a polymer having an MFR of 1.63 g/10 min., an ethylene content of 82.8 mole %, an Mw~Mn of 1.92 and a B value of 1.14.
EXAMPLE lS
Pre-mixing of the catalyst components IA] and lB]
To a 100 ml glass flask fully purged with nitrogen, 4.7 ml of a toluene solution ~Al 0.8S mole/
liter) of the aluminoxane synthesized in Example 1, 2.4 ml of a toluene solution ~Zr 0.01 mole/liter) of bis~cyclo-pentadienyl)zirconium dichloride and 12.9 mol of toluene were added, and stirred at 22 C for 1 hour to give a yellow transparent solution.
Polymerization A 2-liter stainless steel autoclave fully purged with nitrogen was charged with 500 ml of hexane, 500 ml of 4-methyl-1-pentene and O.S millimole of tri-isobutyl aluminum, and heated to 47 C. Thereafter, 2.5 ml of the solution prepared as above was forced into the autoclave under ethylene pressure, and the polymerization wa~ started. Ethylene was continuously fed 80 as to maintain the total pressure at 7 kg/cm2-G, and the polymerization was carried out at 50 C for 1 hour.
There was obtained 71.4 g of a polymer having an MFR of 1.08 g/10 min., a density of 0.902 g/cm3, an Mw/Mn of 2.90 and a decane-soluble portion weight fraction at room temperature of of 1.5 ~ by weight.

~Pre-mixinq of catalYst components lA] and lB]
The procedure described in Example 15 was repeated except that 4.8 ml of a toluene solution ~Zr 0.01 mole/l~ter) of bis(cyclopentadienyl)zirconium di-chloride and lO.S ml of toluene were used.
Polymerization Example lS wa~ repeated except that 1.2S ml of the olution pr-pared above was used. Tbere was obtain-d .

.

13~5Z~Z

46.1 g of a polymer having an MFR of 0.82 g/min., a density of 0.904 g/cm3, an Mw/Mn of 2.86 and a decane-soluble portion weight fraction at room temperature of 1.3 % by weight.

Pre-mixing of catalyst components lA] and lBl In Example lS, 12.0 ml of a toluene solution (Zr 0.04 mole/liter) of bis~cyclopentadienyl)zirconium dichloride, 6.3 ml of a toluene solution ~Al 2.55 moles/
liter) of the aluminoxane synthesized in Example 1 and 1.7 ml of toluene were stirred at 22 C for 30 minutes to give a deep yellow transparent solution.
Polsmerization Example lS was repeated except that 0.125 ml of the solution prepared above and 1.0 millimole of triiso-butyl aluminum were used and the polymerization was carried out at 60 C for 1 hour. There was obtained 38.5 g of a polymer having an MFR of 1.09 9/10 min., a density of 0.902 g/cm3, an Mw/Mn of 2.82 and a decane-soluble portion weight fraction at room temperature of 1.3 ~ by weight.

Polvmerization A 2-liter stainless steel autoclave fully purged with nitrogen was charged with 500 ml of toluene, 1 milligram-atom, calculated as aluminum atom, of the aluminoxane ~ynthesized in Example 1, and 2 millimoles of triisobutyl aluminum.
Furthermore, propylene was introduced at 5 kg/cm2-G at 30 C. Thereafter, the introduction of propylene was stopped, and the mixture was cooled to -10 C. Then, 1 x 10 3 millimole of ethylenebis-~indenyl)zirconium dichloride was introduced into the autoclave, and the polymerization was started. By per-forming the polymerization at -10 C for 6 hours, 44.2 g of a polymer was obained.

13~`S282 Example 18 was repeated except that in the polymerization of Example 18, triisobutyl aluminum was not used. There was obtained 2.4 g of a polymer.

