CA2069602A1 - Process for the preparation of polyolefins having a broad molecular weight distribution - Google Patents
Process for the preparation of polyolefins having a broad molecular weight distributionInfo
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- CA2069602A1 CA2069602A1 CA002069602A CA2069602A CA2069602A1 CA 2069602 A1 CA2069602 A1 CA 2069602A1 CA 002069602 A CA002069602 A CA 002069602A CA 2069602 A CA2069602 A CA 2069602A CA 2069602 A1 CA2069602 A1 CA 2069602A1
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- rac
- indenyl
- group
- methyl
- dichloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/09—Cyclic bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is part of a cyclic group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Abstract
ABSTRACT OF THE DISCLOSURE
Process for the preparation of polyolefins having a broad molecular weight distribution Polyolefins having a molecular weight distribution Mw/Mn of ? 3 and which may be monomodal, bimodal or multimodal are obtained by polymerization or copolymerization of olefins of the formula RCH=CHR, in which a catalyst system comprising an aluminoxane and a transition-metal component (metallocene) is used, the transition-metal component comprising at least one zirconocene of the formula I
Process for the preparation of polyolefins having a broad molecular weight distribution Polyolefins having a molecular weight distribution Mw/Mn of ? 3 and which may be monomodal, bimodal or multimodal are obtained by polymerization or copolymerization of olefins of the formula RCH=CHR, in which a catalyst system comprising an aluminoxane and a transition-metal component (metallocene) is used, the transition-metal component comprising at least one zirconocene of the formula I
Description
~O~CHST A~TI~ESELLSCHAFT - HO~ 9lJF 158 ~r. LO/St Description Proce~s for the preparation of polyolefins having a broad molecular weight distrihution It is known that metallocene catalyst~ in combination with al~Dminoxanes are capable of polymerizing olefi~s to give polyolefins ha~ing a narrow molecular weight di~-tribution (~,,,/M" of 2-3 ) ( J . Pol~n. Sci ., Pol . t:hem . Ed .
23 (1985) 2117; EP-A 302 424). Polyolefins of thi~ type : 10 with a narrow distribution are suitable, for example, for applications in preoision in~ection molding, injection molding in general and for the production vf fiber~. For numerous applicatio~s, 6uch as, for example, thermo-fonmingr extru~ion, blow molding and for the production of polyolefin fOam6 and films, broader or bimo~al molecu-: lar weight distributions are required.
' .
For polyethylene, it has been proposed to a~hieve such products by using two or moxe metallocene cataly~ts in the polymerization (EP-A 128 045); however, the sy6tems described are achiral ca~aly~ts and would give atactic polypropylene on polymermization of propene. However, ~, atactic polypropylene is unsuitable a~ a structuxal material.
:~' The preparation of stereoblock polypropylen0 where ~/M~
is 13-15 is disclosed in DE-A 3 640 924. These cataly~t systems are likewise unsuitable for the formation ~f polyolefins of high tacticity. Furthermore, the metallocene activitie~ which can be achieved at indus-:~ trially relevant polymerization temperatures and the ~: 30 molecular weights of polymer product~ axe too low. In addition, the proposed catalyst~ give only an atactic ., : polymer at such polymerization temperatures.
;, EP-A 310 734 proposes catalyst systems comprising a ', 2 ~
mixture of a hafnocene and a zirconocene for the prepara-tion of polypropylene. Products have broad to bimodal distributions where N~/N~ is from 3.7 to 10.3 If only the hafnocene catalyst is used, polypropylene with a broad di~tribution is obtai.ned at a csrtain polymerization temperature, according to EP A 355 439.
Syndiotactic polypropylene having a broad distribution is described in EP-A 387 691 (M~/M~ up to 6.4) if a hafnocene is used.
These proce~ses have the comm~n disadvantages of hafnium catalyst costs which are ~oo high for indu~trial applica tions, together with a low polymerization activity, which additionally makes it necessary to carry out thorou~h, ~: high-cost purification o the prepared polymer to remove cataly~ residues.
The object was thus to find a catalyst ~ystem and a proces~ by means of which polyolefin~ ha~ing a broad, bimodal or multLmodal distriblltion can be prepared and ; which avoid the disadvantages known from the prior art.
.
20 The object is achieved by using a catalyst system com-.~; prising at lea~t two ætereorigid zirconocenes and an aluminum compound as cocatalyst.
The invention thus xelates to a process for the prepara-tion of a polyolefin which has a molecular weight dis-~:: 25 tribution N~lN~ of ~ 3.0 and which may be monomodal, bimodal or mult~nodal, by polymerization or copol~nerization of an olefin of the formula R~C~=CHRb in which R~ and Rh are identical or different and a hydro-~ ge~ atcm or a alkyl radical having 1 to 14 carbon atom~, i 30 or R~ and Rb, together with the atoms connecting them, can .: ~orm a ring, at a tempera~ure of from -60 to 200C, at a ~; pressure of from 0.5 to 100 bar, in solution, in suspen-sion or in the gas phase, in the presence of a catalyst . ~ ~
:
.. 2 ~ ? ` .
comprising a ~ransi~iGn-metal component (metallocene) and an aluminoxane of the formula II
_ ~Al--O ~ Al - O ~ R
n R
.~
for the linear type a~d/or of the for~lula III
tAl - 0~ (III) for the cyclic type, where, in the formulae II and III, the radicals R may be identical ~r different ~nd ~re a C1-C6-alkyl group, a Cl-C6-fluoroalkyl group, a C6-C1g-aryl group, a C1-C6~1uor~yl ~roup or a hydrogen, and n is an . 10 integer from O to 50, or~ tead o khe aluminoxane, ~, compri~es a mixture of an aluminoxane o~ the formula II
`' and/or of the ~crmula III with a compound AlR3, ~hich eomprises using, a~ the transition-metal component, at :. ; least one zirconocene of the formula I and st least one ~ 15 zirconocene of ~he formula Ia or alternatively at least ~:
'~ 2 zirconocenes of the formula I
~', ~
(j~ R ~mR14 _ ~CR8R9)m R1 Zr ~ _!C~6B9)~ - IL8R8~n ,~ :
, , ~ 4 _ 2~ 2 in which 1 and R2 are identical or different and are a hydrogen atom, a c1-C10-alkyl qrou~, a C1-C10-alkXY ~roup~
a C6-C10-arYl group, ~ C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C4o-arylalkyl group, a C7-C40-alkylaryl group, a Cg-C40-arylalkenyl group or a halogen atom, R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, a C1-C1o-alkyl group, which may ~e halogenated, a C6-C1o-aryl gr~up, or a -NR210, -SR10, -OSiR310, -SiR310 or -PR210 radical, in which R~ is a halogen atom, a C1-C10-alkyl group or a C6-C1o-aryl group, Rs and R6 are identical or dif~r~n$ ~nd are ~ defined for R3 and R4~ with the proviso that R5 ~nd R~ are j not hydroge~, is -M' -.-M1 ~7 - M~ . -M' ~ (t:Fl2'3) - ' O ' M' ~ 0 R'~ R12 p~2 Rl2 R'l ~M~ - .
` p~12 R12 .
.
.
_AlR~ Sn, -O-, -S- l ~S~:~, =S~2, l~R , ~ IzPRll or =P ( O ) Rll, ' where R11, R12 and Rl3 are identical ~r different and are a hydro-gen atom, a halogen atom, a C1-C1o-alkyl group, a C1-C1o-~:, I, .:: : . . :
, . : ~
2~$~
fluoroalkyl group, a C6-C10-aryl group, a C6-C10-fluoro-aryl group, a C1-C10-alkoxy group, a C2-C1o alkenY
group, a C7-C,~o-arylalkyl ~roup, a C~-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R11 and R12 or . R11 and R13, toge~her with the atoms connecting them, : in each case form a ring, and Ml i~ silicon, germanium or tint Ra and R9 are identical or diffQrent and are ~ defined for R11, ~`
Rl4 and ~15 are identical or di~f~arent and are a mono~clic or polycyclic hydrocarbon radical which can form a ~; sandwich structure together with khe zirconium atom, and ~ .
.~. m and n are identical or di~ferent and are ~ero, l or~
. 2, wh~re m plu~ n i~ ~ero, 1 or ~.
~, ~,~
Alkyl i8 ~traight~hain or branched alky~l. Halo~en `l ~ thalogenated) refer~ t~ flu~rlne, chlosine, bromin~a or ? ~`, iodin~, preferably fluorine or chlorine.
R1 and R2 are identical or different and are a hydrogen atom,: a C1-C10-, preferably C1-C3-alkyl qroup, a C1-C10-, preferably C1-C3-alkoxy group, a C6-C10-, preferably C6-Cg-aryl group, a C6-C1Q-, prefera-ly C6-Cg-aryloxy group, :: : a C2-C10-, preferably C2-C4-alkenyl groupj a C7-C40-, preferably C7-C1o-arylalkyl group, a C7-C40-, preferably C7-C12-alkylaryl group, a Cg-C40-, preferably Cg-C12-arylalkenyl group, or a halogen atom, preferabyl chlorine.
,~, :
R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, prefera-ly fluorine, chlorine or ~l bromine atom, a C1-C10-, preferably C1-C4-alkyl group, l. which may be halogenated, a C6-C10-~ preferably C6-C8-aryl group, a -NR210, -SR10, -OSiR310, -SiR310 or -PR210 radical in which R10 is a halogen atom ~referably a chlorine atom, J~
": ~ :
r;`;~
2 ~
or a C,-C10-, preferably Cl-C3-alkyl group or a C6-~lo~, preferably C6-C~-aryl group. R3 and R4 are particularly preferably hydrogen.
Rs and R6 are identical or differen~ prefexably identi-cal, and are as defined for R3 and R4, with the provi~o that R5 and R6 cannot be hydro~en. R5 and R6 are preferably (Cl-C~)-alkyl, which may be halo~enatecl, ~uch a6 m~thyl r ethyl, propyl, isopropyl, butyl, isob~ltyl or trifluoro-methyl, in particular methyl.
R7 is ~l~ R11 R"
- M' -, -M'-- M' - ,-M' ~ a~R t3~ .0~_ M7~0 p~12 R12 R12 Rl2 R'~
R"
O- M'-Rl2R12 .
=BR , =AlRll, -Ge-, -Sn, -O-, -S-, =SO, =SO2, =NRll, =CO, =PR11 or =P(O)R11, where Rl1, Rl2 and Rl3 are id~ntic~l or different and are hydrogen atoms, halogen ato~s, a C1-C1o-, -~; preferably C1-C4-alkyl group, in particular methy1 group, a C1-C10-fluoroalkyl group, pre~erably CF3 group, a C6 C10-, preferably C6-Cg-aryl group, a C6-C10-fluoroaryl group, preferably penta~luorophenyl group, a C1-C10-, preferably C1-C4-alkoxy group, in particular methoxy group, a C2 C10-l preferably C2-C4-alkenyl group, C7-C40-, preferably C7-C10-~ arylalkyl group, a C8-C40-, preferably C8-C12-arylalkenyl .. group, or a C7-C40-, preferably C7-C12-alkylaryl group, or :~ R11 and R12 or R11 and R13, toqether with the atom~ connecting I them, in each case form a ring.
~ M1 is silicon, germanium or tin, preferably silicon or :;
.
. ~ , . . . .
g germanium.
R7 is preferably =CR1'R12, =SiR1'R1~, =GeR11R'2, O-, -S-, =SO, =PR" or =P(O)R'1.
R8 and R9 are identical or different and are as defined for Rll.
m and n are identical or different and are ~ero, 1 or 2, preferably zero or 1, where m plus n i~ zero, 1 or 2, preferably zero or 1.
R14 and R15 are prefera~ly fluorenyl, indenyl or cyclo-pentadienyI, it being possihle for these parent ~truc-tures also to carry additional substituents as defined f Qr Rll .
: Particularly preferred metallocenes are thu~ tho~e in which, in the formula I, R1 and R2 are identical or lS different and are methyl or chlorine, R3 and R4 are hydrogen, R5 and Rs are identical or di~ferent and are ` methyl, ethyl or tri~luoromethyl, R7 i8 a R~
or -Sl~ radical, and n plus m is 2ero or 1, in ~ p~12 Rt2 particular the compounds listed in the working example~.
Of the compounds I mentioned in the working examples, rac-dimethyl~ilyl(2-methyl-l-indenyl)2zirconium dichloride, rac-ethylene(2-methyl-1-inden~1)2zirconium dichloride, rac-diphenylsilyl(2-methyl-1-indenyl)2zirconium dichloride, rac-methylethylene(2-methyl-l-indenyl~2zirconium dichloride and rac-phenyl(methyl) 9ilyl ( 2-methyl-l-indenyl)2zirconium dichlorid~ are of particular Lmportance.
:. .
.~
: , 2 ~ 3 ro~
-- 8 ~
~he particularly preferred metallocenes of the formula la are those in which Rl and R2 are identical or different and are methyl or chlorine, R~
R7 is a ~ C~ or _~ radical bl2 R12 p~
n ~ m i~ zero or 1 and and R15 are identical vr different and are fluorenyl, indenyl or sub~tituted cyclopentadienyl, in particular the compounds la listed in the working example~.
