Note: Descriptions are shown in the official language in which they were submitted.
" 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
-- 2 --
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~
-- 5 --
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) of5 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 an5 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
-- 10 --
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
-- 11 --
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
- 12 -
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
- 15 -
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
-- 16 --
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
- 17 -
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
- 18 -
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~'~
-- 19 --
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~
- 20 -
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
- 21 -
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
-- 22 --
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 ~
- 23 -
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
- 24 -
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
- 2S -
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
- 26 -
(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
-- 27 --
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
-- 28 --
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
- 29 -
(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~
- 30 -
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
- 31 -
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
-- 32 --
~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
- 33 -
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.
EXAMPLE 1
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
- 34 -
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.
COMPARATIVE EXAMPLE 1
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.
EXAMPLE 10
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
- 35 -
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.
EXAMPLES 11-13 AND COMPARATIVE EXAMPLE 7
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
-- 36 --
. .
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
-- 37 --
~ .
~ 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
- 38 -
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
13Q5282
-- 39 --
_ ~ o o o C o
11 ~ L 5~ ~ ~
. Y
~ oo
_
~ O , ,~ u~, In
~ To To
13Q5Z8Z
-- 40 --
_ ~ ~
~ ~ ~ "
il ~ a ~ ~
~ ~ C
13~5Z82
- 41 -
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
EXAMPLE 14
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 .
COMPARATIVE EXAMPLE 8
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
- 42 -
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.
EXAMPLE 16
~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.
EXAMPLE 17
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.
EXAMPLE 18
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
- 44 -
COMPARATIVE EXAMPE 9
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.
EXAMPLE 19
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
- 45 -
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.
EXAMPLS 20
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.
COMPARATIVE EXAMPLE 10
Polymerization
Example 20 was repeated except that isobutyl
13f~ZbtZ
- 46 -
aluminum was not used. The results are shown in Table 6.
EXAMPLE 21
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.
BXAMPLES 23-26
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~
- 47 -
EXAHPLE 27
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.
COMPARATIVE EXAMPLB 11
Example 2? was repeated except that trii80butyl
aluminum wa8 not used. The result~ are shown in Table 6.
13~tSZ~
--48
E o O ~ , . ~ I . 'a
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c C C ~ ~ "
o a~ a al I ~ o
f Q~ X x _~ X -
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13~iZ~Z
-- 49 --
~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:~
~-~
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~ ,~ o u~ 1
- ~ ~ ~
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O ~ C ~ ~ N
0 1~
In p~ N JJ
a ~
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~. . ,
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-- 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 _ ~
EXAMPLE 28
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~
- 51 -
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.
COMPARATIVE EXAMPLE 12
Example 28 was repeated except that triisobutyl
aluminum was not used in the polymerization of Example
28. No polymer was obtained.
EXAMPLES 29-32
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.
EXAMPLE 33
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
-- 52 --
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.
COMPARATIVE EXAMPLE 13
Example 33 was repeated except that triisobutyl
aluminum wa~ not used in the polymerization of Example
33. Hardly any polymer was obtained.
EXAMPLES 34-40
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.
EXAMPLE 41
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 42
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.
COMPARATIVE EXAMPLE 14
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.
EXAMPLE 43
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
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r- ~ ~ ~ 0~
~ I 1 ~ ~
_ _
_1 ~ ~ ~ ~ ~ O
,I ~ ~
~ ~ e~
_
~ ~ ~ r r~ _
7 r ~1~
-` 13~ Z
- 56 -
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. . ~ ~ .` ~ ' '