Preparation of aluminoxane A 400 ml flask fully purged with nitrogen was charged with 37 9 of A12~SO4)3-14H2O and 125 ml of toluene, and cooled to 0 C. Then, 500 millimoles of trimethyl aluminum diluted with 125 ml of toluene was added dropwise. The temperature was then elevated to 40 C, and the reaction was continued at tbis temperature for 10 hours. After the reaction, the reaction mixture was subjected to solid-liquid separation by filtration.
lS Toluene was removed from the filtrate to obtain 13 9 of aluminoxane as a white ~olid. It had a molecular weight, determined by freezing point depression in benzene, of 930. It shows an m value of 14 in catalyst component ~Bl.
Preparation of a zirconium catalYst A 200 ml flask fully purged with nitrogen was charged with 3.8 g of calcined silica obtained by cal-cining silica ~average particle diameter 70 microns, specific surface area 260 m2/g, pore volume 1.65 cm3/g) at 300 C for 4 hour~, and, 51.5 ml of a toluene ~olution (Al 0.49 mole/liter) of aluminoxane, and they were stirred at room temperature for 10 minutes. Then, toluene was removed by an evaporator at room temperature to give a solid product. To the solid product was added 7.9 ml of a toluene solution ~Zr 0.04 millimole/liter) of bis~cyclopentadienyl)zirconium dichloride, and again toluene wa~ removed by an evaporator at room temperature to give a catalyst component having a Zr content of 0.54 ~ by weight. A gaseou~ mixture of ethylene and n~trogen ~30 liters/hr and 45 liters/hr, respectively) was passed through the resulting cataly~t component at -` 13~5;~2 room temperature for 30 minutes to obtain a solid cata-lyst component in which ethylene was polymerized in an amount of 0.86 9 per gram of the cata}yst.
PolYmerization S A 2-liter stainless steel autoclave fully purged with nitrogen was charged with 900 ml of hexane and 100 ml of l-hexane, and heated to 45 C. Then, 1 millimole of triisobutyl aluminum and 0.015 milligram-atom, calculated as zirconium atom, of the zirconium catalyst subjected to prepolymerization with ethylene were charged. The temperature was then elevated to 60 C. Subsequently, ethylene was introduced and the polymerization was started. Ethylene was continuously fed so as to maintain the total pressure at 7 kg~cm2-G, and the polymerization was carried out at 70 C for 2 hours. After the polymerization, the polymer slurry was added to a large excess of methanol, and the mixture was filtered. The resulting polymer was dried at 80 C for 12 hours under reduced pressure to give 101.2 g of a polymer having an MFR of 0.16 9/10 min., a density of 0.916 g/cm3, an Mw/Mn of 2.98, a bulk density of 0.33 g/cm3 and an n-decane soluble weight fraction at room temperature of 0.31 % by weight. The polymerization conditions, etc. are shown in Table 5.

Example 19 was repeated except that the amount of ethylene prepolymerized was changed to 0.66 g per gram of the catalyst.
Polvmerization Example 19 was repeated except that l-hexane was not used, 1000 ml of hexane was used as a solvent, and ethylene was homopolymer~zed under a total pressure of 6 kg/cm2-G. The results are shown in Table 6.

Polymerization Example 20 was repeated except that isobutyl 13f~ZbtZ

aluminum was not used. The results are shown in Table 6.

Polvmerization A 2-liter stainless steel autoclave purged fully with nitrogen was charged wtih 250 g of sodium chloride (special reagent grade, Wako Pure Chemical6, Co., Ltd.), and dried under reduced pressure at 90 C for 1 hour.
Then, the autoclave was cooled to 65 C, and the inside of the autoclave was replaced by ethylene. Subsequently, 1 millimole of triisobutyl aluminum, 0.015 milligram-atom, calculated as zirconium atom, of the zirco~ium catalyst prepared in Example 19, and 10 ml of l-hexene were introduced. Furthermore, ethylene was introduced, and the total pressure was adjusted to 8 kg/cm2-G. The polymerization was started. Thereafter, only ethylene was supplied, and the polymerization was carried out at 70 C for 2 hours while maintaining the total pressure at 8 kg/cm2-G. After the polymerization, the reaction mixture was washed with water to remove sodium chloride.
The remaining polymer was washed with methanol, and dried overnight at 80 C under reduced pressure. The polymer was ylelded in an amount of 46.8 g, and had an MFR of 1.45 g/10 min., a den~ity of 0.925 g/cm3, an Mw/Mn of 3.03, a bulk density of 0.31 g/cm3 and an n-decane-5 soluble portion weight fraction of 0.10 ~ by weight.EXAMPLE 22 Example 21 was repeated except that in the polymerization of Example 21, l-hexene was not used, triisobutyl aluminum and the zirconium catalyst were added at 75 C, and the polymerization was carried out at 80 C for 1 hour. The results are shown in Table 6.