9~ particular importance are ~h~s rac-phenyl(methyl)-silyl(indenyl) 2zirconium dichloride, diphenylmethyl~ne~9-fluorenyl)(cyclopentadienyl)zirconiumdichloride,i~opro-pylidene(g-fluorenyl)~cyclopen~adienyl)zirconium dichloride, rac-dimethylsilyl(2,3,5-~rimethyl-1-cyclopen-tadienyl~2zirconium dichloride, rac-dimethylsilyl-. 15 (indenyl)2zirconium dichloride, rac-dimethylgermyl-- (indenyl)2zirconium dichloride, rac-d~methyl~ilyl-(indenyl)2dimethylzirconium, rac-phenyl(v~nyl) 5ilyl -(indenyl)2~irconium dichloride, rac-~2C-CH2-CH2~
(indenyl)2zirconium dichloride, rac~dimethylsilyl(2,4-. 20 dimethylcyclopentadienyl)2zixconium dichloride, rac-~; isopropylidena(indenyl)2~irconium dichloride, rac-dimethylsilyl(2-methyl-4 r 5 ~ 6 / 7-tetrahydro-1-indenyl) 2-.. zirconium dichloride, rac-ethylene(indenyl)2zirconium -dichloride,rac-methyl~ne~3-t-butyl-1-cyclopenkadienyl) 2-zixconium dichloride and rac-dimethylsilyl(4,7-dimethyl-: 1-indenyl)2zirconium dichloride.
~ The metallocene~ having C~ symmetry ~subgroup o~ com-: pound~ of the formula Ia; for example RllRl2Ctfluorenyl)-(cyclopen~adienyl)dimethylzirconium) are employed for the ~ 30 preparation of the syndiotactic block in the polyolefin.
.~
::, ' For the purpose~ of the present inventi~n, the term C~
~ , 2 ~
symmetry means that the corresponding metallocenes have a mirror plane perpendicular ~o the plane passing through Zr, R1 and R2. The bisecting line of the angle ~ R1-Zr-R2 extends in this mirror plane. This consideration of s~mmetry is restricted to part of the zirconocene mole-cule, i.e. th~ - ( CR8R9 ) n~R7~ ( CR8R9 ) m~ bridge is not taken into account. Furthermore, the term C~ ~ymmetry should be understood in fonmal ox idealized texms. Thus, for example~ shifts in said moiety which may be ~aused by the bxidge and can only be explained via the structure are not considered for the purpo~es of the present invention.
The chiral metallocenes are employed as racemate~ fox the pxeparation of highly isotactic polyolefins. Howevex~ it is also possible to use the pure R- or S form. These pure stereoisomeric forms allow preparation of an optically active polymer. However, th~ meso-fo~m of the metallo-cenes should be removed since the polymerization-active center (the metal atom) in these compounds is nQ longer chiral due to mirror ~ymmetry at the central metal and can therefore no~ produce any highly i~otactic polymer.
If the meso~~orm is not removed, atactic polymer i~
formed alongside isotactic polymer. For certain applications - soft moldings for example - this may be thoroughly d sirable.
The principle of resolution of stereoisomers is known.
The metallocenes I and Ia can be prepared by the prin-ciple o~ the following reaction scheme:
~2~ t butylLi~RcLi X-(CR8~9)m~R7-(CR~R9)n^X
~Rd ,butylLi - ~RdLi .~ .
- - i- , :: . ..
~
: : :
: ~
.
2 ~ d HRC- ~ CP~8R9 ) m~ R7- ~ CR8R9 ) n^ RdH 2 bUtylLi LiR~- (CR~R9)m-R7- (CR8R9)n-RdLi ZrC14 >
R~ Zr ~ R7 Zr ) _ ~ R~9~:i," - R~
` ( R8R9C ~ m _ RC
R2Li :E~ Zr ~> I 1 ~2 (R8R9C)n - Rd ::
, . R3 X = Cl ~ Br, I or O-tosyl; H2R~ = ~( f or I or R14 for Ia / \ R5 H H
"
' ~ ~1 ' ~ ' ' ' , ' ,.~ ' ` ' : .
2i~
/ fox I or H
or R14 ~ ~uLi~ 7HR14Li ,~
Rl~ R12 a, ~R14hi Rl5H
~ / ~ f ;~ ~c b, ~2 ' Rl1Rl~ 2 Bu~i RlS
~ _ ~15-`,'' ~ llR12 ~ Li2 . .
~ 1 ~ ZrC14 ~ ~.
, :~
~:
~ ~c~ za ~ cl ~ Ll ~ 12~ ~ ~l~ Cl ~ R~
''``', ~ , :
(cf. Journal of Organomet. Chem. (1985) 63-67 and ~P-: A 320762).
,`~,: j The choice of the metallocenes for the polymerization of : olefins to give polyoleins having a broad or multimodal :: ~
.' ,. ~ :
- 12 - 2~$~
dis~ribution can take place by means of a test polymeri~ation for each metallocene.
In this test, the olefin is polymerized to tha polyolefin and the mean molecular weight ~ thereof and the molecu-lar weight dis~ribution M~/Mn thereof are determined bymeans of gel permeation chromatography. Depending on ~he desired molecular weight di~tribution, the metallocenes axe then combinsd.
Taking into accoun~ the polymerization activities, it is then pos~ible, ~y means of computer ~imulation of the combined gel permeation curves, to direct~y produce any desired molecular weight di~tribution via the type of metallocenas and via the ratio of the amounts of the metallocenes to one another.
The number o zirconocenes to be used according to the invention is preferably 2 or 3, in particular 2. However, it i5 also possible to u~e a greater number (such a~, for example, 4 or 5) in any desired combination of I and Ia.
By including the polymerization activities and molecular weights at variou~ polymerization temperatures, in the presence of hydroqen as molecular weight regulator or in the presence of comonomers, ~he computer simulation model can be further refined and the applicability of the process according to the invention urther improved.
~` 25 The cocatalyst u~ed is an aluminoxane of the form~la II
and/or III, where n is an integer from 0 to 50, prefera-bly 10 to 35.
The radicals R are preferably identical and are methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
If the radicals R are different, ~he~ are preferably ~ methyl and hydrogen or alternati~ely meth~l and isobutyl, ,.
I ~: ' ., .' , ' , .
' :~ ' - ,~ ~ ' . . ' .' ,, ' ', . ' ' , .' :
`', , ' ':~ ', ' , ' .~ .. , .
2 0 ~ 9 ~ J
hydrogen or isobutyl preferably being presen~ to the exten~ o~ O.01-40% (num~er of radicals R). The aluminox-ane can be replaced as cocatalyst in the pol~merization by a mixture comprising aluminoxane and AlR3, where R is as defined above.
The aluminoxane can be prepared in variou~ wayæ by known processes. One of the methods is, for example, to react an aluminum hydrocarbon compound and/or a hydridoaluminum hydrocarbon compound with water (gaseous, solid, liquid or bound - for example ~s water of crystallization) in an inert sol~nt ~such as, for example, toluene). To prepare an aluminoxane con~aining different al~yl groups R, two : different trialkylaluminum compounds [AlR3 + AlR'33, corresponding to ~he desired composition, are reacted : 15 with water (cf. S. Pasynkiewicz, Po~yhedron 9 (1990) 429 and EP-~ 302 424).
The precise structure of the aluminoxanes II and III is unknown.
Irrespective of the preparation method, all aluminoxane `~ 24 s~lutions have in common a varyin~ content of unreacted aluminum starting compound, which is in free form or as a~ adduct.
It is possible, before use in the pol~merization reac-~;~ tion, to preactivate the metallocenes, in each case ; 25 separately or together as a mixture, by means of an aluminoxane of the formula (II~ and/or (III). This significantly increases the polymeri~at.ion activity and improves the particle morphology.
, ~
:~ The pre~cti~ation of the metallocenes i6 carried out in ::
~ 30 solution. The metallocenes are preerably dissolved, as `:
~ , solids, in a 601ution of the alumino~ane in an inert ,: hydrocarbon. Suitable inert hydr~carbons are aliphatic or aromatic hydrocarbons. Toluene or a C6-C1O-hydrocarbon is preferably used.
:.
' ~ .
I' .,:
~,~: : . - -:
;` , ' : ' ~` , ' ~ ' ' ' ' , . ' ' ' The concentration of the aluminoxane in the solution i5 in the range from about 1% by weight to the saturation limit, preferably from 5 to 30~ by weight, in each case based on the total solution. The metallocenes can ~e employed in the same concentration, but are preferably employed in an amount of from 10-4-l mole per mole of alumino~ane. The preactivation time is from 5 minutes to ~0 hours, preferably from S to 60 minutes D ~he tempera-ture used is from -78C to 100C, preferably from 0 to 70C.
The metallocenes may also be prspolymerized or applied to a support. Prepolymerization is preferably carried out using the (or one of the) olefin(s) employed in the polymerization.
Examples of suitable supports axe silica gels, al~ninum oxides, solid ~luminoxane or other inorganic ~upport materialæ. Another suitable support material is a poly-~lefin powder in finely divided form.
A further possible embodiment o the process according to the invention comprises using a salt~ e compound of the formula RXNH4XBR~4 or of the formula R3PHBR'4 as cocatalyst in place of or in addition to an aluminoxane. In these formulae, x = 1, 2 or 3, R = alkyl or aryl, identical or different, and R' = aryl, which may also be fluorinated or partially fluorinated~ In thi~ case, the catalyst comprises the product of the reaction of the metallocenes with one of said compounds (cf . EP-A 277 004 ) .
In order to remove the catalyst poisons present in the olefin, purification by means of an alkylaluminum com-pound, for example AlMe3 or AlEt3, is advantageous. Thispurification can be carried out either in the ; polymerization system itself, or the olefin is brought into contact with the Al compound before addition to the polymerization system and is subsequently removed again.
~' .` ' ' ' 2 0 ~
_ 15 -The polymerization or copolymer:ization is carried out in a known manner in solution, in suspension or in the ga~
phase, con~inuously or batchwise, in one or more step~, at a temperature of from -60 to 200C, preferably from 20 to 80C. Olefins of the formula R~-CH=CH-Rb are polymerized or copol~merized. In this formula Ra and Rb are identical or different and are hydrogen atoms or alkyl radicals having 1 to 14 carbon atoms. However, R~
and Rb may also form a ring with the carbon atoms con-necting them. Ex~mples of such olefins are ethylene,propylene, l-~utene, l-hexene, 4-methyl 1-pentene, l-octene, nor~rnene and norbornadiene. In particular, propylene and ethylene are polymerized.
If necessary, hydrogen i~ added as molecular weight regula~or. The various hydrogen-reactivities of the metallocenes and the possibility of changing the amount of hydrogen during the polymerization can result in a further desired broadening of the molecular weight distribution.
The overall pressure in the polymerization system is from O.5 to 100 bar. The polymerization i~ preferably carried out in the industrially particularly interesting pressure range of from 5 to 64 bar.
; The metallocenes are used in a concentration, based on the txansition metal, of from 10-3 to 10-8 mol, prefe:rably from 10-4 to 10-7 mol, of transition metal pex dm3 of solvent or per dm3 of reactor volume. The aluminoxane or the aluminoxane/AlR3 mixture is used in a concentration of from 10-5 to 10~1 mol, preferably frcm 10-4 t~ 10-2 mol, per dm3 of solvent or per dm3 of reactor ~ol~me. In principle, however, higher concentrations are also possible.
':
If the polymerization is carried out as a suspension or solution polymerization, an inert solvent which i9 ' '~
':~
.- , ' .
~- I
~ 3 customary ~or the Ziegler low-pressure process is used.
For example r the polymerization is carried ~u~ in an aliphatic or cycloaliphatic hydrocarbon; the examples of these which may be mentioned are ~utane, pentane, hexane, heptane, decane, isooctane, cyclohexane and methylcyclo-hexane. It is also possible to use a gasoline or hydro-genated diesel oil frac~ion. Toluene can also be used.
The polymerization is pref~rably carried out in the liquid monomer.
If inert solvents are used, the monomers are metered in in gaseous or liquid form.
The polymerization can ta~e as long as desired, since the catalyst system used according to the inven~ion only exhibiks a slight decrease in the polymerization activity lS with time.
The process according ko the invention is distinquished . by the fact that the metallocenes described give polymers having a broad, bimodal or multimodal molecular weight distribution, high molecular weight, high stereospecifi-city and good particle morphology in the industriallyinteresting temperature range between 20 and 80C with high polymerization Activity.
The pol~mers accoxding to the invention are particularly suitable for the production of films, in particul~r transparent films, thermoforming applications~ polyolefin : foams, extrusion applications and for ~he pr~duction of transparent hollow articles and for blow molding in general.
, The examples below are intended to illustrata the inven-tion in greatsr detail.
The following abbreviations are used:
~N = viscosity number in cm3/g , ' , .:
. - . .
:.,:~.
... .
:: , = weight a~erage molecular ~ determined by weight in g/mol ~ gel permeation M~tMn = molecular weigh~ dispersity J chromatography II = i~o~actic index (mm ~ 1i2 mr) 1 determinad by SI = syndiotactic index ~ l3C-NMR
(rr + 1/3 mm) J spectroscopy MFI (230/5) = melt flow index, mea~ured in accordance with DIN 53735; melt temperature 230C
and weight 5 kg.
: 10 Example 1 A dry 24 dm3 reactor was flushed with nitrogen and filled with 12 dm3 of liquid propylene. 39 cm3 of a toluene solution of methylaluminoxane (corresponding to 5~ mmol of Al, mean degree of oligomerization of the methylaluminoxane was n = 19) were then added, a.nd the batch was ~tirred at 30C for l~ minutes.
In parallel, 13.5 mg (0.025 mmol) of rac-phenyl(methyl)-:~ silyl(2-methyl-1-indenyl)2zirconium dichloride and 51.0 mg (O.10 mmol) of rac~phenyl(met~yl)silyl(l-~ 2G indenyl)zirconium dichloride were di~solved in 15 cm3 of - a toluene eoluti~n ~f methylaluminoxane (20 mmol), and the ~ution was introduced i~to the reactor after 15 minutes.
