2 ~ 6 7
PRODUCTION OF ~-OLEFIN POLYMERS
B~CKGROUND OF THE INVENTION
The present invention relates to a process for
preparing a-olefin polymers. More particularly, the
present invention relates to a catalyst for
polymerization of ~-olefins comprising a specific
transition metal compound and a specific novel
methylisobutylalumoxane and a process for preparing poly-
~-olefins-
Related Art
The methods of preparing poly-~-olefins wherein a
catalyst comprising an alumoxane and a transition metal
compound in combination are well-known (Japanese Patent
Laid-Open Publication Nos. 45205/1983, 19309/1983,
35007/1985, 130314/lg86, 230802/1987, 142004/1988,
234009/1988, 51408/1989 and 66214/1989). These
techniques may, however, have high production cost due to
the low activities per aluminum and industrial
disadvantages due to the large amounts of aluminum
remaining in oleEin polymers.
For the purpose of solving the problems, a variety
of proposals have been disclosed in Japanese Patent Laid~
Open Publication Nos. 211307/1986, 1306()1/198n,
16803/1989, 22308/:l~90 and 167307/19g0. 'rhe activity per
aluminum have been improved to some extent in these
proposals. However, alumoxane has poor solubility and is
hard to deal with in its nature, and the diiculty of
removiny aluminum may bring about the lowering oE quality
or the deterioralioll oE hue of o].eEin polymers thereby
produced, so that Eurther improvement is required.
As alternative propoc;als, the methods where use is
made oE another organoaluminum compound or the like in
addition to methylalumoxane have also been described in
Japanese Patent Laid-Open Publication Nos. 260602/1985,
130604/1985, 89506/1988, 178108/1988, 21~707/1988,
9206/1989, 315407/1989, 22306/1990 and 167310/1990.
ri ~ ~
~lthough these methods have successively decreased the
amount of methylalumoxane used, the activity per aluminum
may still be unsatisfactory and thus further improvement
may be desired.
On the other hand, a catalyst component for olefin
polymerization comprising an alumoxane compound
containing at least two alkyl groups has been described
as a new proposal in Japanese Patent Laid-Open
Publication Nos. 247201/19~0, and 250886/1990 and U. S.
Patent No. 5,003,095. To the best of our knowledge,
however, the method may improve the activity only
insuffici.ently, and thus further improvement of the
activity may be desired.
SUMMARY OF THE INV~NTION
The ob~ect of the present invention is to solve
aforementioned many problems in the prior art.
The present invention in one aspect, provides
catalyst for a-olefin polymerization which comprises the
following components (A) and (B):
component (A), which is a transition metal compound
represented by the formula
Q ( C5H4 _,"Rl,n, ) ( C5H4 -nR2n ) MeXY
wherein (C5H~_mRl,n) and (C5l~ ~R2,l) respective].y represerlt
a conjugated five-membered rirlg :ligalld coordinaking to a
metal Me; R1 and R~, wriicll may be the same or cdiEEerent
and a plurali.ty of each o which can be bonded together,
respectively represent a hydrocarbyl group having 1 to 20
carbon atoms~ a halogen atom, an alkoxy group, a silicon-
containing hydrocarbyl group, a phosphorus-containing
hydrocarbyl group, a nitrogen-containing hydrocarbyl
group or a boron-contailling hydrocarbyl group; Q
represent:s a bonding group which crosslinks the two
conjugated five-membered ring ligands; Me represents a
transition metal of the IVB-VIB group in the Periodic
- 35 Table; X and Y, which may be the same or different,
respectively represent hydrogen, a halogen atoms, a
hydrocarbyl group, an alkoxy group, an amino group, a
2 ~ 7
phosphorus-containing hydrocarbyl group or a silicon-
containing hydrocarbyl group; m denotes an integer of 0
< m < 4 and n denotes an integer of 0 < n < 4;
component (B), which is a methylisobutylalumoxane
which satisfies the following conditions (a), (b) and
(c):
(a) the molar ratio of a methyl group to an isobutyl
group is in the range of 4:1 to 1:4,
(b) the chemical shift of 27~1-NMR is in the range
of 160 ppm to 250 ppm and the peak has a half-height
width of no smaller than 3000 Hz, and
(c) it has a repeating unit of A1-0 in an amount of
2 to l.00.
'I'he present inventioll, in another aspect, provides a
process for preparing a-olefin polymers which comprises
contacting an ~-olefin with a catalyst for a-olefin
polymerization thereby to polymerize the ~-olefins, the
catalyst comprising the following components (A) and (B):
component (A), which is a transition metal compound
represented by the Eormula
Q(c5H4-mRlm)(c5H4-nR2n)Mexy
wherein (C5Hq_mRlm) and (C5H4_nR2n) respectively represent
a conjugated :Eive-membered ring ligand coo~dinati.ng to a
metal Me; ~1 and ~2, which may be the t,ame or diEferent
and a plurality of each oE whi.ch can be bollded together,
respectively represellt a hydrocarbyl group having 1. to 20
carbon atoms, a halogen atom, an alkoxy group, a sllicon-
containing hydrocarbyl group, a phosphorus~containing
hydrocarby:L group, a nitrogen-colltainillg hydrocarbyl
group or a boron-contail~ g hydrocarbyl group; Q
represents a bonding group which crosslinks the two
conjugated five-membered ring ligands; Me represents a
transition metal oE the IVB-VIB group in the Periodic
Table; X and Y, which may be the same or different,
respectively represent hydrogen, a ha:Logen atoms, a
hydrocarby:l. group, an alkoxy group, an amino group, a
phosphorus-containing hydrocarbyl group or a silicon-
containing hydrocarbyl group; m denotes an integer of 0< m < 4 and n denotes an integer of 0 < n < 4;
component (B), which is a methylisobutylalumoxane
which satisfies the following conditions (a), (b) and
S (c):
(a) the molar ratio of a methyl group to an isobutyl
group is in the range of 4:1 to 1:4,
(b) the chemical shift of 27Al-NMR is in the range
of 160 ppm to 250 ppm and the peak has a half-height
10 width of no smaller than 3000 Hz, and
(c) it has a repeating unit of Al-O in an amount of
2 to 100.
BRIEF DESCRI_ ION OF THE DRAWINGS
Fig. 1 is a 13C--NMR spectrum of the component (B)
15 prepared in Example 1,
Fig. 2 is a 27Al-NMR spectrum of the component (B)
prepared in Example 1,
Fig. 3 is a 27Al-NMR spectrum of the component (B)
prepared in Example 2,
Fig. 4 is a 27Al-NMR spectrum of a commercially
available polymethylalumoxane,
Fig. 5 is a 27Al-NMR spectrum of a commercially
available polymethyJalumoxane,
Fig. G is a 27Al-NMR F~pectrUIn of a Gomlller~ially
25 available polyisobutylalumoxalle,
Fig. 7 is a 27Al-NMR spectrum of the alumoxane in
Comparative Example 4, and
Fig. ~ is a 27Al--NMR spectrum of the alumoxane ln
Comparative Example 5.