Polymerization was carried out under the con-ditions indicated in Table 5 in the same way as in Example 19. The results are shown in Table 6.

~3~SZ~

PreParation of a zirconium catalyst A 200 ml flask purged fully with nitrogen was charged with 5.8 g of calcined alumina obtained by cal-cining alumina (average particle diameter 60 microns,specific surface area 290 m2~g, pore volume 1.05 ml/g) at 500 C for s hours, 17 ml of a toluene solution (Al 1 mole/liter) of dimethylaluminum monochloride, and SO ml of toluene, and they were heated at 80 C for 2 hours.
The reaction mixture was then subjected to solid-liquid separation by filtration. The solid portion was trans-ferred to SO ml of toluene, and 32 ml of a toluene solu-tion (Zr 0.04 mole~liter) of bis~cyclopentadienyl)-zirconium dichloride was added. The mixture was heated lS at 80 C for 1 hour. Again, the mixture was subjected to solid-liquid separation by filtration to give a solid catalyst. The zirconium content of the solid catalyst was 0.27 S by weight. 0.1 milligram, calculated as zirconium atom, of the solid catalyst, 20 ml of a toluene solution ~Al 0.49 mole/liter) of the aluminoxane syn-the~ized in Example 19, and 20 ml of toluene were added to the solid catalyst, and the mixture was stirred at room temperature for 30 mlnutes. Toluene was then re-moved by an evaporator at room temperature. A gaseous mixture of ethylene and nitrogen ~30 liters/hr and 45 liter~/hr, respectively) wa~ passed through the resulting cataly~t component at room temperature for 30 minutes to give a solid cataly~t component in which ethylene was polymerized in an amount of 0.30 9 per gram of the cata-lyst.
Polymerization Polymerization was carried out in the same way a8 in Example 22. The results are shown in Table 6.

Example 2? was repeated except that trii80butyl aluminum wa8 not used. The result~ are shown in Table 6.

13~tSZ~

E o O ~ , . ~ I . 'a ~ ~ 3 L~ ~ O
~ C Ql c C C ~ ~ "
o a~ a al I ~ o f Q~ X x _~ X -o :~ al I a) I I ~ e t I I ~ .
C~ E~ .C .C ~.C

_ ~y u~ E~ ~ ~D CO e ~-- ~ e e c .J~
O
E~ C

a-- ~ ,~ . e o ~ - ~ ~ l -E-- . 0 :~
~ ~ ~ 0 ~ ~ ~ JJ-~
o :~ ~ ~ ~ ~ c ~o ~ ~ ~ ~ c~ ~ ~x d ~ 0~ ~ ~ ~ ~ C ^ '~
1 _I .c o E~ m e . em, Q. E~ a~ I e 3 '~ , JJ.C
C ~
O ~ ~
'~ ~ ~ ,~ _~ E~ E~
.,.~ O O
0 0 ~ ~ c ~ ~ c c c c c C ~ ~ ~ o o .~ .~
8- . ~
<~ o ,~ o ~1 ,, ~ ~ ~ ~ ~ ~ ~ ~ ,, , .~ ~C
',, ~x~

14 ~ W

, ~, .... .. .

.

13~iZ~Z

~e CJ O O O O O O O O O O O
I I 11~ CO ~ ~ O t~
O ~ ~ r o ~ O
~ tJ` E3 ~: c~ 1 ~ ~ O ~ U:~
~-~
O ~-- ~ N ~ o o ~ t~
~ ,~ o u~ 1 - ~ ~ ~
-l ~l O ~ C ~ ~ N
0 1~
In p~ N JJ
a ~
~ C ~J O O O O O
~3 ~- ~
o ~ ~
P~ N JJ
~ o ~ o ~1 Q. P.
e ~ ' ' ' O ~X