The mixture was polymerize~ at 30C for 3 hours. The ; 25 pol~merization was terminated by addition of 12 1 of CO2 ga~O 1.85 kg of polypropylene were obtained, correspo~d-ing to an activi~y of the metallocene mixture of 9.6 kg of PP~g of metallocene x h.
VN = 331 cm3/g; M~ = 411,000 g/mol, M~/M~ = 8.5; II =
96.g%.
Example ~
Example 1 wa9 repeated, but ~he metallocene mixture ~;~ components employed were 11. 2 mg (0.025 ~unol) of rac-ethylenet2-me~hyl l-indenyl)2zirconium chloride and 13.9 mg (0.025 mmol) of diphenylmethylene(9-fluoren~
~cyclopentadienyl)zirconium dichloride; the `:: `: :
2 ~ J
polymeri~ation tempera~ure was 60C and the polymerization t.ime was 1 hour.
2.45 k~ of polypropylene were obtained, corresponding to an activity of the metallocene mixture of 9706 kg of PP/g of metallocene x h.
VN = 255 cm3/g; M~ = 38$,000 g/mol, M~/M~ = 7.5.
The resultant pol~mer could be separated b~ fractionation into a fraction of isotactic p~lypr~pylene (II > 96%) and a fraction of syndiotactic polypropylene (SI > 96~ he mixing ratio was about 1 Example 3 Example 1 was repeated, but the metallocene mixture components employed were 5.4 mg ~0.010 mmol) of rac-- phenyl(methyl)silyl(2-methyl-1-indenyl)2zirconium dichloride and 5.4 mg (O.013 mmol) of dimethylmethylene-(9-fluorenyl)~cyclopentadienyl)zirconium dichloride, the polymerization temperature was 70~C and the polymerization time was 1 hour.
2.2 kg of a mixture of about two part~ of isotactic polypropylene and one part of syndio$actic polypropylene were obtainedl corresponding to an activity of the metallocene mixture of 203.7 kg of PP/g o~ metallocene x . ~.
VN = 172 cm3/g; M~ - 186,~00 g/mol, N~/N~ = 3Ø
Example ~
Example 1 wa~ repeated, but the metal}ocene mixture components employed were 4.8 mg (0.01 mmol) of rac-Me2Si(2-methyl-1-indenyl~2zirconium dichloride and21.2 mg (O.05 mmol) of rac-Me2Si(2,3,5-trimethylcyclopenta-dienyl)2zirconium dichloride, and the polymerization ~ temperature was 50C.
- 2.57 kg of polypropylene were obtained, corresponding to an activiky of the metallocene mixture of 32.9 kg of PP/g ~ of metallocene x h.
:, :~ .
. :
~ : ~
!
2~5~ 3J
- lg -VN = 194 cm3/g; M~ - 261,000 ~/mol, ~/N~ = 7.9, II =
98.5%~
Example 5 Example 1 was repea~ed, but the metalloc2ne mixture components employed were 4.5 mg (0.008 mmol) of rac~
phenyl(methyl~sil~l~2-methyl-l-indenyl)2zirconium dichloride and 6 . 6 mg (0.015 mmol) of xac-dLmethylsilyl-(indenyl)2zirconium dichloride. The polymerization time was one hour~ iand the polymerization temperature was 50C~
1.35 kg of pol~propylene were obtained, corresponding to an activity of the metallocene mixture of 121.6 kg of PP/g of metallocene x h.
VN = 154 cm3/g; N~= 133,000 g/mol, ~ = 5.2, II = 96.0~.
Example 6 ~xample 1 wa~ repeated, but the metallocene mi~tur~
components employed were 2.4 mg (0.005 mmol) of rac-dimethylsilyl(2-methyl-1-indenyl~zirconium dichloride and 2.5 mg (0.005 mmol) of rac-dimethylgerm~l~inde~yl)2-zirconium dichloride. ~he two metallocene~ were dissol~ed separately, each in 7.5 cm3 of a toluene solution of methylaluminumoxane, and after 15 minutes these solutions were metered into the polymerization ~ystem. The mixture wa6 polymerized at 70~C for 1 hour.
1.57 kg of polypropylene were obtained, corresponding to an activity of the metallocene sy6tem of 320.4 kg of PP/g of me~allocene x h.
VN = 105 cm3/g; M~ = 114,000 g/mol, M~/M~ = 4.1, II =
96.3~.
Example 7 Ex~mple 6 was repeated, but the metallocenes used were 4.8 mg tO.Ol mmol) of rac-dimethylsilyl(2-m~th~
indenyl~2zirconium dichloride and 1.5 mg (O.004 mmol) of I rac-dimethylsilyl(indenyl)2dimethylzirconium.
;' ~, ,~:.. : .. . . .
2 ~ 2 2.08 kg of polypropylene were obtained, corresponding to an activity of the metallocene system of 330.2 kg of PP/g of metallocene x h.
VN = 121 cm3/g; N~ = 101,900 g/mol, N~/M~ = 4.0t II =
96.0~.
Example 8 Example 6 was repeated, but the metallocenes used were 2.7 mg (0.005 n~ol) of rac-phenyl(methyl)silyl(2-methyl-l-indenyl)2zirconium dichloride and 2~,5 mg (O~04 mmol) of rac-phenyl~inyl)silyl(indenyl) 2Z irconium dichloride.
: 2.17 kg of polypropylene were obtained, corresponding to an activity of the metallocene ~ystem of 93.5 kg of PP~g of metallocene x h.
VN = 102 cm3~g; MW = 79,400 g/mol, ~ 3.3, II = 96.9%.
Example 9 Ex~mple 6 wa~ repeated, but the metallocene~ used were 4.8 mg (0.01 mmol) of rac-dimethylsilyl(2-methyl-1-inden~l)2zirconi~m dichloride and 9.2 mg ~ n .02 mmol) of rac-Hz~-CH2-CH2-Si(indenylj~zirconium diGhloride.
1.82 kg of polypropylene were o~tained, corresponding to an activity of the metallucene system of 130 kg of PP/g of metallocene.
VN = 145 cm3/g; M~ = 185~5no g/mol~ N~ = 3.6, II =
96.8%.
Example 10 Example 6 was repeated, but the metallocenes u~ed were 2.7 mg ~O.005 mmol) of rac-phenyl(methyl)silyl(2-methyl-; 1-indenyl)2zirconi~m dichloride and 2.4 mg (O.006 ~mol) of rac-dimethylsilyl(2,4-dimethylcyclopentadienyl) 2-zirconium dichloride.
1.31 kg of polypropylene were obtainedl corresponding to an activity of the metallocene system of 256.9 kg of PP/g ~;i ,:~
- .
--:
: - - , , :
- ~ .
- 21 _ 2~
of metallocene x h.
VN = 118 cm3/g; ~ = 129,500 g/mol, ~ 3.B, II =
g8.0%.
E~ample 11 Example 1 was repeatedl but the metallocenes u~ed were 26.9 mg (O.05 mmol) of rac-phenyl(methyl)silyll~-methyl-1-indenyl)zzircvnium dichloride and 32.5 mg (O.08 mmol) of rac-dim2thylsilyl~2,4-dimethylcyclopentadienyl) 2 zirconium dichloride. The polymer Lzation time was 2 hours. 2.32 kg of polypropylene were obtained, corres-ponding to an activity of the metallocene sy~tem of 19.5 kg of PP/g of metallocene x h.
VN - 386 cm3/g; ~ = 436,000 g/mol, M~/M~ = ~.2, II =
98.5%.
Example 12 Example 1 was repPated, but the metallocenes used were 9.2 mg (0.02 mmol) of rac-methylethylene(2-methyl-1-;:~ indenyl)2zirconium dichloride and 8.6 mg (0.0~ mmol) of rac-dLmethylmethylenetI-indenyl)2~irconium dichloride, and the polymer.ization temperature was 50C. 1.42 kg of polypr~py1ene were obtained, corxeæponding to an activity of the metallocene system of 26.6 k~ of PP/g of metallocene x h.
VN -~ 101 cm3~g; M~ = 123,000 g/mol, M~/M~ = 8.5, II =
91.6%.
~xample 13 A dry 24 dm3 reactor was ~lu~hed with nitrogen and filled with 24 dm3 (s.t.p.) of hydr~gen and 12 dm3 of liquid propylene.
10 ml of a toluene ~olution of trimethylaluminu~ (corres-ponding to 2~ mol of AlMe3) were then added, and the batch was ~tirred at 40C for 15 minutes.
In parallell 5.4 mg (0.01 mmol) of rac-phenyl(methyl)-silyl(2-methyl-l-indenyl~2zirconium dichloride and 4.9 mg " ~ .
, ~
2 ~
(0.01 mmol) of rac-dimethylgermyl(indenyl)azirconi~m dichloride were dissolved in 15 cm3 of methylaluminoxane solution (20 mmol of Al, toluene)y and, after 15 minutes, the solution was introduced into the reactor. Th~ reactor contents were heated to 65C in 3 minutes and polymerized at this temper~ture for on~ hour.
~he polymerization was terminated by addition of 12 1 of CO2 gas, exces~ propylene was removed in gaseous form, and the p~l~mer p~wder was dried at 80~CJ100 mbar.
2.25 kg of polypropylene were obtain~d, corre~ponding to an activity of the metallocene mi~ture o 218.5 kg of PP/g of metallocene x h.
VN = 91 cm3/g; M~ = 72,800 g/mol; MW/M~ = 4.~, II = 96.8~.
Example 14 Example 1 was repeatedl but the metallocenes u~ed were 5.4 mg (O.010 mmol) of rac-phenyl(methyl)silyl(2-methyl-l-indenyl)2zirconium dichloride and 2700 m~ (0.056 mmol) of rac-dimethy~silyl(2-methyl-4,5,6,7 tetrahydro-l-: indenyl)2zirconium dichloride, the polymerization tem-perature was 50C, and the polymerization time was :~ 1.5 hours.
~'~
1.51 kg of polypropylene were obtained, corresponding to : an activity of the metallocene ~ystem of 31.1 kg of PP/g : of metallocene x h.
VN = 187 cm3/g; M~ - 132,500 g/mol, M~N~ = 4.1, II =
; 97.6%.
Example 15 ;~ Example l was repeated, but the metallocenes used were 4.8 mg tO.O10 mmol) of rac-dimethy~ yl(2-methy~
~: 30 indenyl)2zirconium dichloride and 7.0 mg ~0.017 mmol) of rac-ethylene~l-indenyl)2zirconium dichloride. The polymerization temperature was 50C and the :: polymerization duration was 1 hour.
,',~ '.
,;:
.
' ~
: ,.~
-; : . . :
.
.:. : : , 2 ~ 6 ~3 1~50 kg o polypropylen0 were o~tained, corresponding to an activity of the metallocene system of 127.1 kg of PP/g o metallocene x h.
VN = 125 cm3~g; M~ = 129,500 g/mol, N~/M~ = 5.3r II =
- 5 9~.4%.
Example 16 : Example 1 was repeated, but the metallocenes used were 6.0 mg ~0.010 mmol) of rac-diphenylsilyl(2-methyl-1-indenyl)2zirconium dichloride, 6.0 mg ~0.013 mmol) of rac-dimethylsilyl(l-indenyl)2zirconium dichloride and 36.0 mg ~O.083 mmol) of rac-dimethylsilyl~2,3 r 5 ~ri-methylcyclopentadienyl)zzisconium dichloride, the polymerization temperature was 40C and the polymeriza~ion duration was 2 hours.
1.79 kg of polypropylene were obtained, corresponding to an activity of the metallocene 3ystem of 18.6 lcg of PP/q ~ of metallocene x h.
: VN = 267 cm3/g~ N~ ~ 293,000 g/mol, N~ = 5.7, II =
98~0%, MFI (230~5) = 24.6 g/10 min.
~xample ~7 A dry 24 dm3 reactor was flushed with propylene and ~- filled with 12 dm3 of liquid propylene and with 2~ ml of a toluene solution of trimethylaluminum ~corresponding to ~ 52 mmol of AlMe3)O ~he batch was 6tirred at 30C for : 2~ lS minutes.
In parallel, 3.0 mg (O.005 mmol) of rac-diphenyl~ilyl(2-methyl~1-indenyl)2zirconium dichloride, 2.n mg (0.004 mmol) of rac-dimethylsilyl(2-methyl-l-indenyl) 2-zirconium dichloride and 2.0 mg (O.004 mmol) of rac ~0 dimethylgermyl(1 indenyl)2zirconium dichloride were dissol~ed in 20 cm3 of methylalumino~ane ~o~ution ~ (27 mmol of Al, toluene), and, after 15 minutes, the :; solution was introduced into the reactor. I'he mixture was ~ polymeriæed at 65C for 1.5 hours.
"' .
: - . ::
2 ~ ?.
~ 24 -1.59 kg of polypropylene were obtained, co~responding to an activity of the metallocene system of 1~1.4 kg of PP/g of metallocene x h.
: VN = 153 cm3tg; M~ = 195,000 g/mol, N~/M~ = 5.8, II -9600%, MEI (230/51 = B7 g/10 min.
Example 18 Example 1 was repeated, but the metallocenes used were 6 . O mg ( O . 01 mmol ) of rac diphenylsilyl ( 2-methyl-1-indenyl)2zirconium dichloride and 4S.0 mg (0.10~ mmol3 O:e rac-methylene(3~t-butyl-1-cyc~opentadienyl) 2Z irconium dichloride, the polymeri~ation temparature was 4~DC and the polymerization duration wa~ 4 hours.