DETAILED DESCRIPTION OF '1'HE_INV_NTION
<Catalyst of a-olefin polYmerization>
The catalyst of ~-olefin polymerization of the
present invention comprises the components (A) and (B).
The term "comprises" herein used does not intend to
35 exclude any optional or third component as far as they
will not adversely afect the effects of the components
(A) and (B).
r~ ~ 7
ComPonent ( Al
The component (A) is a transition metal eompound
represented by the formula:
Q(c5H4-~Rlm)(c5H4-nR2n)MeX~
The compound has a structure in whieh two conjugated
five-membered ring groups C5H4_mRlm and C5H4_~lR n
erosslinked with the crosslinking group Q, that is,
Q(C5H~ mRlm)(C5H4 nR2n), coordinate the transition metal
eompound MeXY of the IVB-VIB group in the Periodic Table.
In this connection, while the conjugated five-
membered ring groups C5H~ mRlln and C5H4_nR2n have been
separately defined, m and n and Rl and R2 have the same
meaning, respectively (as will be described in detail),
so that it is needless t:o ~ay that these two conjugatecd
t5 five--membered rilly groups may be (he same or diEferent.
A specific example oE the conjugated five-membered ring
groups is the one wherein m = 0 (or n = 0), i.e. a
cyclopentadienyl group (having no substituent other than
the crosslinking group Q). In the ease of the conjugated
Eive-membered ring groups having a substituellt wherein m
0 (or n ~ ()), a speeific example of Rl (or R2) is a
hydrocarbyl group having l to 20 carbon atoms, preferably
l to 12 carbon atoms. The hydrocarbyl group may be
bonded as a monovalent grouE) t:o a cycLopentadienyl group
or two o~ the hydlocalt)yi c;roup~; may be bQIldecl wittl eclch
other to orm a ring togrttler with pOItiOIl of ttle
cyclopentadienyl group to wtlicll they are attached.
Typical example o~ the latter is the ol~e in which two o~
Rl (or R2) orm a ~used six-membered ring with a double
bond of t:h-~ c:yclopelltadiellyL group in common, i.e. the
one in which the conjugated five-membered ring groups is
an indenyl group or a ~luorellyl group. The typical
examples o~ the conjugated five-member:ed ring groups are
thus cyclopentcldiellyl group, an indenyl group and a
fluorerlyl group.
Rl and R2, respective]y, inc]ude, in addit;on to the
above-described hyclrc)carbyl group havillg l to 20 carbon
6 ~&~7~31~
atoms, preferably 1 to 12 carbon atoms, a halogen atom
such as chlorine, fluorine, bromine, an alkoxy group such
as the one having 1 to 12 carbon atoms r a silicon-
containing hydrocarbyl group such as the one which
5 contains silicon atom in the form of -Si(Ra)(Rb)(RC)
wherein Ra, Rb and Rc each have 1 to 24 carbon atoms, a
phosphorus-containing hydrocarbyl group such as the one
which contains phosphorus atom in the form of -P(Ra)(Rb)
wherein Ra and Rb each have 1 to about 18 carbon atoms, a
10 nitrogen-containing hydrocarbyl group such as the one
which contai.ns nitrogen atom in the form of -N(Ra)(Rb)
wherein Ra and Rb each have 1 to about 18 carbon atoms,
and a boron-containing hydrocarbyl group such as the one
which contains boron atom in the ~orm of -E3(Ra)(Rb)
15 wherein Ra and Rb each ~lave 1 to about 18 carbon atoms.
When m (or n) is at least 2 and at least two Rls (or R2s)
are present, these groups may be the same or different.
Q is a bonding group which crosslinks the two
conjugated five-membered ring groups. Particularly, it
is (a) a lower alkylene group or a cycloalkylene group
which may or may not be substituted by an alkyl,
alicyclic and/or aromatic group having 1 to 15 carbon
atoms, such as a methylene group, an ethylene group, an
isopropylene group, a phenyllTlettly~l.lllettlylene group, a
25 diphenylmethylelle grollp, a cyc:lohexylene y~oup and the
like, (b) a substituted or non-substituted silylene or
oligosily].ene group which may or may not be substituted
by an alkyl, alicyclic and/or aromatic group having 1 to
12 carbon atoms suctl as a silylene group, a
30 dimethylsilylene group, a phenylmethyl.si].ylene group, a
diphenylsilylene group, disilylene group, a
tetramethyldisilylene group and the ].ike, and (c) a
hydrocarby] group containi.ng germanium, phosphorus,
nitrogen or aluminum such as (CH3)2Ge=, [C6H5)2Ge=,
(CH3-)-P=, (C6Hs-)-P=, (C4EIg-)-N=, (C6EI5-)-N=, (CH3-)-B=,
(C4E-Ig-)-B=, (C6Ei5-)-B-, (C6EI5-)-Al=, (CH30-)-Al= and the
like. Q is preferably an alkylene group or a substituted
silylene group.
Me is a transition metal of the IVB-VIB group in the
Periodic Table, preferably titanium, zirconium or
hafnium.
X and Y, respectively, include hydrogen atom, a
halogen atom, a hydrocarbyl group having 1 to 20,
preferably 1 to 12 carbon atoms, an alkoxy group having 1
to 20, preferably 1 to 10 carbon atoms, an amino group, a
10 phosphorus-containing hydrocarbyl group having 1 to 20,
preferably 1 to 12 carbon atoms such as diphenylphosphine
group, and a silicon-containing hydrocarbyl group having
1 to 20, preferably 1 to 10 carbon atoms such as
trimethylsilyl. X and Y may be the same or different. m
15 and n denote an integer of 0 < m < 4 and 0 < n < 4,
respectively.
Specific examples of the transition metal compound
in which Me is zirconium are speciied in the Eollowing.