~. . , ~3~ 2 -- so --Table 6 MFR Density ~ sulk n-decane-soluble (g/10 min.) (g/cm3) density portion at room (g/cm3) temperatures Example 19 0.16 0.916 2.9B 0.33 0.31 n 20 0.03 _ 2.79 0.40 _ n 21 1.45 0.925 3.03 0.31 0.10 n 22 0.19 _ 2.88 0.36 n 23 0.25 0.920 3.10 0.34 0.25 n 24 0.13 0.915 2.93 0.33 0.29 n 25 0.10 0.914 3.08 0.35 0.27 26 0.28 0.918 3.01 0.34 0.24 n 27 0.11 _ 3.00 0.38 E~ple 10 0.04 _ 2.70 0.41 11 0.14 _ 3.24 0.34 _ ~

Preparation of aluminoxane A 400 ml flask fully purged with nitrogen was charged wtih 37 g of A12(SO4)3.14H2O and 125 ml of toluene, and cooled to 0 C. S00 millimoles of trimethyl aluminum diluted withll25 ml of toluene was added drop-wise. The mixture was heated to 40 C, and reacted at this temperature for 10 hours. After the reaction, the reaction mixture was subjected to solid-liquid separation by filtration, and toluene was removed from the filtrate to give 13 g of aluminoxane as a white solid. It had a molecular weight, determined by freezing point depression in benzene, of 930. It showed an m value of 14 in cata-lyst component lB].

~ .

z~

Polymerization A l-liter glass autoclave fully purged with nitrogen was charged with 500 ml of toluene, and a gase-ous mixture of ethylene and propylene (120 liters/hr, and 80 liters/hr, respectively) was passed through the auto-clave and left to stand for 20 C for 10 minutes. There-after, 0.5 millimole of triisobutyl aluminum was added.
Five minutes later, 0.25 milligram-atom, calculated as aluminum atom, of aluminoxane and subsequently, 2.5 x 10 3 millimole of bis~cyclopentadienyl)phenoxy-zirconium monochloride were added, and the polymerization was started. A gaseous mixture of ethylene and propylene was continuously fed, and polymerized at 20 C under atmospheric pressure for 1 hour. After the polymeriza-tion, a small amount of methanol was added to ~top thepolymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer. The polymer precipitate was dried at 130 C under reduced pressure for 12 hour~. The polymer was yielded in an amount of 10.9 g, and had an MF~ of 0.21 9/10 min., an ethylene content, determined by 13C-NMR, of 85.5 mole %, an Mw/Mn of 2.35 and a B value of 1.11. The poly-merization conditions are shown in Table 7.

Example 28 was repeated except that triisobutyl aluminum was not used in the polymerization of Example 28. No polymer was obtained.

Polymerization was carried out under the con-ditions shown in Table 7 by the same procedure as in Example 28. The results are shown in Table 7.

PreParation of catalYst comPonent tA) Fifty milliliters of a solution of bistcyclo-pentadienyl)ethoxyzirconium monochloride tZr 1.3S milli-moles/liter) in toluene was introduced into a 200 ml ~,., 13~iZ~tZ

glass flask fully purged with nitrogen. Furthermore, 34 ml of dimethylaluminum chloride (Al 4 millimoles/liter) was added. The mixture was reacted at 25 C for 30 minutes to give a catalyst component (A).
Polymerization Example 28 was repeated except that the catalyst component (A) prepared as above was used instead of bis(cyclopentadienyl)phenoxyzirconium monochloride.

Example 33 was repeated except that triisobutyl aluminum wa~ not used in the polymerization of Example 33. Hardly any polymer was obtained.

Polymerization was carried out under the con-ditions indicated in Table 7 by the same operation as inExample 28. The results are shown in Table 7.

PôlYmerization A 2-liter ~tainless steel autoclave fully purged with nitrogen was charged with 2SO ml of hexane and 750 ml of 4-methyl-1-pentene, and heated to 35 C.
Thereafter, 0.25 millimole of triisobutyl aluminum, 0.5 milligram-atom, calculated a~ aluminum atom, of the aluminoxane synthesized in Example 1, and 1 x 10 3 milligram-atom, as zirconium atom, of the catalyst component ~A) synthe~ized in Example 6 were introduced.
8ubsequently, ethylene was introduced, and the poly-merization was started. Ethylene was continuously fed so as to maintain the total pres~ure at 8 kg/cm2-G, and the polymerization was carcied out at 45 C for 1 hour. The polymerization product was worked up as in Example 1 to give 30.5 g of a polymer having an M~R of 0.62 9/10 min., a den~ity of 0.902 g/cm3, an Mw/Mn of 2.98 and a decane-soluble partion weight fraction at room temperature of 1.9 ~ by weight.