1. 63 kg of polypropylene were obtained, corresponding to : ~ an activity of the mekallocene system of 8.0 kg of PP/g of metallocene x h.
VN = 358 cm3~g; M~, = 3S4~000 g/mol, ~/Mn = 12.5, ll =
9 3 . 5 % .
,, ExampLe 19 Example 1 was repeated, but the m~tallocena~ u3ed were 6.0 mg (0.010 mmol) of rac-diphenyl~îlyl(2-methyl-1-indenyl)zzirconium dichloride and 6.0 mg (0.012 mmo~) of rac-dimethylsilyl(4,7-dimethyl-l-indenyl~2zirconium l dichloride~ the polymerization temperature was 40C and ;~ the polymerization duration was 2 hours.
0.85 kg o~ polypropylene were obtained, corresponding to ~ an activity of the metallocene 8y tem of 35.4 kg of PP/g : of metallocene x h.
`~ VN = 324 cm3/g; ~ = 352,500 g/mol, M~/M~ = lS.5, II =
:~' 95.~%.
' Example 20 ,~; Example 1 was repeated, but the metallocenes used were : 6.0 mg (0.010 mmol) of rac-diphenyl~ilyl~-methyl-l-indenyl)2zirconium dichloride and 7.2 mg (0.016 mmol) of ~ rac-ethylene(2-methyl-1-indenyl)2zirconium dichloride.
.:
'':
.: ~
,. . .
- 25 - 2~ tJ
The polymerization tempexature was 50C and the polymerization duration was 2 hours.
1.44 kg of polypropylene were obtained, corresponding to an activity of the metallocene system o 54.S kg o~ PP/g of metallocene x h.
VN = 227 cm3/g; H~ = 406,000 g/mol, ~JM~ = 8.0 97.1%.
Example 21 Example 20 was repeated, but in addition 75 g of ethylene were metered in continuously during the polymerization.
The polymerization temperature was 60C and the polymerization time was 1 hour.
1.65 ~g of ethylene propylene copolymer were obtained, corresponding to an acti~ity of the metallocene system o~
1~5.0 kg of copolymer/g of metallocene x h.
VN = 291 cm3/g; M~ = 387,000 g/mol, N~/N~ = 7.4; 4.2%
ethylene content with ethy~ene units predominantly incorporated in an i~olated manner (l3C NMR analysis~.
Example 22 ~ 20 Example 21 was repeated, but 300 g of ethylene were only ; added after a polymerization time of 30 minut~s.
1.49 ~g of copolymer were obtained, ~orresponding to an acti~ity of the metallocene system of 112.9 kg of copolymer/g of metallocene x h.
VN = 357 cm3g; M~ = 449,000 g/mol, M~/M~ = 8.8. The polymer product can be ~eparat~d by fractionation (decane, diethyl ether) into a polypropylene component and an ethylene-propylene rubber component.
Ethylene content of the copolymer 18.4%.
Example 23 A dry lS0 dm3 reactor wa~ flushed with nitrogen and fi~le~ at 20CC with 80 dm3 of a gasoline fraction with the aromatic~ removed and with a boiling range o~
, :
:
.- .
_ 26 -100-120C. The gas space was then flushed free from nitrogen by injecting 2 bar of propylene and releasing the pressure, and rep~ating this cycle four times.
50 1 of liquid propylene were added, and 64 cm3 of a toluene solution of methylaluminoxane (corresponding to 100 mmol of Al, molecular weight 390 g/mol according to cryoscopic determina~ion) ~ere added and the reactor contents were heated to 50C.
Hydrogen was me~ered in to give a hydr~gen co~tent in the gas space of ~he reactor of 0.1%, and this content was then main~ained during the entire polymeri2ation time ~y topping up (monitoring on-line by gas chromato~raphy).
15.3 mg of rac methylethylene(2-methyl-1-ind~nyl)2-zirconium dichloride (0.033 mmol), 6.3 mg of rac-phenyl~
; 15 ~methyl)silyl(2-methyl-l-indenyl)2zirconium dichloride (0.012 mmol) and 7.0 mg of rac-diphenylsilyl~2-methyl-1-indenyl)22irconium dichloride (0.012 mmol) were di~solved in 32 ml of a toluene solution of methylaluminoxane (corresponding to 50 mmol of Al) and, after 15 minutes, the solution was i~troduced into the reactor.
., The reactor ~as kept at a polymerization temFerature of 50C for 7 hours by cooling, the polymeri~ation was then terminated by addition of 2 bar of C2 gas, and the ` polymer formed was separated from the suspension medium i~ 25 in a pressure filter. The product wa~ dried for 24 hours at 80C/~00 mbar, 16.4 kg of polymer powder, were obtained corresponding to a metallocene activity of 81.~ kg of PP/g of metallocene x h.
:~ VN = ~06 cm3/g; M~ = 248,000 g/mol; M~/Mn = 3.4 - 30 II = 97.9~; MFI (230/5) = 32 g/10 min, m.p.: 151C
The product had the following mechanical data:
Modulus of elasticity in tension (in accordance with DIN 53457-Z) 1,430 N/mm2; ~otched impact strength (an in accordance with DIN ~3453) 5 mJ/mm2 a~ ~3C; Izod impact ~;
2 ~ r~J
~ 27 -strength (in accordance with ISO 180/1 C) 69 mJ/mm2 at ~3C and 12 mJ/mm2 at -30C; Izod notched Lmpact strength (according ~o ISO 180/1 ~) 3 m~/mm2 at 23C and 2 mJ/mmZ
at -30C; ball indentation hardness (p~essing, condi-tioned, 358 ~) 84 ~/mm2 and ball inden~ation hardness (injection molding, 358 N, in accordance with DIN 53456) 75 N/mm2.
Example 24 Exam~le 23 was repeated but the metallocene mixture comprised 6.3 mg of rac-phenyl~methyl)silyl(2-methyl-1-indenyl)2zirconium dichloride ~O.nl2 mmol) and 2.9 mg of rac-d~methylsilyl(l-indenyl) 2Z irconium dichloride (0.006 mmol). Polymerization was carried out without hydrogen.
The polymerization was complete after 20 hours.
18.7 kg of polymer powder were ~tained~ corresponding to a metallocene activi~y of 101.6 kg of PP/g of metallocene x h.
VN = 202 cm3/g; M~ = 296,000 g/mol; M~/M~ = 7.9 II = 96.4%; NFI (230/5) = 39 g/10 min; m.p.: 148C
The product had the foll~wing mechanical da~a:
Modulus o~ elasticity in tensi~n (in accordance with DIN 5347-Z) 1,28a N/mm2; notched impact ~trength (an in accordancP with DIN S3453) 3 mJ/mm2 at 23~C; I~od impact .: 25 strength (in accordance with ISO 180/1 C) 65 mJ/mm2 at 23C and 11 m~/mm2 at -30C; Izod notched Lmpact strength (according to ISO 180/l A) 3 mJ/mm2 at 23C and 2 mJ~mm2 a~ -30JC; ball indentation hardness 77 N/mm2 (pr~sing, conditioned, 358 N) and 71 N/mm2 (injection molding, 358 N, in accordance with DIN 53 456).
~. :
....
~,
23 (1985) 2117; EP-A 302 424). Polyolefins of thi~ type : 10 with a narrow distribution are suitable, for example, for applications in preoision in~ection molding, injection molding in general and for the production vf fiber~. For numerous applicatio~s, 6uch as, for example, thermo-fonmingr extru~ion, blow molding and for the production of polyolefin fOam6 and films, broader or bimo~al molecu-: lar weight distributions are required.
' .
For polyethylene, it has been proposed to a~hieve such products by using two or moxe metallocene cataly~ts in the polymerization (EP-A 128 045); however, the sy6tems described are achiral ca~aly~ts and would give atactic polypropylene on polymermization of propene. However, ~, atactic polypropylene is unsuitable a~ a structuxal material.
:~' The preparation of stereoblock polypropylen0 where ~/M~
is 13-15 is disclosed in DE-A 3 640 924. These cataly~t systems are likewise unsuitable for the formation ~f polyolefins of high tacticity. Furthermore, the metallocene activitie~ which can be achieved at indus-:~ trially relevant polymerization temperatures and the ~: 30 molecular weights of polymer product~ axe too low. In addition, the proposed catalyst~ give only an atactic ., : polymer at such polymerization temperatures.
;, EP-A 310 734 proposes catalyst systems comprising a ', 2 ~
mixture of a hafnocene and a zirconocene for the prepara-tion of polypropylene. Products have broad to bimodal distributions where N~/N~ is from 3.7 to 10.3 If only the hafnocene catalyst is used, polypropylene with a broad di~tribution is obtai.ned at a csrtain polymerization temperature, according to EP A 355 439.
Syndiotactic polypropylene having a broad distribution is described in EP-A 387 691 (M~/M~ up to 6.4) if a hafnocene is used.
These proce~ses have the comm~n disadvantages of hafnium catalyst costs which are ~oo high for indu~trial applica tions, together with a low polymerization activity, which additionally makes it necessary to carry out thorou~h, ~: high-cost purification o the prepared polymer to remove cataly~ residues.
The object was thus to find a catalyst ~ystem and a proces~ by means of which polyolefin~ ha~ing a broad, bimodal or multLmodal distriblltion can be prepared and ; which avoid the disadvantages known from the prior art.
.
20 The object is achieved by using a catalyst system com-.~; prising at lea~t two ætereorigid zirconocenes and an aluminum compound as cocatalyst.
The invention thus xelates to a process for the prepara-tion of a polyolefin which has a molecular weight dis-~:: 25 tribution N~lN~ of ~ 3.0 and which may be monomodal, bimodal or mult~nodal, by polymerization or copol~nerization of an olefin of the formula R~C~=CHRb in which R~ and Rh are identical or different and a hydro-~ ge~ atcm or a alkyl radical having 1 to 14 carbon atom~, i 30 or R~ and Rb, together with the atoms connecting them, can .: ~orm a ring, at a tempera~ure of from -60 to 200C, at a ~; pressure of from 0.5 to 100 bar, in solution, in suspen-sion or in the gas phase, in the presence of a catalyst . ~ ~
:
.. 2 ~ ? ` .
comprising a ~ransi~iGn-metal component (metallocene) and an aluminoxane of the formula II
_ ~Al--O ~ Al - O ~ R
n R
.~
for the linear type a~d/or of the for~lula III
tAl - 0~ (III) for the cyclic type, where, in the formulae II and III, the radicals R may be identical ~r different ~nd ~re a C1-C6-alkyl group, a Cl-C6-fluoroalkyl group, a C6-C1g-aryl group, a C1-C6~1uor~yl ~roup or a hydrogen, and n is an . 10 integer from O to 50, or~ tead o khe aluminoxane, ~, compri~es a mixture of an aluminoxane o~ the formula II
`' and/or of the ~crmula III with a compound AlR3, ~hich eomprises using, a~ the transition-metal component, at :. ; least one zirconocene of the formula I and st least one ~ 15 zirconocene of ~he formula Ia or alternatively at least ~:
'~ 2 zirconocenes of the formula I
~', ~
(j~ R ~mR14 _ ~CR8R9)m R1 Zr ~ _!C~6B9)~ - IL8R8~n ,~ :
, , ~ 4 _ 2~ 2 in which 1 and R2 are identical or different and are a hydrogen atom, a c1-C10-alkyl qrou~, a C1-C10-alkXY ~roup~
a C6-C10-arYl group, ~ C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C4o-arylalkyl group, a C7-C40-alkylaryl group, a Cg-C40-arylalkenyl group or a halogen atom, R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, a C1-C1o-alkyl group, which may ~e halogenated, a C6-C1o-aryl gr~up, or a -NR210, -SR10, -OSiR310, -SiR310 or -PR210 radical, in which R~ is a halogen atom, a C1-C10-alkyl group or a C6-C1o-aryl group, Rs and R6 are identical or dif~r~n$ ~nd are ~ defined for R3 and R4~ with the proviso that R5 ~nd R~ are j not hydroge~, is -M' -.-M1 ~7 - M~ . -M' ~ (t:Fl2'3) - ' O ' M' ~ 0 R'~ R12 p~2 Rl2 R'l ~M~ - .
` p~12 R12 .
.
.
_AlR~ Sn, -O-, -S- l ~S~:~, =S~2, l~R , ~ IzPRll or =P ( O ) Rll, ' where R11, R12 and Rl3 are identical ~r different and are a hydro-gen atom, a halogen atom, a C1-C1o-alkyl group, a C1-C1o-~:, I, .:: : . . :
, . : ~
2~$~
fluoroalkyl group, a C6-C10-aryl group, a C6-C10-fluoro-aryl group, a C1-C10-alkoxy group, a C2-C1o alkenY
group, a C7-C,~o-arylalkyl ~roup, a C~-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R11 and R12 or . R11 and R13, toge~her with the atoms connecting them, : in each case form a ring, and Ml i~ silicon, germanium or tint Ra and R9 are identical or diffQrent and are ~ defined for R11, ~`
Rl4 and ~15 are identical or di~f~arent and are a mono~clic or polycyclic hydrocarbon radical which can form a ~; sandwich structure together with khe zirconium atom, and ~ .
.~. m and n are identical or di~ferent and are ~ero, l or~
. 2, wh~re m plu~ n i~ ~ero, 1 or ~.
~, ~,~
Alkyl i8 ~traight~hain or branched alky~l. Halo~en `l ~ thalogenated) refer~ t~ flu~rlne, chlosine, bromin~a or ? ~`, iodin~, preferably fluorine or chlorine.