(a) Transition metal compounds containing a five-
20 membered ring ligand crosslinked with an alkylene group:Methylenebis(indenyl)zirconium chloride,
Ethylenebis(indenyl)zirconium chloride,
Ethylenebis(indenyl)æircollium mollohydri,de
monochloride,
Ethylenebis~indenyl)methylzirconium monochlorlde,
Ethylenebis(indenyl)zirconium monomethoxy
monochloride,
Ethylenebis(indenyl)zircollium diethoxide,
Ethylenebis(illdenyl)zirconium dimethyl,
Ethylenebis(4,5,6,7-tetrahydroindellyl)zirconium
dichloride,
Ethylenebis(2-methylindenyl)zirconium dichloride,
Ethylenebis(2,4-dimethylindenyl)zirconium dichloride,
Ethylenebis(2,4,7-trimethylindenyl)zirconium
dichloride,
Ethylene(2,4-dimethylcyclopentadienyl)(3',5'-
dimethylcyclopentadienyl)zirconium dichloride,
8 ~ rl~ ~ 7
Ethylene(2-methyl-4-tert-butylcyclopentadienyl)(3'-
tert-butyl--5'-methylcyclopentadienyl)zirconium
dichloride,
Ethylene(2,3,5-trimethylcyclopentadienyl)(2',4',5'-
trimethylcyclopentadienyl)zirconium dichloride,
Isopropylidenebis(indenyl)zirconium dichloride,
Isopropylidenebis(Z,4-dimethylcyclopentadienyl)(3',5'-
dimethylcyclopentadienyl)zirconium dichloride,
Isopropylidenebis(2-methyl-4-tert-
butylcyclopentadienyl)(3'-tert-butyl-5'-
methylcyclopentadienyl)zirconium dichloride,
Methylene(cyclopentadienyl)(3,4-
dimethylcyclopentadienyl)zirconium dichloride,
Methylene(cyclopentadienyl(3,4-
dimethylcyclopentadienyl)zirconium chloride hydride,
Methylene(cyclopentadienyl)(3,4-
dimethylcyclopentadienyl)zirconium dimethyl,
Methylene(cyclopentadienyl(3,4-
dimethylcyclopentadienyl)zirconium diphenyl,
Methylene(cyclopentadienyl)(trimethylcyclopentadienyl)
zirconium d:ichloride,
Methylene(cyclopentadienyl)(tetramethylcyclopenta-
dienyl)zirconium dichloride,
Isopropylidene(cyclopentadienyl)(3,4-
dimethylcyc::Lopentadiellyl)zircol~ d;.ch:lo~ide,
Isopropylidlene(cyc:l.opentadi.enyl)(~,3,~,5--
tetramethylcyclopentadienyl)zircollium dlchlor;.de,
Isopropylidene(cyclopentadiellyl)(3-
methy:Lindenyl)zirconium dichloride,
Isopropylidene(cyclopentadienyl)(fluorellyl)zirconium
dichloride,
Isopropylidene(2-methylcyclopentadienyl)-
(fluorenyl)zirconium dichloride,
Isopropylidene(2,5-dimethylcyclopentadienyl)(3,4-
dimethylcyclopentadiellyl)zirconium dichloride,Isopropylidene(2,5-dimethylcyclopentadienyl)-
(fluorenyl)zirconium dichloride,
9 ~ 7 ~ 1
Ethylene(cyclopentadienyl)(3,5-
dimethylcyclopentadienyl)zirconium dichloride,
Ethylene(cyclopentadienyl)(fluorenyl)zirconium
dichloride,
Ethylene(2,5-dimethylcyclopentadienyl)-
(fluorenyl)zirconium dichloride,
Ethylene(2,5-diethylcyclopentadienyl)-
(fluorenyl)zirconium dichloride,
Diphenylmethylene(cyclopentadienyl)(3,4-
dimethylcyclopentadienyl)zirconium dichloride,
Diphenylmethylene(cyclopentadienyl)(3,4-
diethylcyclopentadienyl)zirconium dichlor.ide,
Cyclohexylidene(cyclopentadieny])(~luorenyllzirconium
dichloride, and
Cyclohexylidene(2,5-dimethylcyclopentadienyl)(3',4'-
dimethylcyclopentadienyl)zirconium dichloride.
(b) Transition metal compounds containing a five-
membered ring ligand crosslinked with a silylene group:
Dimethylsilylenebis(indenyl)zirconium dichloride,
Dimethylsilylene(4,5,6,7-tetrahydroindenyl)zirconium
dichloride,
Dimethylsilylenebis(2-methylindenyl)zirconium
dichloride,
Dimethylsi.].ylenebis(2,4-di.lnethyli,tldelly~ ,irc~lllu
dichloride,
Dimethylsilylenebis(2,4,7-trimethylilldellyl)~irconium
dichloride,
Dimethylsilylene(2,4-dimethylcyclopentadi.enyl)(3',5'-
dimethylcyclopentadienyl)zirconi.um dichloride,
Phenylmethylsi].y].enebis(irldenyl)%irconium dichloride,
Phenylmethylsilylenebis(4,5,6,7-
tetrahydroindenyl)zirconium dichloride,
Phenylmethylsilylene(2,4-dimethylcyclopentadienyl)-
(3',5'-dimethylcyclopentadienyl)zirconium dichloride,
Phenylmethylsily].ene(2,3,5-trimethylcyclopentadienyl)-
(2,4,5-trimethylcyclopentadienyl)zirconium dichloride,
Phenylmethylsilylenebis(tetramethylcyclopentadienyl)-
l o ~ 7
zirconium dichloride,
Diphenylsilylenebis(indenyl)zirconium dichloride,
Tetramethyldisilylenebis(indenyl)zirconium dichloride,
Tetramethyldisilylenebis(cyclopentadienyl)zirconium
dichloride,
Tetramethyldisilylene(3-methylcyclopentadienyl)-
(indenyl)zirconium dichloride,
Dimethylsilylene(cyclopentadienyl)(3,4-
dimethylcyclopentadienyl)zirconium dichloride,
Dimethylsilylene(cyclopentadienyl)-
(trimethylcyclopentadienyl)zirconium dichloride,
Dimethylsilylene(cyclopentadienyl)-
(tetramethy].cyclopentadienyl)zirconium dichloride,
Dimethylsilylene(cyclopentadierlyl(3,4-
diethylcyclopentadienyl)zirconium dichloride,
Dimethylsilylene(cyclopentadienyl)-
(triethylcyclopentadienyl)zirconium dichloride,
Dimethylsilylene(cyclopentadienyl)-
(tetraethylcyclopentadienyl)zi.rconium dich].oride,
Dimethylsilylene(cyclopentadienyl)-
(fluorenyl)zirconium dichloride,
Dimethylsilylene(cyclopentadienyl)(2,7-di-tert-
butylEluorenyl)zirconium dich:Loride,
Dimethylsilylene(cyclopentadienyl)-
(octahydro~l.uorenyl)zircorl.ium dich.Loride,
Dimethylsilylene(2-methylcyclopentadienyl)-
(fluorenyl)zirconium dichloride,
Dimethylsilylene(2,5-dimethylcyclopentadienyl)-
(~luorenyl)zirconium dichloride,
Dimethylsilylene(2-ethylcyclopentadienyl)-
(fluorenyl)zirconium dichloride,
Dimethylsilylene(2,5-diethylcyclopentadienyl)-
- (Eluorenyl)zirconium dichloride,
Dimethy].silylene(2-methylcyclopentadienyl)(2,7-di-
tert-butylfluorenyl)zirconium dichloride,
Dimethylsilylene(2,5-dimethylcycLopentadienyl)(2,7~di-
tert-butyl.Eluorenyl)zirconi.um dichloride,
Dimethylsilylene(2-ethylcyclopentadienyl)(2,7-di-tert-
butylfluorenyl)zirconiun~ dichloride,
Dimethylsilylene(diethylcyclopentadienyl(2,7-di-tert-
butylfluorenyl)zirconium dichloride,
Dimethylsilylene(methylcyclopentadienyl)-
(octahydrofluorenyl)zirconi.um dichloride,
Dimethylsilylene(dimethylcyclopentadienyl)-
(octahydrofluorenyl)zirconium dichloride,
Dimethylsilylene(ethylcyclopentadienyl)-
(octahydrofluorenyl)zirconium dichloride, andDimethylsilylene(diethylcyclopentadienyl)-
(octahydrofluorenyl)zirconium dichloride.