,~",.. .. ...

~l3~ Z

Example 41 was repeated except that in the polymerization of Example 41, 750 ml of l-hexene was used instead of 4-methyl-1-pentene. There was obtained 28.5 g of a polymer having an MFR of 1.01 g/10 min., a density of 0.891 g/cm3 and an Mw/Mn of 2.79.

Example 41 was repeated except that in the polymerization of Example 41, triisobutyl aluminum was not used. There was obtained 2.5 g of a polymer having an MFR of 1.94 g/10 min., a density of 0.908 g/cm3, an Mw/Mn of 2.95 and a decane-soluble portion weight fraction at room temperature of 1.1 % by weight.

A l-liter continuous polymerization reactor was charged continuously with 500 ml/hr of toluene, 0.5 millimole/hr of tributyl aluminum, 0.5 milligram-atom/hr, calculated as aluminum atom, of the aluminoxane syn-thesized in Example 28, and S x 10 3 milligram-atom/hr, calculated as zirconium atom, of the catalyst compnent ~A) synthesized in Example 40. Simùltaneously, 150 liters/hr of ethylene, 100 liters/hr of propylene, and 1.2 g/hr of ethylidene-2-norbornene ~ENB) were continu-ously fed into the reactor. The polymerization was carried out at a temperature of 20 C under atmospheric pressure with a residence time of 1 hour and a polymer concentration of 14 g/liter. The resulting polymeriza-tion product was worked up as in Example 28 to give an ethylene/propylene/ENB copolymer having an MFR of 2.04 g/10 min., an ethylene content, determined by 13C-NMR, of 85.8 mole %, an aw/an of 2.49 and an iodine value of 10.

13Q5~82 ___ ~ ~ o.,~e~ '' ~
.~ _ _, ~ ~ , I
~ ~ ' ~

_ ~ ~ 1~ , , , N u~
~8 o o o ;~-__ ~ ~ K c C e c c c X X e e X C
,~ l~i .,. ~`1,. ...
~ ~ ~ l ~ ~,~ ~ U U ~) O ~ U ~ ~ U ' ~ .~ ~ æ ~
~ ~ ~_ ~ _ .0 0 0 .0 _ L~ ~ U ~J ~ e ~ L~ ~ C e E~ w w w w w ~ ~ ~ c~
~ ~ c~ ~ ~~ ~C~ ~
, ~ ~ I ~
~ ~ _ o~ o- o ~ ~ I~ co ~ o e~ ~
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ , ~ ~
~ e e ~
~, ': ~ ' : ' .

13~ 2 ~ ooooooooooooo ~
~ ~ ~r o ~ ~ o o ~ ~ D O I I ~1 .~ ~ ~ r~ B
o.u~ o.
o~ O
.l .c ,~ o _~ ' ' ' o ,~ ' ' ' ' ' ~ ' 3 .
o o o, , , ~o, _~
r- ~ ~ ~ 0~
~ I 1 ~ ~
_ _ _1 ~ ~ ~ ~ ~ O
,I ~ ~
~ ~ e~
_ ~ ~ ~ r r~ _ 7 r ~1~

-` 13~ Z

Tzble 7 ~continued) MFR Ethylene - B value ~12) ~9/10 ~ a)ntent tdl~9) .

Exæmple 28 0.21 8s.5 2.351.11 n 29 0.42 85.0 2.291.12 n 30 0.19 83.9 2.301.12 -n 31 O .18 83 .0 2.421.13 n 32 1.54 86.2 2.451.10 n 33 0.33 83.9 2.341.12 _ ~ 34 0.62 83.2 2.051.13 n 35 0.25 85.8 2.251.10 n 36 _ 60.7 2.01 _ 0.22 n 37 0.28 81.2 2.161.18 n 38 0.67 86.0 2.331.10 _ n 39 0.40 82.9 2.291.13 _ 0.37 84.4 2.301.12 _ ~1-1~ _ _ _ _ _ Oph: Phenoxy group Sph7 Thiophenyl gro4p CEtS Ethoxy group abu; t-Ehtoxy group 1) Mole ratio at the time of treatment 2) Measured in decalin at 135qC
3) Tri~2 _ thylpentyl)aluminum 4) Trit2-ethylhexyl)aluminum :

.A. . ~ ~ .` ~ ' '

Claims (17)

1. A process for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of a catalyst composed of (A) a solid catalyst component composed of a compound of a transition metal of Group IVB of the periodic table supported on an inorganic carrier, (B) an aluminoxane, and (C) an organoaluminum compound having a hydro-carbon group other than n-alkyl groups.