R1 and R2 are identical or different and are a hydrogen atom,: a C1-C10-, preferably C1-C3-alkyl qroup, a C1-C10-, preferably C1-C3-alkoxy group, a C6-C10-, preferably C6-Cg-aryl group, a C6-C1Q-, prefera-ly C6-Cg-aryloxy group, :: : a C2-C10-, preferably C2-C4-alkenyl groupj a C7-C40-, preferably C7-C1o-arylalkyl group, a C7-C40-, preferably C7-C12-alkylaryl group, a Cg-C40-, preferably Cg-C12-arylalkenyl group, or a halogen atom, preferabyl chlorine.
,~, :
R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, prefera-ly fluorine, chlorine or ~l bromine atom, a C1-C10-, preferably C1-C4-alkyl group, l. which may be halogenated, a C6-C10-~ preferably C6-C8-aryl group, a -NR210, -SR10, -OSiR310, -SiR310 or -PR210 radical in which R10 is a halogen atom ~referably a chlorine atom, J~
": ~ :
r;`;~
2 ~
or a C,-C10-, preferably Cl-C3-alkyl group or a C6-~lo~, preferably C6-C~-aryl group. R3 and R4 are particularly preferably hydrogen.
Rs and R6 are identical or differen~ prefexably identi-cal, and are as defined for R3 and R4, with the provi~o that R5 and R6 cannot be hydro~en. R5 and R6 are preferably (Cl-C~)-alkyl, which may be halo~enatecl, ~uch a6 m~thyl r ethyl, propyl, isopropyl, butyl, isob~ltyl or trifluoro-methyl, in particular methyl.
R7 is ~l~ R11 R"
- M' -, -M'-- M' - ,-M' ~ a~R t3~ .0~_ M7~0 p~12 R12 R12 Rl2 R'~
R"
O- M'-Rl2R12 .
=BR , =AlRll, -Ge-, -Sn, -O-, -S-, =SO, =SO2, =NRll, =CO, =PR11 or =P(O)R11, where Rl1, Rl2 and Rl3 are id~ntic~l or different and are hydrogen atoms, halogen ato~s, a C1-C1o-, -~; preferably C1-C4-alkyl group, in particular methy1 group, a C1-C10-fluoroalkyl group, pre~erably CF3 group, a C6 C10-, preferably C6-Cg-aryl group, a C6-C10-fluoroaryl group, preferably penta~luorophenyl group, a C1-C10-, preferably C1-C4-alkoxy group, in particular methoxy group, a C2 C10-l preferably C2-C4-alkenyl group, C7-C40-, preferably C7-C10-~ arylalkyl group, a C8-C40-, preferably C8-C12-arylalkenyl .. group, or a C7-C40-, preferably C7-C12-alkylaryl group, or :~ R11 and R12 or R11 and R13, toqether with the atom~ connecting I them, in each case form a ring.
~ M1 is silicon, germanium or tin, preferably silicon or :;
.
. ~ , . . . .
g germanium.
R7 is preferably =CR1'R12, =SiR1'R1~, =GeR11R'2, O-, -S-, =SO, =PR" or =P(O)R'1.
R8 and R9 are identical or different and are as defined for Rll.
m and n are identical or different and are ~ero, 1 or 2, preferably zero or 1, where m plus n i~ zero, 1 or 2, preferably zero or 1.
R14 and R15 are prefera~ly fluorenyl, indenyl or cyclo-pentadienyI, it being possihle for these parent ~truc-tures also to carry additional substituents as defined f Qr Rll .
: Particularly preferred metallocenes are thu~ tho~e in which, in the formula I, R1 and R2 are identical or lS different and are methyl or chlorine, R3 and R4 are hydrogen, R5 and Rs are identical or di~ferent and are ` methyl, ethyl or tri~luoromethyl, R7 i8 a R~
or -Sl~ radical, and n plus m is 2ero or 1, in ~ p~12 Rt2 particular the compounds listed in the working example~.
Of the compounds I mentioned in the working examples, rac-dimethyl~ilyl(2-methyl-l-indenyl)2zirconium dichloride, rac-ethylene(2-methyl-1-inden~1)2zirconium dichloride, rac-diphenylsilyl(2-methyl-1-indenyl)2zirconium dichloride, rac-methylethylene(2-methyl-l-indenyl~2zirconium dichloride and rac-phenyl(methyl) 9ilyl ( 2-methyl-l-indenyl)2zirconium dichlorid~ are of particular Lmportance.
:. .
.~
: , 2 ~ 3 ro~
-- 8 ~
~he particularly preferred metallocenes of the formula la are those in which Rl and R2 are identical or different and are methyl or chlorine, R~
R7 is a ~ C~ or _~ radical bl2 R12 p~
n ~ m i~ zero or 1 and and R15 are identical vr different and are fluorenyl, indenyl or sub~tituted cyclopentadienyl, in particular the compounds la listed in the working example~.
9~ particular importance are ~h~s rac-phenyl(methyl)-silyl(indenyl) 2zirconium dichloride, diphenylmethyl~ne~9-fluorenyl)(cyclopentadienyl)zirconiumdichloride,i~opro-pylidene(g-fluorenyl)~cyclopen~adienyl)zirconium dichloride, rac-dimethylsilyl(2,3,5-~rimethyl-1-cyclopen-tadienyl~2zirconium dichloride, rac-dimethylsilyl-. 15 (indenyl)2zirconium dichloride, rac-dimethylgermyl-- (indenyl)2zirconium dichloride, rac-d~methyl~ilyl-(indenyl)2dimethylzirconium, rac-phenyl(v~nyl) 5ilyl -(indenyl)2~irconium dichloride, rac-~2C-CH2-CH2~
(indenyl)2zirconium dichloride, rac~dimethylsilyl(2,4-. 20 dimethylcyclopentadienyl)2zixconium dichloride, rac-~; isopropylidena(indenyl)2~irconium dichloride, rac-dimethylsilyl(2-methyl-4 r 5 ~ 6 / 7-tetrahydro-1-indenyl) 2-.. zirconium dichloride, rac-ethylene(indenyl)2zirconium -dichloride,rac-methyl~ne~3-t-butyl-1-cyclopenkadienyl) 2-zixconium dichloride and rac-dimethylsilyl(4,7-dimethyl-: 1-indenyl)2zirconium dichloride.
~ The metallocene~ having C~ symmetry ~subgroup o~ com-: pound~ of the formula Ia; for example RllRl2Ctfluorenyl)-(cyclopen~adienyl)dimethylzirconium) are employed for the ~ 30 preparation of the syndiotactic block in the polyolefin.
.~
::, ' For the purpose~ of the present inventi~n, the term C~
~ , 2 ~
symmetry means that the corresponding metallocenes have a mirror plane perpendicular ~o the plane passing through Zr, R1 and R2. The bisecting line of the angle ~ R1-Zr-R2 extends in this mirror plane. This consideration of s~mmetry is restricted to part of the zirconocene mole-cule, i.e. th~ - ( CR8R9 ) n~R7~ ( CR8R9 ) m~ bridge is not taken into account. Furthermore, the term C~ ~ymmetry should be understood in fonmal ox idealized texms. Thus, for example~ shifts in said moiety which may be ~aused by the bxidge and can only be explained via the structure are not considered for the purpo~es of the present invention.
The chiral metallocenes are employed as racemate~ fox the pxeparation of highly isotactic polyolefins. Howevex~ it is also possible to use the pure R- or S form. These pure stereoisomeric forms allow preparation of an optically active polymer. However, th~ meso-fo~m of the metallo-cenes should be removed since the polymerization-active center (the metal atom) in these compounds is nQ longer chiral due to mirror ~ymmetry at the central metal and can therefore no~ produce any highly i~otactic polymer.
If the meso~~orm is not removed, atactic polymer i~
formed alongside isotactic polymer. For certain applications - soft moldings for example - this may be thoroughly d sirable.
The principle of resolution of stereoisomers is known.
The metallocenes I and Ia can be prepared by the prin-ciple o~ the following reaction scheme:
~2~ t butylLi~RcLi X-(CR8~9)m~R7-(CR~R9)n^X
~Rd ,butylLi - ~RdLi .~ .
- - i- , :: . ..
~
: : :
: ~
.
2 ~ d HRC- ~ CP~8R9 ) m~ R7- ~ CR8R9 ) n^ RdH 2 bUtylLi LiR~- (CR~R9)m-R7- (CR8R9)n-RdLi ZrC14 >
R~ Zr ~ R7 Zr ) _ ~ R~9~:i," - R~
` ( R8R9C ~ m _ RC
R2Li :E~ Zr ~> I 1 ~2 (R8R9C)n - Rd ::
, . R3 X = Cl ~ Br, I or O-tosyl; H2R~ = ~( f or I or R14 for Ia / \ R5 H H
"
' ~ ~1 ' ~ ' ' ' , ' ,.~ ' ` ' : .
2i~
/ fox I or H
or R14 ~ ~uLi~ 7HR14Li ,~
Rl~ R12 a, ~R14hi Rl5H
~ / ~ f ;~ ~c b, ~2 ' Rl1Rl~ 2 Bu~i RlS
~ _ ~15-`,'' ~ llR12 ~ Li2 . .
~ 1 ~ ZrC14 ~ ~.
, :~
~:
~ ~c~ za ~ cl ~ Ll ~ 12~ ~ ~l~ Cl ~ R~
''``', ~ , :
(cf. Journal of Organomet. Chem. (1985) 63-67 and ~P-: A 320762).
,`~,: j The choice of the metallocenes for the polymerization of : olefins to give polyoleins having a broad or multimodal :: ~
.' ,. ~ :
- 12 - 2~$~
dis~ribution can take place by means of a test polymeri~ation for each metallocene.
In this test, the olefin is polymerized to tha polyolefin and the mean molecular weight ~ thereof and the molecu-lar weight dis~ribution M~/Mn thereof are determined bymeans of gel permeation chromatography. Depending on ~he desired molecular weight di~tribution, the metallocenes axe then combinsd.
Taking into accoun~ the polymerization activities, it is then pos~ible, ~y means of computer ~imulation of the combined gel permeation curves, to direct~y produce any desired molecular weight di~tribution via the type of metallocenas and via the ratio of the amounts of the metallocenes to one another.
The number o zirconocenes to be used according to the invention is preferably 2 or 3, in particular 2. However, it i5 also possible to u~e a greater number (such a~, for example, 4 or 5) in any desired combination of I and Ia.
By including the polymerization activities and molecular weights at variou~ polymerization temperatures, in the presence of hydroqen as molecular weight regulator or in the presence of comonomers, ~he computer simulation model can be further refined and the applicability of the process according to the invention urther improved.
~` 25 The cocatalyst u~ed is an aluminoxane of the form~la II
and/or III, where n is an integer from 0 to 50, prefera-bly 10 to 35.
The radicals R are preferably identical and are methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
If the radicals R are different, ~he~ are preferably ~ methyl and hydrogen or alternati~ely meth~l and isobutyl, ,.
I ~: ' ., .' , ' , .
' :~ ' - ,~ ~ ' . . ' .' ,, ' ', . ' ' , .' :
`', , ' ':~ ', ' , ' .~ .. , .
2 0 ~ 9 ~ J
hydrogen or isobutyl preferably being presen~ to the exten~ o~ O.01-40% (num~er of radicals R). The aluminox-ane can be replaced as cocatalyst in the pol~merization by a mixture comprising aluminoxane and AlR3, where R is as defined above.
The aluminoxane can be prepared in variou~ wayæ by known processes. One of the methods is, for example, to react an aluminum hydrocarbon compound and/or a hydridoaluminum hydrocarbon compound with water (gaseous, solid, liquid or bound - for example ~s water of crystallization) in an inert sol~nt ~such as, for example, toluene). To prepare an aluminoxane con~aining different al~yl groups R, two : different trialkylaluminum compounds [AlR3 + AlR'33, corresponding to ~he desired composition, are reacted : 15 with water (cf. S. Pasynkiewicz, Po~yhedron 9 (1990) 429 and EP-~ 302 424).
The precise structure of the aluminoxanes II and III is unknown.
Irrespective of the preparation method, all aluminoxane `~ 24 s~lutions have in common a varyin~ content of unreacted aluminum starting compound, which is in free form or as a~ adduct.
It is possible, before use in the pol~merization reac-~;~ tion, to preactivate the metallocenes, in each case ; 25 separately or together as a mixture, by means of an aluminoxane of the formula (II~ and/or (III). This significantly increases the polymeri~at.ion activity and improves the particle morphology.
, ~
:~ The pre~cti~ation of the metallocenes i6 carried out in ::
~ 30 solution. The metallocenes are preerably dissolved, as `:
~ , solids, in a 601ution of the alumino~ane in an inert ,: hydrocarbon. Suitable inert hydr~carbons are aliphatic or aromatic hydrocarbons. Toluene or a C6-C1O-hydrocarbon is preferably used.
:.
' ~ .
I' .,:
~,~: : . - -:
;` , ' : ' ~` , ' ~ ' ' ' ' , . ' ' ' The concentration of the aluminoxane in the solution i5 in the range from about 1% by weight to the saturation limit, preferably from 5 to 30~ by weight, in each case based on the total solution. The metallocenes can ~e employed in the same concentration, but are preferably employed in an amount of from 10-4-l mole per mole of alumino~ane. The preactivation time is from 5 minutes to ~0 hours, preferably from S to 60 minutes D ~he tempera-ture used is from -78C to 100C, preferably from 0 to 70C.
The metallocenes may also be prspolymerized or applied to a support. Prepolymerization is preferably carried out using the (or one of the) olefin(s) employed in the polymerization.