(c) Transiti.on metal compounds containing a ive-
membered li~and crossl.inked with a hydrocarbylated
15 germanium, alumillum, boron, phosphorus or nitrogen:
Dimethylgermaniumbis(indenyl)zirconi.um dichloride,
Dimethylgermanium(cyclopentadienyl)-
(fluorenyl)zirconium dichloride,
Methylaluminumbis(indenyl)zirconium dichloride,
Phenylaluminumbis(indenyl)zirconium dichloride,
Phenylphosptlinobis(indenyl)zirconium dichloride,
Ethylboranobis(indenyl)zirconium dichloride,
Yhenylaminobis(indenyl)zirconium dichloride, and
Phenylamino(cycloperltadienyl)(fl.uol-elly~ z.i.rcolli.u
dich1ori-le.
(cl) 'J'lle afOrelllCllt;Cll('d COlllpOllllC~ c) (C) o.E whictl
chlorine has been substituted by the otl-ler substituents
such as bromine, iodine, hydride, methyl, phelly:L, butoxy,
phenoxy, tri.methy:l.s;.Lyl. or trimettlylsi.:Lyl.methy.l. can al.:o
be used.
In the present invent.i.oll, the aforementioned
compounds (a) to (d) of WtliCtl the central metal,
zircollium, has been substituted by the other metal. such
as titanium, haEni.um, ni.obium, molybdenum or wolfram can
35 also be used. Among these compounds, the zirconium
compounds, the hafl~ m compounds and the titanium
compoullds are preEerrLd. 'I'tle zircollium compounds and
12
hafnium compounds crosslinked with an alkylene group or a
silylene group are more preferred.
Component (B)
The component (B~ used in the present invention is a
novel methylisobutylalumoxane represented by the formula
(I) or tII):
R3 R4 R3
R3~ Al--O ) p-l~ Al~O~qAl-R3 ( I )
or
R3 R4
(II)
1 5 ~l-O -~
wherein R3 and R4 represent a methyl group or an isobutyl
group, respectively. The methyl group and the isobutyl
group are arranged in block or at random in the molecule,
the latter being preEerable. p and q denote an integer
of at least 1, respectively, and the sum of p+q is
generally in the range of 2 to 100, preferably 4 to 50,
more preferably 8 to 20. The ratio of p to q is in the
range of 4:1 to 1:4, pre~erably 2:1 to ~ 2. IE the ratio
is not within the range, the property o~ the component
25 (B) approaches the one oE methylalumoxatle or
isobutylalumoxane, and the speciEic advantages inherent
in the present invention will not be attainable.
It is to be understood that the sufEix "p" in the
formulae (I) and (II) indicates the amount in the
molecule of the unit R3 but does not indicate, when
I
t Al-0~
it is 2 or more, that units are in block connected in
succession. The unit can thus be comprised in the
molecule in block or at random. The same applies to the
su~fix "q".
13 ~ 7
A methyl group and an isobutyl group can be
determined quantitatively by the l3C-NMR or lH-NMR
measurements of these groups or by the gas
chromatographical analysis of hydrolysates generated by
the reaction with water.
The polymerization degree or the molecular weight of
the alurnoxane compound can be determined, for example, by
the cryoscopic method of benzelle.
The alumoxarle oE the present invention gives a
characteristic spectrum in the 27A1-NMR measurement. In
other words, while an ordinary alkylaluminum shows a peak
at a chemical shift in the range of 150 to 155 ppm which
i5 charact~ristic to the coordination number of ~ and
havirlg a hal~--wiclth of 2,000 ~z or less, the alumoxane of
~~5 the present invention distinctively shows a peak at a
chemical shift in the range of 160 ppm to 250 ppm and
having a half-width of no smaller than 3,000 Hz.
According to the present invention, t:he alumoxane shows
preferably a peak at a chemical shift in the range of 160
ppm to 200 ppm, more preferably in the range of 165 ppm
to 190 ppm, most preferably in the range of 165 ppm to
180 ppm and having a half-width of 3 t 000 Hz or more, more
preferably 3,50() H% or mc)re, most preft~ )ly i.n the rallge
o(~ ~, 00() ~1% ~,c) :1.(), ~)OU 1~
In this c~onnect:ioll, tlle NMR spectrd (l3G: 67.9 MLIz;
27A1: 70.~ M~iz) or the alumoxane compo~ d are those
obtained whell 2.5 ml of a solution in toluene o~ the
alumoxclne compc)un(l in a concelltL-atiorl of 6 to 7~ by
weight based on al Illlli.llUIII atom and 0.5 ml of deutero--
benzene anci admixed and by the mcasurelllent is performedwith an NMR spectrograph GSX-270 model manufactured by
Japan Electron Optics Laboratory Co., Ltd. at 27C.
27Al-NMR spectra are those measured under the conditions
c~ a pulse width of 90, a pulse interva] of 0.06 second
and a scanning number oE 10,000 at the non-decoupling
mode. 'L'hc chemical shirt of 27Al is measured in relation
to the [Al(~i2O)~]3+ ions in an aqueous aluminum sulfate
14 2~ ~ ~7~7
soiution as the external standard (0 ppm). The half-
widths of spectra are calculated from the peak width at
the half height and represented by Hz. l3C-NMR spectra
are measured under the conditions of a pulse width of
S 45, a pulse interval of 5 seconds and a scanning number
of 1,000 at the proton-decoupling mode with a
tetramethylsilane as the external standard (0 ppm).
~ n y m e t h od s f o r p r e p a r i ng t h e
methylisobutylalumoxane compound which satisfies the
conditions that the molar ratio of the methyl group to
the isobutyl group is in the range of 4:1 to 1:4 and the
27Al-NMR spectrum has a chemical shift in the range of
160 to 250 ppm arld a hal-width in the range of no
srnalLer than 3,00n flz can be used as far as the alumoxane
having such features can be obtained, but speciEic
examples of the methods include:
(i) a method where trimethylaluminum and
triisobutylaluminum are admi.xed in a mole ratio of 4:1 to
1:4 and the admixture is reacted under heating with a
controlled amount of water or an inert organic solvent
such as toluene, benzene or ether to which water has been
saturated,
(ii) a method where tr.i.rnethy1alumirlum and
triisobutylaluminulll are adlll;.xe(l ;n a mole ratio o 4:.l. to
~5 1:4 and the admixture i.s relcted ull(ler heat.ing at a
temperature no lower thatl S0C wi.th a sa:lt hydrate having
water of crystallization such as a hydrate o copper
su:Lfate or aluminum sul.fate,
t;.ii) a method where sil.ica gel is impregnated with
water, whi.ch is treated wi.th trii.sobuty:Lalumillum and then
with trimethylaluminum under heatirlg,
(iv) a method where methy:lal.ullloxane and
isobutylalumoxane are synthesized respectively according
to the well-known methods, the predetermined amounts of
these two products are admi.xed, fol.lowed by heating to
conduct the reactioll and
2~C~3~16 7
(v) a method where dimethylaluminum ehloride are
reacted with water and then, under heating, with
isobutylmagnesium ehloride.
It is preferable that the reactions in the methods
(i) to (v) given above be conducted, or eomprise a step
condueted, at a temperature no lower than 50C. The
reaetion or step at such a high temperature may produce
the ehange in the spectrum of 27Al-NMR required in the
present invention.
Formation of C_talyst
The catalyst of the present invention ean be
obtained by eontaeting the aforementioned eomponents (A)
and (B) within or outside a polymerization vessel in the
presence or absenee o a monomer to be polymerized.
Althougn the colnpollelltC~ (A) and (B) used in the
present invention may be used in any amounts, they are
generally used in sueh amounts that the atomie ratio of
the aluminurn atom in the component (B) to the transition
metal in the eomponent (A) (Al/Me) are in the range of
20 0.01 to 100,000, preferably 0.1 to 30,000. The eontaet
methods oE these eomponents being not eritieal, the
eomponents may be introclueed separately and eontaeted
with eaeh other, or the eornponents whieh have been
preliminarily contacte(l may al~o he used.
The catalyt;t a((or(l;llc3 lo ~ e prer~etll ; nvetlLiorl, as
deserlbed above, call com~ ir;( otllcr conlponents in
addition to t:he components (A) and (B). A third or
optional eomponent wnich can be added to the components
(A) and (B) include, ior example, an active hydrogen
30 COIltaillill9 COmpOUIlCI SUCil as i'l~O, metl-lanol, ethanol and
bulanol, an eLectrc>n donatillg compoulld sueh as an etiler,
an ester and an amirle, a hydrocari)yloxy-eontairling
compound such as pihellyl borate, dimetitlylmethoxyaluminum,
phenyl phosphite, tetraethoxysilane and
diphenyldimethoxysilalle, and a Lewis acid sueh as
triphenylborane, tris(pentairluoropilellyl)borane and
triptlelly~ t~ot;ptlille.
16
7 ~ 7
<Polymerization of Olefins>
The catalyst for olefin polymerization according to
the present invention is applied not only to the ordinary
slurry polymerization but also to the liquid phase
5 solvent-free polymerization in which substantially no
solvent is used, the solution polymerization or the vapor
phase polymerization methods. It is also applied to the
fashions or modes of continuous polymerization, batchwise
polymerization or preliminary polymerization. Therefore,
the process for producing olefin polymers according to
the present invention comprises contacting an olefin with
the catalyst i.n the aforementioned polymerization methods
or the polymeriz.ation fashi.ons.
As the polymerizatlon solvent in the case of slurry
15 polymerization, saturated aliphatic or aromatic
hydrocarbons such as hexane, heptane, pentane,
cyclohexane, benzene or toluene are used alone or in
combination. Polymerization is carried out at a
temperature of -78C to about 200C, preferably 0C to
~0 150C, and hydrogen can be used subsidiarily as a
molecular weight modifier. In the case of slurry
polymerization, the component (~) is used preferably in
an amount of ().0001 to 1.0 g per :Li.ter ol. the solvent.
'rhe olefins polymerized ;.n tt-le presellce of the
25 catalyst systc-m according to the presellt invelltion, or in
other words, the olefins to be contacted with the
catalyst according to the present invention for
polymerization, are represented by the formula R-CH=C~2,
wherein R is a hydrogell atom or a hydrocarbyl group
30 having 1 to 10 carbon atoms, whi.ch may or may not be
branched. Specific examples of the olefins include
ethylene, propylene, butene-l, pentene-l, hexene-l, 4-
methylpentene-l and the like, preferably ethylene and
propylene. In the case of the polymerizati.on of these
35 olefins, copolymerization of ethylene with the
aforementioned olefin in an amount of up to 50% by
weight, preferably up to 20~ by weight of ethylene can be
17 ~a~i~7
carried out, and copolymerization of propylene with the
aforementioned olefin, particularly ethylene, il~ an
amount of up to 30% by weight of propylene can be carried
out. Copolymerization of the olefin and the other
5 copolymerizable monomers such as vinyl acetate, cyclic
olefins or diolefins can also be carried out.
EXAMPLE
Example 1
Preparation of the component_~
Ethylenebis(indenyl)zirconium dichloride was
synthesized in accordance with the method described in J.
Orgmet. Chem., (288) 63-67, 1985.
Preparation _ _the component ~
In a 500 ml flask eyuipped with a stirrer and a
reElux condenser wh;ch had been thoroughly purged with
nitrogen, 200 ml of a dilute solution in hexane oE
isobutylalumoxane (manufactured by TOSO-AKZO; molecular
weight: 1,525) (0.06 M based on an aluminum atom) and 50
ml of a dilute sclution in toluene of methylalumoxane
(manufactured by ~OSO-AKZO; molecular weight: l,232)
(0.06 M based on an aluminum atom) were admixed. The
admixture was heated to a temperature of 70C and reacted
for 4 hours. After the reaction was completed, the
solvent was removed by dis(:illation ullder reduced
25 pressure to give I~.l g o a wll i te sJO l; d which was
methylisobutylalumoxane. The whitc solid was dis~olved
in toluene and the ]~C-NMR measurernent was conducted to
give a spectrum illustrated in Fig. l, in which the ratio
of the methyl group to the isobutyl group was 1.16:1.
30 The polymeLizrltion degree or the number of repeating of
Al-0 was 20 determined by the cryoscopic method of
benzene. 'rhe 27Al-NMR measurement was condllcted to give
a spectrum as illustrated in Fig. 2, which had a peak at
a chemical shift of 179 ppm with a half-width of 6196 Hz.
35 _olymeri _tion of propylene
Into a stainless steel autoclave having an internal
volume of :l.0 liter and equipped with a stirrer and a
18 s~o~ ~ (6~
temperature regulator, 400 ml of thoroughly dehydrated
and deoxygenated toluene, the catalyst component (B) of
the present invention in an amount of 4 mmole based on an
aluminum atom and ethylenebis(indenyl)zirconium
S dichloride in an amount of 0.418 mg (0.001 mmole) were
ir,troduced and propylene was polymerized at a propylene
pressure of 7 kg/cm2G and a polymerization temperature of
30C for 4 hours. After the polymerization was
completed, the process product was taken into 3 liters of
10 methanol, and the polymer was filtrated and dried to give
155 g of a product. The gel permeation chromatography of
the polymer gave a number average molecular weight (Mn)
of 25.1 x 103 and a molecular weight distribution as a
ratio of we1ght average molecular weight to number
15 average molecular weight of 1.92. As the 13C~NMR
measurement with JEOL FX-200, the [mm] fraction of triad
was 0.925.
Example 2
Preparation of the component (Bl
Into a 1000 ml flask equipped with a stirrer and a
reflux condenser which had been thoroughly purged with
nitrogen was introduced 100 ml of dehydrated and
deoxygenated toluene. Then, 0.72 g (10 mmole) oE
trimethylaluminum alld 1.96 g (10 InmoLe) oE
triisobutylaluminulll were dissolvell in 5~ ml. o toluelle in
one of two dropping unnels and toluene saturated with
water was introduced into another dropping Eunnel. The
mixed aluminum solution and the saturated water
containing to:Luene were Eed at an equimolar rate of Al
and I~2O over a period o 3 hours. After the Eeeding was
completed, the mixture was heated up to a temperature of
50C and reacted for 2 hours. After the reaction was
completed, the solvent was removed by distillation under
reduced pressure to give 1.9 g of a white solid. The
white solid was dissolved in toluene and the 13C-NMR
measurement was conducted to give a spectrum, in which
the ratio of the methyl group to the isobutyl group was
19
~ rl ~ 7
1:1.35. The polymerization degree was 17. The 27Al-NMR
measurement was conducted to give a spectrum as
illustrated in Fig. 3, which had a peak at a chemical
shift of 174 ppm with a half-width of 5844 Hæ.
5 Polymerization of propylene
Polymerization was carried out under the same
condition as in Example 1 except that the catalyst
component prepared above was used. There was recovered
148 g of a polymer, which had a number average molecular
10 weight (Mn) of 23.7 x 103 and a molecular weight
distribution of 1.95. The stereoregularity was 0.930 by
the ~mm] fraction of triad.
Comparative Examples 1, 2
The component (B) in Example 1 was replaced by a
15 polymethylalumoxane (manufactured by TOSO-AKZO; molecular
weight: 1,232) or a polymethylalumoxane (manufactured by
SCHERING; molecular weight, not specified). The 27Al-NMR
measurement gave spectra ill.ustrated in Figs. ~ and 5,
which had a peak at a chemical shift of 152 ppm with a
half-width of 1690 Hz and a peak at a chemical shift of
154 ppm with a half-width of 1549 EIz. An a-olefin was
polymerized in the same manner as i.n E:xample 1. The
resul.ts are shown .in 'l'able 1
_mpara~1ve Example 3
The component (B) in Example 1 was replaced by a
polyisobutylalumoxalle (rnanufactured by TOSO-AKZO;
molecul.ar weight: 1,525) which gave the 27Al-NM~ spectrum
in l~'ig. 6. An ~x-olefi.rl was polymerized in the same
manner as in Example 1.. 'l'he results are shown in Table
1.
ompar_tive Example 4
An olefin polymer was prepared in the same method as
in Preparation Example 1 in Japanese Patent Laid-Open
Publication No. 247201/1990. That is, in a 500 ml flask
thoroughly purged with nitrogerl were placed 18.0 g of an
isobutylalumoxane (manufactured by TOSO-AKZO; molecular
weight: 1.,525), 3.3 g of trimethylaluminum and 150 ml of
2~7~7
toluene, and after it had been cooled to -10C, 0.83 g of
deaerated water was dropped in the mixture over a period
of 90 minutes. After the mixture was reacted at -10C
for 30 minutes, the temperature of it was raised up to
room temperature over a period of 2 hours. The solvent
of the reaction liquid thus obtained was removed by
distillation under reduced pressure to give l9.1 g of
white solid as a product. The 27Al-NMR spectrum of the
alumoxane is illustrated in Fig. 7, and the results of
the evaluation of the polymerization are shown in Table
1.
Comparative Example 5
_~
An olefin polymer was prepared in the same method as
in Preparation Example 2 in Japanese Patent Laid-Open
Publication No. 247201/1990. That is, in a S00 ml flask
equipped with a stirrer and thoroughly purged with
nitrogen were placed 26.0 g of an isobutylalumoxane
(manufactured by TOSO-AKZO; molecular weight: 1,525),
11.4 g of methylalumoxane and 350 ml of toluene, and
20 after it had been cooled to -10C, 0.53 g of deaerated
water was dropped in the mixture over a period of 1 hour.
After the mixture was reacted at -10C for 30 minutes,
the temperature of it was raised up to room tempe~ature
over a period o 2 h~urs. q'he solvent of the reaction
25 solution thus obtained was removed by distillation undec
reduced pressure to give 30.6 g o an alumoxane as a
product. The 27Al-NMR spectrum of the alumo~ane is
illustrated in Fig. ~, and the results o the evaluation
of the polymeri~ation are shown in Table l.
21 ~ V ~
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O ' N ro rrn~ ~ N
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LJ O O O O O O
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U ,~,~~ Sl ~ O) r~ n cn
~ ~ ~ ~ ~1 ~ ::~ ~ ~
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a.) ~ 3 In r~ O O Co rn
F~ N N N N ~1 r-l
._.. ... _.. ........ .. __ _ .,, _, .,_.. _._ .. . . _ _ __.. __ __ ._ ___ _ . _ _ ._ .. ____.. __
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~r -r -r -r cr
~N) ~ O o o C~ O O
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L, . ~ ~1 ~ ~n ~ ~1 ~o
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OI .C_~ ~O ~r O rn~r O
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r.r~ $ ~1 ~r~n ~O m 'n N __
___ _. _ _----------- 1
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z U ~,~ E. n ~r N ~ ~ ~O Ll
~, r ~ o. r- r 'n Ln ~o ~ m
_.. ________.___ __ ... _ _._ ... .. .. . . , I
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i ''o ';( 0 (~ l l l ~ 1~
a7 E 0 o _t .-1 ..... _
______ ___ __ _, __ _ __ ____ ~D __ j__ _ _ rll O;
vl X o X r ~ t . r 0 -0 u n ~.7 P~
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e 0 0 n~, 1 o ~ 1_ r.~ r~ ~ ~
_. __ ____ ___ .. _ . I W ,,. W W L~ ~ ,w ~
r rD rDCJ rll
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11~ ~D 0 ~D 0 ~D 0 ~D 0 ~D nJ ~D
r ~ ~--1 ~ L~ L~ ~ ~ ~ L~
P. n. 0 o,0 n. 0 o. 0 n. 0 n.
1 r. o. r.D. E~ O. r-. o. r. o. E.
x x ~ o 0xrO 0 ~l r nJ
~.J ~.1 U ~.1 t.) 1~1 tJ ~1 U ~.1 U ~.1
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22 2Q~7~ ~
Example 3
Preparation of the catalyst component (A)
Dimethylsilylenebis(tetrahydroindenyl)zirconium
dichloride was synthesized by the method described in J.
Orgmet. Chem., (342) 21-29, 1988 and J. Orgmet. Chem.,
(369) 359-370, 1989.
Specifically, in a 300 ml flask which had been
thoroughly purged with nitrogen, 5.4 g of
bis(indenyl)dimethylsilane was diluted in 150 ml of
tetrahydrofuran and cooled to a temperature of no higher
than -~0C, and the 23.6 ml of n-butyllithium (1.6
M/liter) was added dropwise to the solution over a period
o 30 minutes. Ater the addition was completed, the
mixture was raised to room temperature over a period of 1
hour and reacted at room temperature for four hours to
give the reaction liquid A.
Into a 500 ml flask purged with nitrogen, 200 ml of
tetrahydrofuran was introduced and cooled to a
temperature of no higher than -50C, and 4.38 g of
zirconium tetrachloride was slowly introduced. After the
total amount of the reaction liquid A was then introduced
into the flask, the mixture was slowly warmed to room
temperature over a period oE 3 hours. After the mixture
was reacted at room temperal.ure ~or 2 hour.q~ i~ wàs
warmed to a te!mperature oE G0~C and furti-her reac~ed or 2
hours. Ater the react iOIl was completed, the solvent was
removed by distillation under reduced pressure, and the
residue was dlssolved in l00 ml of toluene. The solvent
was removed ayain by distillation under reduced pressure
to yive 3.8G y of crude crystals of
dimethylsilylenebis(indellyl)zirconium dichloride.
The crude crystals were then dissolved in 150 ml of
dichloromethane and introduced into a 500 ml autoclave.
After a platinum-on-carbon catalyst (0.5% by weight of
platinum supported on carbon) was introduced into the
autoclave, hydrogenation was conducted under a hydrogen
pressure of 50 kg/cm2G at 50C for 5 hours. After the
23 ~ 0 i67
hydrogenation was completed, the catalyst was removed by
filtration and the solvent was removed by distillation
under reduced pressure. The residue was subjected to
extraction with toluene and recrystalli~ed from a solvent
to give 1.26 g of the dimethylsilylenebis(tetrahydro-
indenyl)zirconium dichloride desired.
Polymerization of propylene
Propylene was polymerized in the same manner as in
Example l except that 0.456 mg (0.001 mmole) of
dimethylsilylenebis(tetrahydroindenyl)zirconium
dichloride obtained above was introduced. The results
are shown in Table 2.
_s~arative F_ mple 6
Propylene was polymerized under the same conditions
as in Example 3 except that 0.001 g of the component (A)
in Example 3 and 4 mmole of methylalumoxane (manufactured
by TOSO-AKZO) were used. The results are shown in Table
2.
_ample 4, Comparative Example 7
Preparation of the component (Al
Preparation of isopropylidene(cyclopentadienyl)-
(Eluorenyl)zirconium dichloride
After 200 ml o~ THF and 16.5 g oE Eluorene weee
introduced into a 50() ml f:Lask purged wlth nitrogen and
cooled to a temperature oE no higher thàn -50C, ~/ ml o
a dilute solut:ion in diethyl ether o methyllithium (1.~
mole) was added dropwise over a period oE 30 minutes and
the mixture was slowly warmed to room temperature and
reacted or 3 hours. A~ter the mixture was cooled again
to a temperature of at least -50C, 10 g of 6,6-
dimethylfulvene was added dropwise to the mixture over a
period of 30 minutes. After the addition was completed,
the mixture was warmed to room temperature and reacted
for two days. After the reaction was completed, 60 ml of
H2O was added to stop the reaction, and the ether layer
was separated and dried over anhydrous MgSO~. The
~4 ~ d ~~ 7
solvent was evaporated to dryness to give 17.6 9 of crude
crystals of 2-cyclopentadienyl-2-fluorenylpropane.
Next, 10 g of the aforementioned crude crystals were
dissolved in 100 ml of THF and cooled to a temperature of
no higher than -50C, and 46.0 ml (0.0736 mole) of n-
butyllithium was added dropwise over a period of 10
minutes. The mixture was warmed to room temperature over
1 hour and reacted at the temperature for 2 hours. After
the solvent was evaporated to dryness under nitrogen
stream, 1~0 ml of dichloromethane was added and the
mixture was cooled to a temperature of no higher than
-50C. A solution of 8.16 g of zirconium tetrachloride
in 50 ml of dichloromethane prepared at a lower
temperature was then poured in lump into the mixture.
15 After mixing, the resulting mixture was slowly warmed to
room temperature over a period of 3 hours and reacted at
room temperature for one day. After the reaction was
completed, solids were removed by filtration and the
filtrate was concentrated and recrystallized from a
solvent to give 4.68 g of isopropylidene-
(cyclopentadienyl)(fluorenyl)zirconium dichloride as a
red product.
Polymerization of propYlene
Polymerization was conducted in the same manner as
in Example 3 and Comparative Example 6 except that the
aforementioned component (A) was used. The results are
shown in Table 2.
Example 5
Polymerization of ethYlene
After a stainless steel autoclave having an internal
volume of 1.5 liters and equipped with a stirrer and a
temperature regulator was thoroughly purged with
ethylene, 500 ml of thoroughly dehydrated and
deoxygenated n-heptane was introduced into the autoclave
and ~ mmole of the component (B) obtained in ~xample 1,
0.46 mg (0.001 mmole) of the component (A3 obtained in
Example 3 and 300 cc of hydrogen were next introduced.
25 ~ 7
Then, polymerization was conducted under an ethylene
pressure of 7 kg/cm2G at 75C for 2 hours. The results
are shown in Table 2.
Comparative Example 8
Polymerization was conducted under the same
conditions as in Example 5 except that methylalumoxane of
TOSO-AKZO was used in place of the component (B). The
results are shown in Table 2.
_omparative Examples 9, 10
Polymerization was conducted under the same
conditions as in Example 3 and Comparative Example 6
except that the component (A) used in these runs was
replaced respectively by bis(cyclopentadienyl)zirconium
dichloride. The results obtailled are shown in Table 2.
~5
3()
26
O o ~E rl ~ -- I` ~ _ z
o _O ~o o _O o
C - _ _ _ _
'~ C ~ Q (n N r-- a~ ~ ~
~ ~ t'l N ~ N ~ ~D ~D
0 3 ~" _ _~ ~`J ~`J N r~ N _I ~1
. __ __ _
n " U ~ c o o o N O N O N
_
~-
V :~ O O O O o O NO o
V o V N ~D N O O O _1
O _ 01
P. _
~1 CJ ~ C
~I O :>~ N ~ ~:) ~ ~ ~ ~
11~ C ~ 1 Cl~ O .o ~o .C .cl a, o
O ~0 ~ O r~ r~ . ~J . O
~ al r~ C m r~ C ~ _~ ~ m -~
C~ ~ E3 ~ C Cl~ X O ~J c~ E3 ~ C Cl- E3
~, E r~ I C EX 1~l C ~ ~ O E r-l I
W r1 ~ r 1 1~ r~ CL 14 ~ O
Cl~ E3 ~ .C ~ E3 c~ C E~ ~ a .c ~ t! ~ ~
~ U _ __ _ __.. _ .. . ~______ ____ _ _ _ U
_ __ I
', ' ~ , e ~ _
r~ I r~ . rl r~
a ~u c O ~ ~ CO 'a~ c o ~ o
_ ~ al al C ~ r~
oJ ~ ~ ~, ~. ~ a~ ~ C ~ ~
C r~ c u 'CJ I ~a ~ r r~ i~ ~ E E ~r
C~ ~ h ~ a~ rl ~ ~
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t~ V U ~ ~ e ~ ,. v u
rl V rl U ~ .~ IJ .rl U1 ~r1
a _ N _ n _ N . rl N
_._ _ __ _ _ m
~ C~ aJ ~ ~o
~ rl ~D ~ rl 1~ ~n rl ¢~ .~1 J.
_l d Cl r~ h ~ r~ h r~ Id I I h ~
Q. n~ Cl, O, ~ C~ C~. Il~ Cl, a~ Ql ~d Cl,
e ~ e E ~ e. E. ~ e c~- E O~ E
~ e d ~ E. Ia /~ E al E3 n~ E3 ~
_ ~1 _ _U ~ _~ U W X U ~-i U W U ~
____ __ _ _ __ _ .
27 ~ r~ 7
Example 6
Polymerization of ethylene/l-hexene
After a stainless steel autoclave having an internal
volume of 1.5 liters and equipped with a stirrer and a
temperature regulator was thoroughly purged with
ethylene, 415 ml of thoroughly dehydrated and
deoxygenated n-heptane and 85 ml of hexene were
introduced into the autoclave. Then, 3 mmole of the
component (B) obtained in Example 1 and 0.~6 mg (0.001
mmole) of the component (A) obtained in Example 3 were
introduced, and polymerization was conducted under an
ethylene pressllre of 7 kg/cm2G at 70C for 2 hours.
~Eter the polymerization was completed, 50 m]. of ethanol
and 500 ml of water were added to the slurry obtained,
and the organic layer was dried by evaporation to give
52.6 g of a polymer. Therefore, the polymerization
activity of the catalyst was 114,300 (g polymer/g
catalyst), the number average molecular weight was
57,000, Mw/Mn - 2.62, and melting point was 107.2C.
Example 7
Polymerization of ProPylene/l-hexene
Into a stainless steel autoclave having an internal
volume of 1.0 liter and e~uipped with a stirrer and ~
temperature regulator, 4U0 m:l of thoroughly dehydrated
and deoxygenated toluene, 10 ml o l-hexene, ~ tnmoles
based on an aluminum atom o the component (B) obtained
in Example 1 and 0.418 mg (0.001 mmole) oE
ethylenebi6(itldetlyl)æirconium dichloride were introduced
into the autoclave, and polymerization was conducted
under an ethylene pressure oE 5 kg/cm2G at a
polymerization temperature oE 50C Eor 2 hours. After
the polymerization was completed, the process product was
taken into methanol and the polymer was separated by
filtration and dried. ~s a result, the polymer was
recovered in an amount oE 121.3 g. Gel permeation
chromatoyraphy conducted on the polymer gave the number
average mo]ecular weight (Mn) of 18.7 x 103 and the
28 ~ f ~ 7
molecular weight distribution as the ratio of weight
average molecular weight/number avera~e molecùlar weight
of 1.78. The [mm] fraction of triad was 0.841 and the
hexene content was 3.4% by mole.
Example 8
In a 500 ml autoclave was introduced a solution in
150 ml of 2.0 g of ethylenebis(indenyl)zirconium
dichloride obtained in Example 1. 5 g of a catalyst of
platinum-on-carbon containing 0.5% by weight of platinum
was introduced, and hydrogenation was conducted under a
hydrogen gas pressure o~ 50 kg/cm2G at 50C for 5 hours.
After the reaction, the catalyst was removed and the
solvent was distilled o~ ln vacuo, and the residue was
subjected to extraction with toluene and then to re-
crystallization, whereby 1.7 g oE ethylenebis(4,5,6,7-
tetrahydroindenyl'zirconium dichloride was recovered.
1.~ g of the crystal thus recovered was dissolved in
200 ml of tetrahydrofuran and cooled to -50C. 10 mmol
of methyllithium diluted in diethylether was added
thereto, fo]lowed by warming to room temperature over 1
hour and then by reaction at room temperature for 8
hours. After the reaction, the solvent was distilled off
in vacuo, the residue was subjected to ext-raction with
toLuene, ollowed by re--cryst:a:lliz.rlt;oll, wllereby 0.9 tJ oE
ethylenebis(~,~,6,'/-t~t:rahydroilldenyl)zirconium dimethyL
was obtained.
Polymerization of propylene was conducted in the
same manner as in Exalllple ] except that the component (A)
thus obtained was used.
Ttle result obtained was StlOWIl ;n Table 3.
Comparative Example 11
Polymerization o propylel~e was conducted in the
same manner as in Comparative RxampLe 1 except that the
component (A) prepared in Example 8 was used.
The result obtained is shown in Table 3.
g ~ ~
2g
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,
~ o o
r~ ~ ~ ~ ~ ra
~ co ~ ~ ~ ~
~ o o ~ o .~
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