2. The process set forth in claim 1 wherein the transition metal is titanium, zirconium or hafnium.

3. The process set forth in claim 1 wherein the transition metal compound is represented by the following formula (I) ..... (I) wherein R1 represents a cycloalkadienyl group, R2, R3 and R4 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 -ORa, -SRb or -NR? in which each of Ra, Rb and Rc represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, Me represents zirconium, titanium or hafnium, k is 1, 2, 3 or 4, ?, m and n are each 0, 1, 2 or 3, and k+?+m+n=4.

4. The process set forth in claim 1 wherein the aluminoxane is represented by the following formula (II) (II) wherein R is a hydrocarbon group, X is a halogen atom, and a and b, independently from each other, represent a number of 0 to 80 with the proviso that a and b are not simultaneously zero, or the following formula (III) (III) wherein R, X, a and b are as defined above with regard to formula (II).

5. The process set forth in claim 1 wherein the inorganic carrier is treated with an organometallic compound or a halogen-containing silicon compound prior to deposition of the transition metal compound on it.

6. The process set forth in claim 1 wherein the organometallic compound is an organoaluminum compound, and organoboron compound, an organomagnesium compound, an organozinc compound or an organolithium compound.

7. The process of claim 1 wherein the halogen-containing silicon compound is represented by the following formula (IV) SiYdR?(OR6)4-d-e (IV) wherein Y represents a chlorine or bromine atom, R5 and R6, independently from each other, represent a hydrogen atom, 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, with the proviso that the sum of d and e is a number of 1 to 4.

8. The process set forth in claim 1 wherein the inorganic carrier is a porous inorganic oxide.

9. The process set forth in claim 1 wherein the organic group of the organoaluminum compound is a branched alkyl group, a cycloalkyl group or an aryl group.

10. A process for producing olefins, which com-prises polymerizing or copolymerizing the olefins in the presence of a catalyst composed of (A)' a compound of a transition metal of Group IV of the periodic table containing a ligand having a conjugated .pi.-electron and a ligand containing a hetero atom capable of being bonded to the transition metal and selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus, (B) an aluminoxane, and (C) an organoaluminum compound having a hydro-carbon group other than n-alkyl groups.

11. The process set forth in claim 10 wherein the transition metal is titanium, zirconium or hafnium.

12. The process set forth in claim 10 wherein the transition metal compound is represented by the following formula (I)' wherein R11 is cycloalkadienyl, R12 is selected from the class consisting of -ORa, -SRb, -NR? and -PR?, R13 and R14, independently from each other, represent cyclo-alkadienyl, aryl, aralkyl, alkyl, halogen or hydrogen, Ra, Rb and Rc represent alkyl, cycloalkyl, aryl, aralkyl or organic silyl, Me is zirconium, titanium, or hafnium, k and ? are 1, 2 or 3, m and n are 0, 1 or 2 and k+?+m+n=4.

13. The process set forth in claim 10 wherein the aluminoxane is represented by the formula (II) given above.

14. The process set forth in claim 10 wherein the organic group of the organoaluminum compound is a branched alkyl group, a cycloalkyl group or an aryl group.

15. The process of claim 10 wherein the transition metal compound is treated with an organometallic com-pound.

16. The process of claim 15 wherein the organo-metallic compound is an organoaluminum compound, an organoboron compound, an organomagnesium compound, an organozinc compound or an organolithium compound.

17. A process for polymerizing or copolymerizing olefins in the presence of a catalyst composed of (A)" a compound of a transition metal of Group IVB of the periodic table, (B) an aluminoxane in a concentration of not more than 3 milligrams/liter as aluminum atom in the reaction system, and (C) an organoaluminum compounds having a hydrocarbon group other than n-alkyl groups.