Examples of suitable supports axe silica gels, al~ninum oxides, solid ~luminoxane or other inorganic ~upport materialæ. Another suitable support material is a poly-~lefin powder in finely divided form.
A further possible embodiment o the process according to the invention comprises using a salt~ e compound of the formula RXNH4XBR~4 or of the formula R3PHBR'4 as cocatalyst in place of or in addition to an aluminoxane. In these formulae, x = 1, 2 or 3, R = alkyl or aryl, identical or different, and R' = aryl, which may also be fluorinated or partially fluorinated~ In thi~ case, the catalyst comprises the product of the reaction of the metallocenes with one of said compounds (cf . EP-A 277 004 ) .
In order to remove the catalyst poisons present in the olefin, purification by means of an alkylaluminum com-pound, for example AlMe3 or AlEt3, is advantageous. Thispurification can be carried out either in the ; polymerization system itself, or the olefin is brought into contact with the Al compound before addition to the polymerization system and is subsequently removed again.
~' .` ' ' ' 2 0 ~
_ 15 -The polymerization or copolymer:ization is carried out in a known manner in solution, in suspension or in the ga~
phase, con~inuously or batchwise, in one or more step~, at a temperature of from -60 to 200C, preferably from 20 to 80C. Olefins of the formula R~-CH=CH-Rb are polymerized or copol~merized. In this formula Ra and Rb are identical or different and are hydrogen atoms or alkyl radicals having 1 to 14 carbon atoms. However, R~
and Rb may also form a ring with the carbon atoms con-necting them. Ex~mples of such olefins are ethylene,propylene, l-~utene, l-hexene, 4-methyl 1-pentene, l-octene, nor~rnene and norbornadiene. In particular, propylene and ethylene are polymerized.
If necessary, hydrogen i~ added as molecular weight regula~or. The various hydrogen-reactivities of the metallocenes and the possibility of changing the amount of hydrogen during the polymerization can result in a further desired broadening of the molecular weight distribution.
The overall pressure in the polymerization system is from O.5 to 100 bar. The polymerization i~ preferably carried out in the industrially particularly interesting pressure range of from 5 to 64 bar.
; The metallocenes are used in a concentration, based on the txansition metal, of from 10-3 to 10-8 mol, prefe:rably from 10-4 to 10-7 mol, of transition metal pex dm3 of solvent or per dm3 of reactor volume. The aluminoxane or the aluminoxane/AlR3 mixture is used in a concentration of from 10-5 to 10~1 mol, preferably frcm 10-4 t~ 10-2 mol, per dm3 of solvent or per dm3 of reactor ~ol~me. In principle, however, higher concentrations are also possible.
':
If the polymerization is carried out as a suspension or solution polymerization, an inert solvent which i9 ' '~
':~
.- , ' .
~- I
~ 3 customary ~or the Ziegler low-pressure process is used.
For example r the polymerization is carried ~u~ in an aliphatic or cycloaliphatic hydrocarbon; the examples of these which may be mentioned are ~utane, pentane, hexane, heptane, decane, isooctane, cyclohexane and methylcyclo-hexane. It is also possible to use a gasoline or hydro-genated diesel oil frac~ion. Toluene can also be used.
The polymerization is pref~rably carried out in the liquid monomer.
If inert solvents are used, the monomers are metered in in gaseous or liquid form.
The polymerization can ta~e as long as desired, since the catalyst system used according to the inven~ion only exhibiks a slight decrease in the polymerization activity lS with time.
The process according ko the invention is distinquished . by the fact that the metallocenes described give polymers having a broad, bimodal or multimodal molecular weight distribution, high molecular weight, high stereospecifi-city and good particle morphology in the industriallyinteresting temperature range between 20 and 80C with high polymerization Activity.
The pol~mers accoxding to the invention are particularly suitable for the production of films, in particul~r transparent films, thermoforming applications~ polyolefin : foams, extrusion applications and for ~he pr~duction of transparent hollow articles and for blow molding in general.
, The examples below are intended to illustrata the inven-tion in greatsr detail.
The following abbreviations are used:
~N = viscosity number in cm3/g , ' , .:
. - . .
:.,:~.
... .
:: , = weight a~erage molecular ~ determined by weight in g/mol ~ gel permeation M~tMn = molecular weigh~ dispersity J chromatography II = i~o~actic index (mm ~ 1i2 mr) 1 determinad by SI = syndiotactic index ~ l3C-NMR
(rr + 1/3 mm) J spectroscopy MFI (230/5) = melt flow index, mea~ured in accordance with DIN 53735; melt temperature 230C
and weight 5 kg.
: 10 Example 1 A dry 24 dm3 reactor was flushed with nitrogen and filled with 12 dm3 of liquid propylene. 39 cm3 of a toluene solution of methylaluminoxane (corresponding to 5~ mmol of Al, mean degree of oligomerization of the methylaluminoxane was n = 19) were then added, a.nd the batch was ~tirred at 30C for l~ minutes.
In parallel, 13.5 mg (0.025 mmol) of rac-phenyl(methyl)-:~ silyl(2-methyl-1-indenyl)2zirconium dichloride and 51.0 mg (O.10 mmol) of rac~phenyl(met~yl)silyl(l-~ 2G indenyl)zirconium dichloride were di~solved in 15 cm3 of - a toluene eoluti~n ~f methylaluminoxane (20 mmol), and the ~ution was introduced i~to the reactor after 15 minutes.
The mixture was polymerize~ at 30C for 3 hours. The ; 25 pol~merization was terminated by addition of 12 1 of CO2 ga~O 1.85 kg of polypropylene were obtained, correspo~d-ing to an activi~y of the metallocene mixture of 9.6 kg of PP~g of metallocene x h.
VN = 331 cm3/g; M~ = 411,000 g/mol, M~/M~ = 8.5; II =
96.g%.
Example ~
Example 1 wa9 repeated, but ~he metallocene mixture ~;~ components employed were 11. 2 mg (0.025 ~unol) of rac-ethylenet2-me~hyl l-indenyl)2zirconium chloride and 13.9 mg (0.025 mmol) of diphenylmethylene(9-fluoren~
~cyclopentadienyl)zirconium dichloride; the `:: `: :
2 ~ J
polymeri~ation tempera~ure was 60C and the polymerization t.ime was 1 hour.
2.45 k~ of polypropylene were obtained, corresponding to an activity of the metallocene mixture of 9706 kg of PP/g of metallocene x h.
VN = 255 cm3/g; M~ = 38$,000 g/mol, M~/M~ = 7.5.
The resultant pol~mer could be separated b~ fractionation into a fraction of isotactic p~lypr~pylene (II > 96%) and a fraction of syndiotactic polypropylene (SI > 96~ he mixing ratio was about 1 Example 3 Example 1 was repeated, but the metallocene mixture components employed were 5.4 mg ~0.010 mmol) of rac-- phenyl(methyl)silyl(2-methyl-1-indenyl)2zirconium dichloride and 5.4 mg (O.013 mmol) of dimethylmethylene-(9-fluorenyl)~cyclopentadienyl)zirconium dichloride, the polymerization temperature was 70~C and the polymerization time was 1 hour.
2.2 kg of a mixture of about two part~ of isotactic polypropylene and one part of syndio$actic polypropylene were obtainedl corresponding to an activity of the metallocene mixture of 203.7 kg of PP/g o~ metallocene x . ~.
VN = 172 cm3/g; M~ - 186,~00 g/mol, N~/N~ = 3Ø
Example ~
Example 1 wa~ repeated, but the metal}ocene mixture components employed were 4.8 mg (0.01 mmol) of rac-Me2Si(2-methyl-1-indenyl~2zirconium dichloride and21.2 mg (O.05 mmol) of rac-Me2Si(2,3,5-trimethylcyclopenta-dienyl)2zirconium dichloride, and the polymerization ~ temperature was 50C.
- 2.57 kg of polypropylene were obtained, corresponding to an activiky of the metallocene mixture of 32.9 kg of PP/g ~ of metallocene x h.
:, :~ .
. :
~ : ~
!
2~5~ 3J
- lg -VN = 194 cm3/g; M~ - 261,000 ~/mol, ~/N~ = 7.9, II =
98.5%~
Example 5 Example 1 was repea~ed, but the metalloc2ne mixture components employed were 4.5 mg (0.008 mmol) of rac~
phenyl(methyl~sil~l~2-methyl-l-indenyl)2zirconium dichloride and 6 . 6 mg (0.015 mmol) of xac-dLmethylsilyl-(indenyl)2zirconium dichloride. The polymerization time was one hour~ iand the polymerization temperature was 50C~
1.35 kg of pol~propylene were obtained, corresponding to an activity of the metallocene mixture of 121.6 kg of PP/g of metallocene x h.
VN = 154 cm3/g; N~= 133,000 g/mol, ~ = 5.2, II = 96.0~.
Example 6 ~xample 1 wa~ repeated, but the metallocene mi~tur~
components employed were 2.4 mg (0.005 mmol) of rac-dimethylsilyl(2-methyl-1-indenyl~zirconium dichloride and 2.5 mg (0.005 mmol) of rac-dimethylgerm~l~inde~yl)2-zirconium dichloride. ~he two metallocene~ were dissol~ed separately, each in 7.5 cm3 of a toluene solution of methylaluminumoxane, and after 15 minutes these solutions were metered into the polymerization ~ystem. The mixture wa6 polymerized at 70~C for 1 hour.
1.57 kg of polypropylene were obtained, corresponding to an activity of the metallocene sy6tem of 320.4 kg of PP/g of me~allocene x h.
VN = 105 cm3/g; M~ = 114,000 g/mol, M~/M~ = 4.1, II =
96.3~.
Example 7 Ex~mple 6 was repeated, but the metallocenes used were 4.8 mg tO.Ol mmol) of rac-dimethylsilyl(2-m~th~
indenyl~2zirconium dichloride and 1.5 mg (O.004 mmol) of I rac-dimethylsilyl(indenyl)2dimethylzirconium.
;' ~, ,~:.. : .. . . .
2 ~ 2 2.08 kg of polypropylene were obtained, corresponding to an activity of the metallocene system of 330.2 kg of PP/g of metallocene x h.
VN = 121 cm3/g; N~ = 101,900 g/mol, N~/M~ = 4.0t II =
96.0~.
Example 8 Example 6 was repeated, but the metallocenes used were 2.7 mg (0.005 n~ol) of rac-phenyl(methyl)silyl(2-methyl-l-indenyl)2zirconium dichloride and 2~,5 mg (O~04 mmol) of rac-phenyl~inyl)silyl(indenyl) 2Z irconium dichloride.
: 2.17 kg of polypropylene were obtained, corresponding to an activity of the metallocene ~ystem of 93.5 kg of PP~g of metallocene x h.
VN = 102 cm3~g; MW = 79,400 g/mol, ~ 3.3, II = 96.9%.
Example 9 Ex~mple 6 wa~ repeated, but the metallocene~ used were 4.8 mg (0.01 mmol) of rac-dimethylsilyl(2-methyl-1-inden~l)2zirconi~m dichloride and 9.2 mg ~ n .02 mmol) of rac-Hz~-CH2-CH2-Si(indenylj~zirconium diGhloride.
1.82 kg of polypropylene were o~tained, corresponding to an activity of the metallucene system of 130 kg of PP/g of metallocene.
VN = 145 cm3/g; M~ = 185~5no g/mol~ N~ = 3.6, II =
96.8%.
Example 10 Example 6 was repeated, but the metallocenes u~ed were 2.7 mg ~O.005 mmol) of rac-phenyl(methyl)silyl(2-methyl-; 1-indenyl)2zirconi~m dichloride and 2.4 mg (O.006 ~mol) of rac-dimethylsilyl(2,4-dimethylcyclopentadienyl) 2-zirconium dichloride.
1.31 kg of polypropylene were obtainedl corresponding to an activity of the metallocene system of 256.9 kg of PP/g ~;i ,:~
- .
--:
: - - , , :
- ~ .
- 21 _ 2~
of metallocene x h.
VN = 118 cm3/g; ~ = 129,500 g/mol, ~ 3.B, II =
g8.0%.
E~ample 11 Example 1 was repeatedl but the metallocenes u~ed were 26.9 mg (O.05 mmol) of rac-phenyl(methyl)silyll~-methyl-1-indenyl)zzircvnium dichloride and 32.5 mg (O.08 mmol) of rac-dim2thylsilyl~2,4-dimethylcyclopentadienyl) 2 zirconium dichloride. The polymer Lzation time was 2 hours. 2.32 kg of polypropylene were obtained, corres-ponding to an activity of the metallocene sy~tem of 19.5 kg of PP/g of metallocene x h.
VN - 386 cm3/g; ~ = 436,000 g/mol, M~/M~ = ~.2, II =
98.5%.
Example 12 Example 1 was repPated, but the metallocenes used were 9.2 mg (0.02 mmol) of rac-methylethylene(2-methyl-1-;:~ indenyl)2zirconium dichloride and 8.6 mg (0.0~ mmol) of rac-dLmethylmethylenetI-indenyl)2~irconium dichloride, and the polymer.ization temperature was 50C. 1.42 kg of polypr~py1ene were obtained, corxeæponding to an activity of the metallocene system of 26.6 k~ of PP/g of metallocene x h.
VN -~ 101 cm3~g; M~ = 123,000 g/mol, M~/M~ = 8.5, II =
91.6%.
~xample 13 A dry 24 dm3 reactor was ~lu~hed with nitrogen and filled with 24 dm3 (s.t.p.) of hydr~gen and 12 dm3 of liquid propylene.
