CA2060767A1 - Production of .alpha.-olefin polymers - Google Patents
Production of .alpha.-olefin polymersInfo
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- CA2060767A1 CA2060767A1 CA 2060767 CA2060767A CA2060767A1 CA 2060767 A1 CA2060767 A1 CA 2060767A1 CA 2060767 CA2060767 CA 2060767 CA 2060767 A CA2060767 A CA 2060767A CA 2060767 A1 CA2060767 A1 CA 2060767A1
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Abstract
ABSTRACT OF THE DISCLOSURE
A catalyst for .alpha.-olefin polymerization which comprises the following components (A) and (B):
component (A), which is a transition metal compound represented by the formula Q(C5H4-mR1,n) (C5H4-nR2n)MeXY
wherein (C5H4-mRlm) and (C5H4-nR2n) respectively represent a conjugated five-membered ring ligand coordinating to a metal Me; R1 and R2, which may be the same or different and a plurality of each of which can be bonded together, respectively represent a hydrocarbyl group having l 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-containing hydrocarbyl group; Q
represents a bonding group which crosslinks the two conjugated five-membered ring ligand; Me represents a transition metal of the IVB-VIB group in the Periodic 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 phosphorus-containing hydrocarbyl group or a silicon-containing hydrocarbyl group; m denotes an integer of O
< 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 being in the range of 4:1 to 1:4, (b) the chemical shift of 27Al-NMR
being in the range of 160 ppm to 250 ppm and the peak having 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 100. The methylisobutylalumoxane is assumed to be novel.
A catalyst for .alpha.-olefin polymerization which comprises the following components (A) and (B):
component (A), which is a transition metal compound represented by the formula Q(C5H4-mR1,n) (C5H4-nR2n)MeXY
wherein (C5H4-mRlm) and (C5H4-nR2n) respectively represent a conjugated five-membered ring ligand coordinating to a metal Me; R1 and R2, which may be the same or different and a plurality of each of which can be bonded together, respectively represent a hydrocarbyl group having l 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-containing hydrocarbyl group; Q
represents a bonding group which crosslinks the two conjugated five-membered ring ligand; Me represents a transition metal of the IVB-VIB group in the Periodic 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 phosphorus-containing hydrocarbyl group or a silicon-containing hydrocarbyl group; m denotes an integer of O
< 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 being in the range of 4:1 to 1:4, (b) the chemical shift of 27Al-NMR
being in the range of 160 ppm to 250 ppm and the peak having 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 100. The methylisobutylalumoxane is assumed to be novel.
Description
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 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~ Al--O ) p-l~ Al~O~qAl-R3 ( I ) or (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.
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 ~ 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.
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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.
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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.
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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 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~ Al--O ) p-l~ Al~O~qAl-R3 ( I ) or (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.
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 ~ 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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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.
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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.
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Claims (25)
1. A catalyst for .alpha.-olefin polymerization which comprises the following components (A) and (B):
component (A), which is a transition metal compound represented by the formula Q(C5H4-mR1m)(C5H4-nR2n)MeXY
wherein (C5H4-mR1n) and (C5H4-nR2n) respectively represent a conjugated five-membered ring ligand coordinating to a metal Me; R1 and R2, which may be the same or different and a plurality of each of 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-containing hydrocarbyl group; Q
represents 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 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 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 27Al-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 Al-O in an amount of 2 to 100.
component (A), which is a transition metal compound represented by the formula Q(C5H4-mR1m)(C5H4-nR2n)MeXY
wherein (C5H4-mR1n) and (C5H4-nR2n) respectively represent a conjugated five-membered ring ligand coordinating to a metal Me; R1 and R2, which may be the same or different and a plurality of each of 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-containing hydrocarbyl group; Q
represents 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 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 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 27Al-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 Al-O in an amount of 2 to 100.
2. The catalyst for .alpha.-olefin polymerization according to Claim 1, wherein the groups (C5H4-mR1m) and (C5H4-nR2n) of said transition metal compound are the same.
3. The catalyst for .alpha.-olefin polymerization according to Claim 1, wherein the groups (C5H4-mR1m) and (C5H4-nR2n) are selected from the group consisting of substituted or non-substituted cyclopentadienyl, indenyl and fluorenyl groups, respectively.
4. The catalyst for .alpha.-olefin polymerization according to Claim 1, wherein Q is (a) a lower alkylene group or a cycloalkylene group which may or may not have a substituent that is an alkyl, alicyclic and/or aromatic group and has 1 to 15 carbon atoms, (b) a silylene or oligosilylene group which may or may not have a substituent that is an alkyl, alicyclic and/or aromatic group and has 1 to 12 carbon atoms, and (c) a hydrocarbyl group containing therein an element selected from the group consisting of germanium, phosphorus, nitrogen, boron and aluminum.