10 ml of a toluene ~olution of trimethylaluminu~ (corres-ponding to 2~ mol of AlMe3) were then added, and the batch was ~tirred at 40C for 15 minutes.
In parallell 5.4 mg (0.01 mmol) of rac-phenyl(methyl)-silyl(2-methyl-l-indenyl~2zirconium dichloride and 4.9 mg " ~ .
, ~
2 ~
(0.01 mmol) of rac-dimethylgermyl(indenyl)azirconi~m dichloride were dissolved in 15 cm3 of methylaluminoxane solution (20 mmol of Al, toluene)y and, after 15 minutes, the solution was introduced into the reactor. Th~ reactor contents were heated to 65C in 3 minutes and polymerized at this temper~ture for on~ hour.
~he polymerization was terminated by addition of 12 1 of CO2 gas, exces~ propylene was removed in gaseous form, and the p~l~mer p~wder was dried at 80~CJ100 mbar.
2.25 kg of polypropylene were obtain~d, corre~ponding to an activity of the metallocene mi~ture o 218.5 kg of PP/g of metallocene x h.
VN = 91 cm3/g; M~ = 72,800 g/mol; MW/M~ = 4.~, II = 96.8~.
Example 14 Example 1 was repeatedl but the metallocenes u~ed were 5.4 mg (O.010 mmol) of rac-phenyl(methyl)silyl(2-methyl-l-indenyl)2zirconium dichloride and 2700 m~ (0.056 mmol) of rac-dimethy~silyl(2-methyl-4,5,6,7 tetrahydro-l-: indenyl)2zirconium dichloride, the polymerization tem-perature was 50C, and the polymerization time was :~ 1.5 hours.
~'~
1.51 kg of polypropylene were obtained, corresponding to : an activity of the metallocene ~ystem of 31.1 kg of PP/g : of metallocene x h.
VN = 187 cm3/g; M~ - 132,500 g/mol, M~N~ = 4.1, II =
; 97.6%.
Example 15 ;~ Example l was repeated, but the metallocenes used were 4.8 mg tO.O10 mmol) of rac-dimethy~ yl(2-methy~
~: 30 indenyl)2zirconium dichloride and 7.0 mg ~0.017 mmol) of rac-ethylene~l-indenyl)2zirconium dichloride. The polymerization temperature was 50C and the :: polymerization duration was 1 hour.
,',~ '.
,;:
.
' ~
: ,.~
-; : . . :
.
.:. : : , 2 ~ 6 ~3 1~50 kg o polypropylen0 were o~tained, corresponding to an activity of the metallocene system of 127.1 kg of PP/g o metallocene x h.
VN = 125 cm3~g; M~ = 129,500 g/mol, N~/M~ = 5.3r II =
- 5 9~.4%.
Example 16 : Example 1 was repeated, but the metallocenes used were 6.0 mg ~0.010 mmol) of rac-diphenylsilyl(2-methyl-1-indenyl)2zirconium dichloride, 6.0 mg ~0.013 mmol) of rac-dimethylsilyl(l-indenyl)2zirconium dichloride and 36.0 mg ~O.083 mmol) of rac-dimethylsilyl~2,3 r 5 ~ri-methylcyclopentadienyl)zzisconium dichloride, the polymerization temperature was 40C and the polymeriza~ion duration was 2 hours.
1.79 kg of polypropylene were obtained, corresponding to an activity of the metallocene 3ystem of 18.6 lcg of PP/q ~ of metallocene x h.
: VN = 267 cm3/g~ N~ ~ 293,000 g/mol, N~ = 5.7, II =
98~0%, MFI (230~5) = 24.6 g/10 min.
~xample ~7 A dry 24 dm3 reactor was flushed with propylene and ~- filled with 12 dm3 of liquid propylene and with 2~ ml of a toluene solution of trimethylaluminum ~corresponding to ~ 52 mmol of AlMe3)O ~he batch was 6tirred at 30C for : 2~ lS minutes.
In parallel, 3.0 mg (O.005 mmol) of rac-diphenyl~ilyl(2-methyl~1-indenyl)2zirconium dichloride, 2.n mg (0.004 mmol) of rac-dimethylsilyl(2-methyl-l-indenyl) 2-zirconium dichloride and 2.0 mg (O.004 mmol) of rac ~0 dimethylgermyl(1 indenyl)2zirconium dichloride were dissol~ed in 20 cm3 of methylalumino~ane ~o~ution ~ (27 mmol of Al, toluene), and, after 15 minutes, the :; solution was introduced into the reactor. I'he mixture was ~ polymeriæed at 65C for 1.5 hours.
"' .
: - . ::
2 ~ ?.
~ 24 -1.59 kg of polypropylene were obtained, co~responding to an activity of the metallocene system of 1~1.4 kg of PP/g of metallocene x h.
: VN = 153 cm3tg; M~ = 195,000 g/mol, N~/M~ = 5.8, II -9600%, MEI (230/51 = B7 g/10 min.
Example 18 Example 1 was repeated, but the metallocenes used were 6 . O mg ( O . 01 mmol ) of rac diphenylsilyl ( 2-methyl-1-indenyl)2zirconium dichloride and 4S.0 mg (0.10~ mmol3 O:e rac-methylene(3~t-butyl-1-cyc~opentadienyl) 2Z irconium dichloride, the polymeri~ation temparature was 4~DC and the polymerization duration wa~ 4 hours.
1. 63 kg of polypropylene were obtained, corresponding to : ~ an activity of the mekallocene system of 8.0 kg of PP/g of metallocene x h.
VN = 358 cm3~g; M~, = 3S4~000 g/mol, ~/Mn = 12.5, ll =
9 3 . 5 % .
,, ExampLe 19 Example 1 was repeated, but the m~tallocena~ u3ed were 6.0 mg (0.010 mmol) of rac-diphenyl~îlyl(2-methyl-1-indenyl)zzirconium dichloride and 6.0 mg (0.012 mmo~) of rac-dimethylsilyl(4,7-dimethyl-l-indenyl~2zirconium l dichloride~ the polymerization temperature was 40C and ;~ the polymerization duration was 2 hours.
0.85 kg o~ polypropylene were obtained, corresponding to ~ an activity of the metallocene 8y tem of 35.4 kg of PP/g : of metallocene x h.
`~ VN = 324 cm3/g; ~ = 352,500 g/mol, M~/M~ = lS.5, II =
:~' 95.~%.
' Example 20 ,~; Example 1 was repeated, but the metallocenes used were : 6.0 mg (0.010 mmol) of rac-diphenyl~ilyl~-methyl-l-indenyl)2zirconium dichloride and 7.2 mg (0.016 mmol) of ~ rac-ethylene(2-methyl-1-indenyl)2zirconium dichloride.
.:
'':
.: ~
,. . .
- 25 - 2~ tJ
The polymerization tempexature was 50C and the polymerization duration was 2 hours.
1.44 kg of polypropylene were obtained, corresponding to an activity of the metallocene system o 54.S kg o~ PP/g of metallocene x h.
VN = 227 cm3/g; H~ = 406,000 g/mol, ~JM~ = 8.0 97.1%.
Example 21 Example 20 was repeated, but in addition 75 g of ethylene were metered in continuously during the polymerization.
The polymerization temperature was 60C and the polymerization time was 1 hour.
1.65 ~g of ethylene propylene copolymer were obtained, corresponding to an acti~ity of the metallocene system o~
1~5.0 kg of copolymer/g of metallocene x h.
VN = 291 cm3/g; M~ = 387,000 g/mol, N~/N~ = 7.4; 4.2%
ethylene content with ethy~ene units predominantly incorporated in an i~olated manner (l3C NMR analysis~.
Example 22 ~ 20 Example 21 was repeated, but 300 g of ethylene were only ; added after a polymerization time of 30 minut~s.
1.49 ~g of copolymer were obtained, ~orresponding to an acti~ity of the metallocene system of 112.9 kg of copolymer/g of metallocene x h.
VN = 357 cm3g; M~ = 449,000 g/mol, M~/M~ = 8.8. The polymer product can be ~eparat~d by fractionation (decane, diethyl ether) into a polypropylene component and an ethylene-propylene rubber component.
Ethylene content of the copolymer 18.4%.
Example 23 A dry lS0 dm3 reactor wa~ flushed with nitrogen and fi~le~ at 20CC with 80 dm3 of a gasoline fraction with the aromatic~ removed and with a boiling range o~
, :
:
.- .
_ 26 -100-120C. The gas space was then flushed free from nitrogen by injecting 2 bar of propylene and releasing the pressure, and rep~ating this cycle four times.
50 1 of liquid propylene were added, and 64 cm3 of a toluene solution of methylaluminoxane (corresponding to 100 mmol of Al, molecular weight 390 g/mol according to cryoscopic determina~ion) ~ere added and the reactor contents were heated to 50C.
Hydrogen was me~ered in to give a hydr~gen co~tent in the gas space of ~he reactor of 0.1%, and this content was then main~ained during the entire polymeri2ation time ~y topping up (monitoring on-line by gas chromato~raphy).
15.3 mg of rac methylethylene(2-methyl-1-ind~nyl)2-zirconium dichloride (0.033 mmol), 6.3 mg of rac-phenyl~
; 15 ~methyl)silyl(2-methyl-l-indenyl)2zirconium dichloride (0.012 mmol) and 7.0 mg of rac-diphenylsilyl~2-methyl-1-indenyl)22irconium dichloride (0.012 mmol) were di~solved in 32 ml of a toluene solution of methylaluminoxane (corresponding to 50 mmol of Al) and, after 15 minutes, the solution was i~troduced into the reactor.
., The reactor ~as kept at a polymerization temFerature of 50C for 7 hours by cooling, the polymeri~ation was then terminated by addition of 2 bar of C2 gas, and the ` polymer formed was separated from the suspension medium i~ 25 in a pressure filter. The product wa~ dried for 24 hours at 80C/~00 mbar, 16.4 kg of polymer powder, were obtained corresponding to a metallocene activity of 81.~ kg of PP/g of metallocene x h.
:~ VN = ~06 cm3/g; M~ = 248,000 g/mol; M~/Mn = 3.4 - 30 II = 97.9~; MFI (230/5) = 32 g/10 min, m.p.: 151C
The product had the following mechanical data:
Modulus of elasticity in tension (in accordance with DIN 53457-Z) 1,430 N/mm2; ~otched impact strength (an in accordance with DIN ~3453) 5 mJ/mm2 a~ ~3C; Izod impact ~;
2 ~ r~J
~ 27 -strength (in accordance with ISO 180/1 C) 69 mJ/mm2 at ~3C and 12 mJ/mm2 at -30C; Izod notched Lmpact strength (according ~o ISO 180/1 ~) 3 m~/mm2 at 23C and 2 mJ/mmZ
at -30C; ball indentation hardness (p~essing, condi-tioned, 358 ~) 84 ~/mm2 and ball inden~ation hardness (injection molding, 358 N, in accordance with DIN 53456) 75 N/mm2.
Example 24 Exam~le 23 was repeated but the metallocene mixture comprised 6.3 mg of rac-phenyl~methyl)silyl(2-methyl-1-indenyl)2zirconium dichloride ~O.nl2 mmol) and 2.9 mg of rac-d~methylsilyl(l-indenyl) 2Z irconium dichloride (0.006 mmol). Polymerization was carried out without hydrogen.
The polymerization was complete after 20 hours.
18.7 kg of polymer powder were ~tained~ corresponding to a metallocene activi~y of 101.6 kg of PP/g of metallocene x h.
VN = 202 cm3/g; M~ = 296,000 g/mol; M~/M~ = 7.9 II = 96.4%; NFI (230/5) = 39 g/10 min; m.p.: 148C
The product had the foll~wing mechanical da~a:
Modulus o~ elasticity in tensi~n (in accordance with DIN 5347-Z) 1,28a N/mm2; notched impact ~trength (an in accordancP with DIN S3453) 3 mJ/mm2 at 23~C; I~od impact .: 25 strength (in accordance with ISO 180/1 C) 65 mJ/mm2 at 23C and 11 m~/mm2 at -30C; Izod notched Lmpact strength (according to ISO 180/l A) 3 mJ/mm2 at 23C and 2 mJ~mm2 a~ -30JC; ball indentation hardness 77 N/mm2 (pr~sing, conditioned, 358 N) and 71 N/mm2 (injection molding, 358 N, in accordance with DIN 53 456).
~. :
....
~,
Claims (6)
1. A process for the preparation of a polyolefine which has a molecular weight distribution Mw/Mn of ? 3.0 and which may be monomodal, bimodal or multimodal, by polymerization or copolymerization of an olefin of the formula RaCH=CHRb in which Ra and Rb are identical or different and are a hydrogen atom or a alkyl radical having 1 to 14 carbon atoms, Ra and Rb, together with the atoms connecting them, can form a ring, at a temperature of from -60 to 200°C, at a pressure of from 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst comprising a transition-metal com-ponent (metallocene) and an aluminoxane of the formula II
(II) for the linear type and/or of the formula III
(III) for the cyclic type, where, in the formulae II and III, the radicals R may be identical or different and are a C1-C6-alkyl group, a C1-C6-fluoroalkyl group, a C6-C18-aryl group, a C1-C6-fluoroaryl group or hydro-gen, and n is an integer from 0 to 50, or, instead of the aluminoxane, comprises a mixture of an aluminoxane of the formula II and/or of the formula III with a compound AlR3, which comprises using, as the transition-metal component, at least one zirconocene of the formula I and at least one zirconocene of the formula Ia or alternatively at least 2 zirconocenes of the formula I
(I) (Ia) in which R1 and R2 are identical or different and are a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryl-oxy group, a C2-C10-alkenyl group, a C7-C40-aryl-alkyl group, a C7-C40-alkylaryl group, a C8-C40-arylalkenyl group or a halogen atom, R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, which may be halogenated, a C6-C10-aryl group, or a , -SR10, , or radical, in which R10 is a halogen atom, a C1-C10-alkyl group or a C6-C10-aryl group, R5 and R6 are identical or different and are as defined for R3 and R4,with the proviso that R5 and R6 are not hydrogen, R7 is , =BR11, =AlR11, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR11, =CO, =PR11 or =P(O)R11, where R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-aryl group, a C6-C10-fluoroaryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R11 and R12 or R11 and R13, together with the atoms connecting them, in each case form a ring, and M1 is silicon, germanium or tin, Ra and Rb are identical or different and are as defined for R11, R14 and R15 are identical or different and are monocyclic or polycyclic hydrocarbon radicals which can form a sandwich structure together with the zirconium atom, and m and n are identical or different and are zero, 1 or 2, where m plus n is zero, 1 or 2.