5. The catalyst for .alpha.-olefin polymerization according to Claim 4, wherein Q is a lower alkylene group which may or may not have a substituent that is an alkyl, alicyclic and/or aromatic group and has 1 to 15 carbon atoms or a silylene or oligosilylene group which may or may not have a substituent that is an alkyl, alicyclic and/or aromatic group and has 1 to 12 carbon atoms.
6. The catalyst for .alpha.-olefin polymerization according to Claim 1, wherein Me is a transition metal of the IVB to VIB group.
7. The catalyst for .alpha.-olefin polymerization according to Claim 6, wherein Me is titanium, zirconium or hafnium.
8. The catalyst for .alpha.-olefin polymerization according to Claim 1, wherein X and Y contain 1 to 20 carbon atoms when they have a hydrocarbyl moiety, respectively.
9. The catalyst for .alpha.-olefin polymerization according to Claim 1, wherein the methylisobutylalumoxane is represented by the following formula (I) or (II):
(I) (II) wherein R3 and R4 represent a methyl group or an isobutyl group, respectively, the methyl group and the isobutyl group being arranged in block or at random in the molecule; p and q denote an integer of at least 1, respectively, the sum of p+q being in the range of 2 to 100; and the ratio of p to q is in the range of 4:1 to
(I) (II) wherein R3 and R4 represent a methyl group or an isobutyl group, respectively, the methyl group and the isobutyl group being arranged in block or at random in the molecule; p and q denote an integer of at least 1, respectively, the sum of p+q being in the range of 2 to 100; and the ratio of p to q is in the range of 4:1 to
10. The catalyst for .alpha.-olefin polymerization according to Claim 9, wherein the sum of p+q is in the range of 4 to 50.
11. The catalyst for .alpha.-olefin polymerization according to Claim 9, wherein the sum of p+q is in the range of 8 to 20.
12. A process for preparing an .alpha.-olefin polymer comprising bringing an .alpha.-olefin into contact with a catalyst for .alpha.-olefin polymerization comprising the following components (A) and (B):
component (A), which is a transition metal compound represented by the formula Q(C5H4-mR1m)(C5H4-nR2n)Mexy wherein (C5H4-mR1m) and (C5H4-nR2n) respectively represent a conjugated five-membered ring ligand coordinating to a metal Me; R1 and R2, which may be the same or different and a plurality of each of 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-containing hydrocarbyl group; Q
represents 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 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 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;
c o m p o n e n t ( B ) , w h i c h i s 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 27Al-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 Al-O in an amount of 2 to 100.
component (A), which is a transition metal compound represented by the formula Q(C5H4-mR1m)(C5H4-nR2n)Mexy wherein (C5H4-mR1m) and (C5H4-nR2n) respectively represent a conjugated five-membered ring ligand coordinating to a metal Me; R1 and R2, which may be the same or different and a plurality of each of 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-containing hydrocarbyl group; Q
represents 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 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 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;
c o m p o n e n t ( B ) , w h i c h i s 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 27Al-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 Al-O in an amount of 2 to 100.
13. The process for preparing an .alpha.-olefin polymer according to Claim 12, wherein the groups (C5H4-mR1m) and (C5H4-nR2n) of said transition metal compound are the same.
14. The process for preparing an a-olefin polymer according to Claim 12, wherein the groups (C5H4-mR1m) and (C5H4-nR2n) are selected from the group consisting of substituted or non-substituted cyclopentadienyl, indenyl and fluorenyl groups, respectively.
15. The process for preparing an .alpha.-olefin polymer according to Claim 12, wherein Q is (a) a lower alkylene group or a cycloalkylene group which may or may not have a substituent that is an alkyl, alicyclic and/or aromatic group and has 1 to 15 carbon atoms, (b) a silylene or oligosilylene group which may or may not have a substituent that is an alkyl, alicyclic and/or aromatic group and has 1 to 12 carbon atoms, and (c) a hydrocarbyl group containing therein an element selected from the group consisting of germanium, phosphorus, nitrogen, boron and aluminum.
16. The process for preparing an .alpha.-olefin polymer according to Claim 15, wherein Q is a lower alkylene group which may or may not have a substituent that is an alkyl, alicyclic and/or aromatic group and has 1 to 15 carbon atoms or a silylene or oligosilylene group which may or may not have a substituent that is an alkyl, alicyclic and/or aromatic group and has 1 to 12 carbon atoms.
17. The process for preparing an (Y-olefin polymer according to Claim 12, wherein Me is a transition metal of the IVB to VIB group.
18. The process for preparing an .alpha.-olefin polymer according to Claim 17, wherein Me is titanium, zirconium or hafnium.
19. The process for preparing an .alpha.-olefin polymer according to Claim 12, wherein X and Y contain 1 to 20 carbon atoms when they have a hydrocarbyl moiety, respectively.
20. The process for preparing an .alpha.-olefin polymer according to Claim 12 , wherein the methylisobutylalumoxane is represented by the following formula (I) or (II):
(I) or (II) wherein R3 and R4 represent a methyl group or an isobutyl group, respectively, the methyl group and the isobutyl group being arranged in block or at random in the molecule; p and q denote an integer of at least 1, respectively, the sum of p+q being in the range of 2 to 100; and the ratio of p to q is in the range of 4:1 to 1:4.
(I) or (II) wherein R3 and R4 represent a methyl group or an isobutyl group, respectively, the methyl group and the isobutyl group being arranged in block or at random in the molecule; p and q denote an integer of at least 1, respectively, the sum of p+q being in the range of 2 to 100; and the ratio of p to q is in the range of 4:1 to 1:4.
21. The process for preparing an .alpha.-olefin polymer according to Claim 20, wherein the sum of p+q is in the range of 4 to 50.
22. The process for preparing an .alpha.-olefin polymer according to Claim 20, wherein the sum of p+q is in the range of 8 to 20.
23. A methylisobutylalumoxane which satisfies the following conditions:
(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 width of no smaller than 3000 Hz, and (c) it has a repeating unit of Al-O in an amount of 2 to 100.
(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 width of no smaller than 3000 Hz, and (c) it has a repeating unit of Al-O in an amount of 2 to 100.
24. The methylisobutylalumoxane as claimed in claim 23, as combined with a compound of the group IVB to VIB
of the Periodic Table having at least one .pi. electron conjugated ligand to form a catalyst for polymerization of .alpha.-olefins.
of the Periodic Table having at least one .pi. electron conjugated ligand to form a catalyst for polymerization of .alpha.-olefins.
25. The methylisobutylalumoxane as claimed in claim 24, wherein the compound of the group IVB to VIB of the Periodic Table has a formula:
Q(C5H4-mR1m) (C5H4-nR2n)MeXY
wherein (C5H4-mR1m) and (C5H4-nR2n) respectively represent a conjugated five-membered ring ligand coordinating to a metal Me; R1 and R2, which may be the same or different and a plurality of each of 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-containing hydrocarbyl group; Q
represents 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 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 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.
Q(C5H4-mR1m) (C5H4-nR2n)MeXY
wherein (C5H4-mR1m) and (C5H4-nR2n) respectively represent a conjugated five-membered ring ligand coordinating to a metal Me; R1 and R2, which may be the same or different and a plurality of each of 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-containing hydrocarbyl group; Q
represents 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 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 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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16583/1991 | 1991-02-07 | ||
| JP3658391A JPH04256809A (en) | 1991-02-07 | 1991-02-07 | Area type flowmeter |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2060767A1 true CA2060767A1 (en) | 1992-08-08 |
Family
ID=12473796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2060767 Abandoned CA2060767A1 (en) | 1991-02-07 | 1992-02-06 | Production of .alpha.-olefin polymers |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH04256809A (en) |
| CA (1) | CA2060767A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5028709B2 (en) * | 2001-02-08 | 2012-09-19 | パナソニック株式会社 | Flow measuring device |
| JP2010243245A (en) * | 2009-04-02 | 2010-10-28 | Tokyo Keiso Co Ltd | Ultrasonic flow meter |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS538672A (en) * | 1976-07-13 | 1978-01-26 | Nitto Electric Ind Co | Method of hydrophilization of formed product of plastic |
| JPS543169A (en) * | 1977-06-09 | 1979-01-11 | Matsushita Electric Ind Co Ltd | Resin surface treating agent |
| EP0025809A1 (en) * | 1979-09-21 | 1981-04-01 | BBC Aktiengesellschaft Brown, Boveri & Cie. | Liquid crystals mixture |
| JPS5775731A (en) * | 1980-10-30 | 1982-05-12 | Hitachi Seiko Ltd | Discharge processing condition setting device |
-
1991
- 1991-02-07 JP JP3658391A patent/JPH04256809A/en active Pending
-
1992
- 1992-02-06 CA CA 2060767 patent/CA2060767A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04256809A (en) | 1992-09-11 |
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