(II) for the linear type and/or of the formula III
(III) for the cyclic type, where, in the formulae II and III, the radicals R may be identical or different and are a C1-C6-alkyl group, a C1-C6-fluoroalkyl group, a C6-C18-aryl group, a C1-C6-fluoroaryl group or hydro-gen, and n is an integer from 0 to 50, or, instead of the aluminoxane, comprises a mixture of an aluminoxane of the formula II and/or of the formula III with a compound AlR3, which comprises using, as the transition-metal component, at least one zirconocene of the formula I and at least one zirconocene of the formula Ia or alternatively at least 2 zirconocenes of the formula I
(I) (Ia) in which R1 and R2 are identical or different and are a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryl-oxy group, a C2-C10-alkenyl group, a C7-C40-aryl-alkyl group, a C7-C40-alkylaryl group, a C8-C40-arylalkenyl group or a halogen atom, R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, which may be halogenated, a C6-C10-aryl group, or a , -SR10, , or radical, in which R10 is a halogen atom, a C1-C10-alkyl group or a C6-C10-aryl group, R5 and R6 are identical or different and are as defined for R3 and R4,with the proviso that R5 and R6 are not hydrogen, R7 is , =BR11, =AlR11, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR11, =CO, =PR11 or =P(O)R11, where R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-aryl group, a C6-C10-fluoroaryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R11 and R12 or R11 and R13, together with the atoms connecting them, in each case form a ring, and M1 is silicon, germanium or tin, Ra and Rb are identical or different and are as defined for R11, R14 and R15 are identical or different and are monocyclic or polycyclic hydrocarbon radicals which can form a sandwich structure together with the zirconium atom, and m and n are identical or different and are zero, 1 or 2, where m plus n is zero, 1 or 2.
2. The process as claimed in claim 1, wherein, in the formula I, R1 and R2 are identical or different and are methyl or chlorine, R3 and R4 are hydrogen, R5 and R6 are identical or different and are methyl, ethyl or trifluoromethyl, R7 is a or radical, and n plus m is zero or 1.
3. The process as claimed in claim 1 or 2, wherein the compound of the formula I is rac-dimethylsilyl(2-methyl-1-indenyl)2zirconium dichloride, rac-ethylene(2-methyl-1-indenyl)2zirconium dichloride, rac-diphenylsilyl(2-methyl-1-indenyl)2zirconium dichloride, rac-methylethylene(2-methyl-1-indenyl)2-zirconium dichloride or rac-phenyl(methyl)silyl(2-methl-1-indenyl)2zirconium dichloride.
4. The process as claimed in one or more of claims 1 to 3, wherein, in the formula Ia, R1 and R2 are identi-cal or different and are methyl or chlorine, R7 is a or radical, n + m is zero or 1 and R14 and R15 are identical or different and are fluor-enyl, indenyl or substituted cyclopentadienyl.
5. The process as claimed in one of claims 1 to 4, wherein the compound of the formula Ia is rac-phenyl(methyl)silyl(indenyl)2zirconium dichloride, diphenylmethylene(9-fluorenyl)(cyclo-pentadienyl)zirconium dichloride, isoproylidene(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, rac-dimethylsilyl(2,3,5-trimethyl-1-cyclopenta-dienyl)2zirconium dichloride, rac-dimethylsilyl-(indenyl)2zirconium dichloride, rac-dimethylgermyl-(indenyl)2zirconium dichloride, rac-dimethylsilyl-(indenyl)2dimethylzirconium, rac-phenyl(vinyl)silyl-(indenyl)2zirconium dichloride, (indenyl)2zirconium dichloride, rac-dimethylsilyl-(2,4-dimethylcyclopentadienyl)2zirconiumdichloride, rac-isopropylidene(indenyl)2zirconium dichloride, rac-dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1-indenyl)2zirconium dichloride, rac-ethylene-(indenyl)2zirconium dichloride, rac-methylene(3-t-butyl-1-cyclopentadienyl)2zirconium dichloride or rac-dimethylsilyl(4,7-dimethyl-1-indenyl)2zirconium dichloride.
6. The process as claimed in one or more of claims 1 to 5, wherein propylene is polymerized.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4117259 | 1991-05-27 | ||
| DEP4117259.0 | 1991-05-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2069602A1 true CA2069602A1 (en) | 1992-11-28 |
Family
ID=6432516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002069602A Abandoned CA2069602A1 (en) | 1991-05-27 | 1992-05-26 | Process for the preparation of polyolefins having a broad molecular weight distribution |
Country Status (10)
| Country | Link |
|---|---|
| US (2) | US5350817A (en) |
| EP (2) | EP0702030B1 (en) |
| JP (1) | JP3404493B2 (en) |
| KR (1) | KR100216331B1 (en) |
| AT (2) | ATE199911T1 (en) |
| AU (1) | AU656968B2 (en) |
| CA (1) | CA2069602A1 (en) |
| DE (2) | DE59205811D1 (en) |
| ES (2) | ES2155492T3 (en) |
| RU (1) | RU2101296C1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0705851A2 (en) | 1994-09-13 | 1996-04-10 | Phillips Petroleum Company | Catalyst systems and process for producing broad molecular weight distribution polyolefin |
| US5696045A (en) * | 1993-09-29 | 1997-12-09 | Winter; Andreas | Process for the preparation of polyolefins |
| US6818585B2 (en) | 1998-12-30 | 2004-11-16 | Univation Technologies, Llc | Catalyst compounds, catalyst systems thereof and their use in a polymerization process |
| EP1917281B2 (en) † | 2005-08-22 | 2019-01-09 | Chevron Phillips Chemical Company Lp | Polymerization catalysts and process for producing bimodal polymers in a single reactor |
Families Citing this family (162)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5466766A (en) * | 1991-05-09 | 1995-11-14 | Phillips Petroleum Company | Metallocenes and processes therefor and therewith |
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| IL80888A (en) * | 1985-12-12 | 1991-12-12 | Exxon Chemical Patents Inc | Olefin polymerization catalysts,their preparation and use thereof |
| DE3640924A1 (en) * | 1986-11-29 | 1988-06-01 | Hoechst Ag | 1-OLEFIN STEREOBLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF |
| JP2618384B2 (en) * | 1986-12-27 | 1997-06-11 | 三井石油化学工業株式会社 | Solid catalyst for olefin polymerization and its preparation |
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| JPH0742301B2 (en) * | 1987-02-14 | 1995-05-10 | 三井石油化学工業株式会社 | Particulate aluminoxane, its manufacturing method and its use |
| US4939217A (en) * | 1987-04-03 | 1990-07-03 | Phillips Petroleum Company | Process for producing polyolefins and polyolefin catalysts |
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| DE3750776T2 (en) | 1987-09-11 | 1995-04-27 | Fina Technology | Catalyst system for polyolefin production with a broad molecular weight distribution. |
| US4975403A (en) * | 1987-09-11 | 1990-12-04 | Fina Technology, Inc. | Catalyst systems for producing polyolefins having a broad molecular weight distribution |
| DE3742934A1 (en) | 1987-12-18 | 1989-06-29 | Hoechst Ag | METHOD FOR PRODUCING A CHIRAL, STEREORIGIDAL METALLOCEN COMPOUND |
| IL89525A0 (en) * | 1988-03-21 | 1989-09-10 | Exxon Chemical Patents Inc | Silicon-bridged transition metal compounds |
| US5001205A (en) * | 1988-06-16 | 1991-03-19 | Exxon Chemical Patents Inc. | Process for production of a high molecular weight ethylene α-olefin elastomer with a metallocene alumoxane catalyst |
| DE3825814A1 (en) | 1988-07-29 | 1990-02-01 | Hoechst Ag | METHOD FOR PRODUCING L-OLEFIN POLYMERS |
| DE3907964A1 (en) | 1989-03-11 | 1990-09-13 | Hoechst Ag | METHOD FOR PRODUCING A SYNDIOTACTIC POLYOLEFIN |
| DE3916555A1 (en) * | 1989-05-20 | 1990-11-22 | Hoechst Ag | PROCESS FOR THE PRODUCTION OF ETHYLENE POLYMERS |
| DE59107973D1 (en) * | 1990-11-12 | 1996-08-08 | Hoechst Ag | Process for producing a high molecular weight olefin polymer |
| US5243001A (en) * | 1990-11-12 | 1993-09-07 | Hoechst Aktiengesellschaft | Process for the preparation of a high molecular weight olefin polymer |
| DE59104869D1 (en) * | 1990-11-12 | 1995-04-13 | Hoechst Ag | 2-Substituted bisindenyl metallocenes, process for their preparation and their use as catalysts in olefin polymerization. |
| EP0516019B1 (en) * | 1991-05-27 | 1995-12-27 | Hoechst Aktiengesellschaft | Process for preparing syndiotactic polyolefins with large molecular weight distribution |
-
1992
- 1992-05-25 EP EP95114875A patent/EP0702030B1/en not_active Expired - Lifetime
- 1992-05-25 AT AT95114875T patent/ATE199911T1/en not_active IP Right Cessation
- 1992-05-25 ES ES95114875T patent/ES2155492T3/en not_active Expired - Lifetime
- 1992-05-25 DE DE59205811T patent/DE59205811D1/en not_active Expired - Lifetime
- 1992-05-25 DE DE59209897T patent/DE59209897D1/en not_active Expired - Lifetime
- 1992-05-25 EP EP92108788A patent/EP0516018B1/en not_active Expired - Lifetime
- 1992-05-25 AT AT92108788T patent/ATE136040T1/en not_active IP Right Cessation
- 1992-05-25 ES ES92108788T patent/ES2087339T3/en not_active Expired - Lifetime
- 1992-05-26 CA CA002069602A patent/CA2069602A1/en not_active Abandoned
- 1992-05-26 AU AU17133/92A patent/AU656968B2/en not_active Expired - Fee Related
- 1992-05-26 RU SU5011766A patent/RU2101296C1/en active
- 1992-05-26 JP JP13402992A patent/JP3404493B2/en not_active Expired - Lifetime
- 1992-05-26 KR KR1019920008893A patent/KR100216331B1/en not_active IP Right Cessation
-
1993
- 1993-09-10 US US08/119,893 patent/US5350817A/en not_active Expired - Lifetime
-
1994
- 1994-09-23 US US08/311,068 patent/US5714427A/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5594078A (en) * | 1991-07-23 | 1997-01-14 | Phillips Petroleum Company | Process for producing broad molecular weight polyolefin |
| US5696045A (en) * | 1993-09-29 | 1997-12-09 | Winter; Andreas | Process for the preparation of polyolefins |
| US5700886A (en) * | 1993-09-29 | 1997-12-23 | Hoechst Aktiengesellschaft | Process for the preparation of polyolefins |
| US6150481A (en) * | 1993-09-29 | 2000-11-21 | Targor Gmbh | Process for the preparation of polyolefins |
| EP0705851A2 (en) | 1994-09-13 | 1996-04-10 | Phillips Petroleum Company | Catalyst systems and process for producing broad molecular weight distribution polyolefin |
| US6818585B2 (en) | 1998-12-30 | 2004-11-16 | Univation Technologies, Llc | Catalyst compounds, catalyst systems thereof and their use in a polymerization process |
| US7446073B2 (en) | 1998-12-30 | 2008-11-04 | Exxonmobil Chemical Patents Inc. | Catalyst compounds, catalyst systems thereof and their use in a polymerization process |
| EP1917281B2 (en) † | 2005-08-22 | 2019-01-09 | Chevron Phillips Chemical Company Lp | Polymerization catalysts and process for producing bimodal polymers in a single reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0702030A1 (en) | 1996-03-20 |
| DE59209897D1 (en) | 2001-04-26 |
| AU656968B2 (en) | 1995-02-23 |
| ES2087339T3 (en) | 1996-07-16 |
| JPH05140227A (en) | 1993-06-08 |
| ATE136040T1 (en) | 1996-04-15 |
| EP0516018B1 (en) | 1996-03-27 |
| US5350817A (en) | 1994-09-27 |
| RU2101296C1 (en) | 1998-01-10 |
| JP3404493B2 (en) | 2003-05-06 |
| EP0702030B1 (en) | 2001-03-21 |
| ES2155492T3 (en) | 2001-05-16 |
| AU1713392A (en) | 1992-12-03 |
| KR920021594A (en) | 1992-12-18 |
| EP0516018A3 (en) | 1993-03-03 |
| US5714427A (en) | 1998-02-03 |
| KR100216331B1 (en) | 1999-08-16 |
| EP0516018A2 (en) | 1992-12-02 |
| DE59205811D1 (en) | 1996-05-02 |
| ATE199911T1 (en) | 2001-04-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |