CA2193319A1 - Supported catalyst system, a process for its preparation and its use for the polymerization of olefins - Google Patents
Supported catalyst system, a process for its preparation and its use for the polymerization of olefinsInfo
- Publication number
- CA2193319A1 CA2193319A1 CA002193319A CA2193319A CA2193319A1 CA 2193319 A1 CA2193319 A1 CA 2193319A1 CA 002193319 A CA002193319 A CA 002193319A CA 2193319 A CA2193319 A CA 2193319A CA 2193319 A1 CA2193319 A1 CA 2193319A1
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- Canada
- Prior art keywords
- group
- catalyst system
- supported catalyst
- solvent
- methyl
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Classifications
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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
-
- 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
- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61912—Component covered by group C08F4/60 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61916—Component covered by group C08F4/60 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/61922—Component covered by group C08F4/60 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
- C08F4/61927—Component covered by group C08F4/60 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
Abstract
Supported catalyst system, a process for its preparation and its use for the polymerization of olefins The present invention relates to a supported catalyst system having a high activity, which is obtained by a) bringing at least one metallocene component in at least one solvent into contact with at least one cocatalyst component, b) adding the soluble product to the support material and c) removing the solvent. A preferred embodiment is a supported catalyst system where d) the supported catalyst system is isolated and e) prepolymerized with at least one olefinic monomer.
The present invention also relates to a process for preparing the supported catalyst systems. Finally, the present invention relates to a process for preparing a polyolefin by polymerization of one or more olefins in the presence of at least one catalyst system. In this process at least one olefin having the formula Rm-CH=CH-Rn is polymerized where Rm and Rn are identical or different and are each a hydrogen atom or a carbon-containing radical having from 1 to 20 carbon atoms and Rm and Rn together with the atoms connecting them can form one or more rings.
The present invention also relates to a process for preparing the supported catalyst systems. Finally, the present invention relates to a process for preparing a polyolefin by polymerization of one or more olefins in the presence of at least one catalyst system. In this process at least one olefin having the formula Rm-CH=CH-Rn is polymerized where Rm and Rn are identical or different and are each a hydrogen atom or a carbon-containing radical having from 1 to 20 carbon atoms and Rm and Rn together with the atoms connecting them can form one or more rings.
Description
~ -- 21 9331~
HOECHSTAKTIENGESELLSCHAFT HOE 95/F 314 DR.LV/as 5 Das~ i~tiGI I
Suppo, l6d catalyst system a process for itS preparation and its use for the poly",eri~tion of olefins 10 The pres~n~ invention relates to a SUppGI led catalyst system having a high activity and to an economical and enviro. ""entally friendly process for pr~paring the catalyst system and also to the use of the catalyst system for poly",eri~dlion.
rr~c~sses for prepari.)g polyolefins with the aid of soluble ho-nogenous catalyst 15 systems cGI~ risi~9 a lfansiliGn metal col"ponent of the met~llocene type and a yst col;"~onent seleGled from the group consisting of alumir,oxanes Lewis acids or ionic cGI"pounds have been des~ ibed. These catalysts have a high activity and give ho."opolymers and copolymers having a narrow molerul^- weight distribution.
When soluble (hol"Ggeneous) met~locene/methylaluminoxane catalyst systems are used in processes in which the polymer for",ed is obtained as a solid heavy deposits on the reactor walls and agiL~lor are frequently formed. These deposits are fol",ed by agglomeration (Polymer Commun. (1991) 32 58) of the polymer particles25 when the metallocene or alu",i"oxane or both are presenl in solution in the suspensio. . medium. Such deposits in the rea~tor systems have to be removed regularly since they rapidly reach considerable thicknesses have a high al(en~Jth and hinder heat ll ansrer to the cooling medium.
30 To prevent these deposits it is advant~geous to use metallocenes in suppol led form.
WO-A 94/28034 discloses a supported catalyst system in which a preactivated (at room te"~peralure) solution of metallocene and the coc~t~lyst methylaluminoxane (MAO) is applied to a porous support material (preferably silica gel). The preliminary r~a~ti~n l~tween MAO and metallocene takes between 1 and 60 minutes pr~fetably 10 minutes.
EP-A 0 518 092 ~isclQses a suppo, led catalyst system in which the prea~;tivatedmetallocene/MAO solution is al.plied to porous polymers as support ",alerials. The preactivation take~ from 1 to 120 minutes preferably from 10 to 100 minutes. Thepreacti~ation takes place at te,.,peralures betwecn 0 and 50C.
The catalyst systems des~ ibed have a low productivity based on the suppo, led system in kg of polymer per g of catalyst when compared with cl ~ssi~l Ziegler-Natta systems.
The catalyst systems les~ il,ecJ also have high catalysts costs which are esse, Itially ~us~ by the fact that the e~e"sive co~t~lyst c~",ponent methylaluminoxane has to be used in excess.
It is an object of the prese- Il invention to provide a SUppGI led catalyst system having a high activity and an econG"~ical and envi~..."entally friendly process for prepa.ing the catalyst system.
The object of the present invention is achieved by a SUppGI led catalyst system having a high activity which is obtainable by a) bringing at least one met- 'locene com~onent in at least one solvent into conlact with at least one cocPt~lyst w",pone"t b) adding the soluble product to the support material and c) removing the solvent.
The advantage of the catalyst system of the invention is a significant increase in the activity and the productivity for the same co,l,posilion of the catalyst system where in particular the ratio of cocAt~lyst to metallocene is not altered.
A prefer.ed e,nbodiment of the invention is a supported catalyst system where -d) the SUppGi led catalyst system is isolated and e) prepoly",eri~ed with at least one olefinic ",G"G,oer.
The metalloce"e cG~"~Gnenl of the catalyst system of the invention can in principle 5 be any metallocene. The metallocene can be either l ridged or u,)bridgeJ and have identical or Ji~rent ii,~dl nls. Preference is given to mePIloc6l ,es of group IVb of the Periodic Table of the El~lllents, for example titanium, zirconium or hafnium.
The metallocene is prdferably a met-'locene of the formula (I) below. Particular10 prefarence is given to ~i, conocel ,es which bear indenyl and tetrah~Jro.ndenyl derivatives as ligands.
R3~ 6 ~ ~R I ( I ) R \ R
~ ~
/ B >--6~
Rs~ R4 25 where M1 is a metal of group IVb of the Periodic Table of the Elements, R1 and R2 are ideutical or dirrerent and are each a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C20-aryl group, a C6-C10-aryloxygroup, a C2-C10-alkenyl group, an OH group, an NR122 group, where R12 is a C1- to 30 C2-alkyl group or a C6-C14-aryl group, or a halogen atom, R3 to R8 and R3 to R8 are identical or dirrere"t and are each a hyJ~-,ge" atom, a C1-C40-hyd~ocarL,on group which may be linear, cyclic or bré."~;l,eJ, e.g. a C1-C10-alkyl group, a C2-C10-alkenyl group, a C6-C20-aryl group, a -C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, or c~, It radicals R4 to R8 and/oder R4 to R8 togetl ,er with the atoms con- ,~clin~ them form a ring system, R9 is a bridge, preferal,ly s R10 R10 R10 R10 R1o _ o _ ~2_ O-- --C-- --o_ ~2-- --C--~2_ R1o Rl Rl R10 R10 Rl Rl Rl _ ~,~2_ --C--C_ _ ~t C ~,~2_ R l ' , R l ~ R l l , R l l R l l , R ' l R l l R l l , -- -- x R10 R10 Rl --C--C--C--~ ~10, >~ . - G ~ - . - O - . - S - . ~5 0, ~5 0 ~ , ~C O . ~ or ~11 ( 0 ) ~ ~ , where R10 and R11 are iWentical or differenl and are each a hydroge" atom, a halogen atom or a C1-C40-group such as a C1-C20-alkyl group, a C1-C10-fluoroalkyl group, a C1-C10-. 'koxy group, a C6-C14-aryl group, a C6-C10-fluoroaryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, or R10 and R1 1 together with theatoms co, In6~Ain!3 them form in each case one or more rings, and x is an integer from zero to 18, M2 is silicon, ger")anium or tin and the rings A and B are identical or difrerent, saturated or unsaturated.
R9 can also link two units of the formula I to one another.
219331~
In formula 1 it is particularly pr~fer,~d that M1 is zirconium or hafnium R1 and R2 are idel ltical and are methyl or chlorine in particular chlorine and R9 =
M2R10R11, where M2 is silicon or germanium and R10 and R11 are each a C1-C20-hydloc~ ol~ group such as C1-C10-alkyl or C6-C14 aryl The indenyl or tetrahydroindenyl ligands of the met-llQcenes of the formula I are ~,r~rer~ly substituted in the 2 2 4 4 7 2 6 2 4 6 2 5 6 2 4 5 6 or 2 4 5 6 7 posilions in particular in the 2 4 positions. Pleferled substituents are C1-C4-alkyl groups such as methyl ethyl or isopropyl or C6-C10-aryl groups such as phenyl naphtl ,yl or mesityl. The 2 position is preferably s~ ~hstit~n~d by a C1-C4-alkyl group such as methyl or ethyl.
If the 2 and 4 positions are s~ ~hstihlted then R5 and R5 are preferably ide"tical or difrerent and are each a C6-C10-aryl group a C7-C10-arylalkyl group a C7-C40-alkylaryl group or a C8-C40- arylalkenyl group.
The following numb~ri,)g is used here for the substitution position:
5~
25 Of particular i,npG"ance are also metallocenes of the formula I in which the substituents in the 4 and 5 positions of the indenyl radicals (R5 and R6 as well as R5 and R6 ) tog~tl .er with the atoms cc"necting them form a ring system pre~erably a six~"e"~bered ring. This condensed ring system can likewise be substituted by radicals having the ,..eanings of R3 - R3. An example which may be mentioned of 30 such cGI"~ounds I is din.etl,ylsilanediylbis(2-methyl4 5-benzoindenyl)zirconium dichloride.
Particular pr~fere"ce is given to those compounds of the formula I which bear a C6--C20-aryl group in the 4 positiGn and a C1-C4-alkyl group in the 2 position. An example of such a cGn"~ound of the formula I is dimetl,ylsilanediylbis(2-methyl4-phenylindenyl)zirconium dichloride.
5 Examples of the met~'locene cori"~onenl of the catalyst system of the invention are:
dimethylsilanediylbis(indenyl)zirconium di~l,loride dimethylsilan~li~rlLis(4~aph~1,ylindenyl)zirconium dichloride dimethylsilan~diylbis(2-methyl~"~oindenyl)zirconium dichloride dimethylsilanediylbis(2-methy,indenyl)~irconium dichloride 10 dimethylsilan~i~lLis(2-methyl4-(1~,aphthyl)indenyl)~irconium dichloride dimethylsilanediylbis(2-methyl4-(2-"aphthyl)indenyl)zirconium dichloride dim~th~lsilanediylbis(2-methyl4-phenylindenyl)zirconium dichloride dirnethylsila"~liylbis(2-methyl4-t-butylindenyl)zirconium dichloride dimethylsilanediyll.is(2-methyl4-isol~ropylindenyl)zirconium dichlorid 15 dimethylsilan~diylbis(2-methyl-4-ethyli"denyl)~ircG"ium dichloride dimethylsilanediylbis(2-methyl4ff-acena~htl,indenyl)zirconium dichloride dimethyl ~ nediylLis(2 4-dimethylindenyl)zirconium dichloride dimethylsilanediylLis(2-ethylindenyl)zirconium dichloride dimethylsil~"ediylbis(2-ethyl4-ethylindenyl)zirconium di~,loride 20 dimethylsil~ lbis(2-ethyl4-phenylindenyl)~i,wnium dichloride dimethylsilanedi~bis(2-methyl4 5-benzoindenyl)zirconium dichloride dimethylsila"ediylbis(2-methyl4 6-diisopropylindenyl)~ ium dichloride dimethylsilaneJi~lbis(2-methyl4 5-diisop,opylindenyl)zirconium dichloride dil "etl ,ylsilanediylbis(2 4 6-l, i" ,e~l ,ylindenyl)~i, conium dichloride 25 dimethylsilanediylbis(2 5 6-t,i"~e~lIylindenyl)zirconium dichloride dimethylsilanedi~lbis(2 4 7-trimethylindenyl)zirconium dichloride dimethylsilanediylbis(2-methyl-5-isobutylindenyl)zirconium dichloride dimethylsilanediylbis(2-methyl-5-t-butylindenyl)zirconium dichloride dimethylsilanediylbis(2-methyl4-,c 1 ,enantl u ylindenyl)~irconium dichloride 30 dimethylsilanediylbis(2-ethyl4-phenanthrylindenyl)zirconium dichloride methyl(phenyl)silanediylbis(2-methyl4-phenylindenyl)zirconiumdichlorid methyl(phenyl)silanediylbis(2-methyl4 6-diisopropylindenyl)zirconium dichloride methyl(phenyl)silanediylbis(2-methyl4-isopropylindenyl)zirconium dichloride -methyl(phenyl)sila"edi~lbis(2-methyl-4 S-l,en~oindenyl)~i,conium dichloride methyl(phenyl)silanediylbis(2-methyl-4 5-(methyll.e"~o)-indenyl)~irconium dichloride methyl(phenyl)sil~,)edi~lbis(2-methyl4 5-(tetr~" ,eli ,ylL,er,~o)indenyl)zirco-nium dichloride methyl(phenyl)silanediylbis(2-methyl-4-a-acenaphtl ,i"clenyl)zirconium dichloride methyl(phenyl)sila"eJ;ylL,is(2-methylindenyl)~irconilJm dichloride methyl(phenyl)sila"eJiylbis(2-methyl-5-isobutylindenyl)zirconium dichloride methyl(phenyl)silanedi~lbis(2-methyl4-pl)enarltl " yl;ndenyl)~irconium dichloride methyl(phenyl)silanediylbis(2-ethyl4-phena, Ithlylindenyl)zirconium dichloride 1 2~th~n~i~1bis(2-methyl-4~henylindenyl)~ircon. ~m dichloride 1 4-bulanediylbis(2-methyl-4-phenylindenyl)zirconium dichloride 1 2 eti .aneJi~lbis(2-methyl-4 6-diisopropylindenyl)~irconium dichloride 1 4-butan~d;ylbis(2-methyl-4-isopr~pylindel "~ ir~n ~rn dichloride 1 4-butsinedi~rlbis(2-methyl-4 5-beri~oindenyl)~irconium dichloride 1 2~ti.~.)eJiylbis(2-methyl-4 5-benzoindenyl)zirconium dichloride 1 2~tl.a,leJiylbis(2 4 7-tri",eU,ylindenyl)zirconium dichloride 1 2~hanedi~1bis(2-methylindenyl)~irconium dichloride 1 4-butanedi~rlbis(2-methylindenyl)~irconium dichloride bis(butylcyclo,.)entadienyl)Zr+CH2CHCHCH2B~(C6F5)3 bis(methylindenyl)Zr+CH2CHCHCH2B~(C6F5)3 dimethylsilal ,e Jiybis(2-methyl4,5-benzoindenyl)Zr+CH2CHCHCH2B~(C6F5)3 1 2~tl,anediylbis(2-methyli"denyl)Zr+CH2CHCHCH2B~(C6F5)3 1 ,4-butaned;~lL,is(2-methylindenyl)Zr+CH2CHCHCH2B~(C6F5)3 dimethylsilanediylbis(2-methyl-4 6~iisopropylindenyl)-Zr+CH2CHCHcH2B (C6F5)3 dimethylsilaneJi~ll,is(2-ethyl-4-phenylindenyl)Zr+CH2CHCHCH2B~(C6F5)3 dimethylsilanediylbis(2-methyl-4-phenylindenyl)Zr+CH2CHCHCH2B~(C6F5)3 methyl(phenyl)silandiylbis(2-methyl-4-phenylindenyl)-Zr+cH2cHcHcH2B (C6F5)3 dimethylsilanedi~rlbis(2-methylindenyl)Zr+CH2CHCHCH2B~(C6F5)3 dimethylsilanediylbis(indenyl)Zr+CH2CHCHCH2B~(C6F5)3 dimethylsilandiyl(tert-butylamido)(tetramethylcyclopentadienyl)-zirconium dichloride [tris(p6, Itanuoro~l ,eny-l)(cyclopenladienylidene)L,orateo](cyclopenladienyl)-1 2 3 4-tetra~l ,e"ylbuta-1 3-dienyl ~i, conium dimethylsilanJiyl [tris(penldlluoropl)eny-l)(2-methyl-4-phenylindenylidene)-boraleo](2-methyl4-phenylindenyl)-1 2 3 4-tetra~l,enylbuta-1 3-dienyl zirconium 5 dimethylsilandiyl-[tris(trifluoromethyl)(2-methylber,~indenylidene)-borateo](2-methyl~,kindenyl-)-1 2 3 4-tet, apl ,eny-lbuta-1 3-dienyl~irconium dimethylsilan~iyl [tris(pent~lluoropl)el,y-l)(2-methylindenylidene)boraleo]
(2-methylindenyl)-1 2,3 4-tetra,c l ,enylbuta-1 3-dienyl ~ircGI)ium dimethylsila. ,eJiylbis(indenyl)dimethyl~ircG"ium 1 0 dimethylsilaneJiylbis(4-naphlhylindenyl)dimethylzirconium dimethylsila"ediylbis(2-methylLe, I~Gil ,Jenyl)dimethykirconium dimethylsilan~Jiylbis(2-methylindenyl)dimethyl~ircGnium dimethylsilaned;ylbis(2-methyl-4-(1 -naphll ,yl)indenyl)di,nethykirconium dimethylsilaneJiylbis(2-methyl-4-(2-nap ht hy-l)indenyl)dimeth-ykirco~ ,ium 15 dimethylsilanediylbis(2-methyl4-phenylindenyl)di",ell,ykirconium dimethylsilan6Jiylbis(2-methyl-4-t-butylinJenyl)dimethykirconium dimethylsilanedi~lbis(2-methyl-4-isopropylindenyl)dir"etl ,ykirconium dimethylsilanediylbis(2-methyl-4-ethylindeny-l)dimethyl~irconium dimethylsilaneJiylbis(2-methyl-4~-acena,chtl ,indenyl)dimethyl~i, cGnium 20 dimethylsilan~Jiylbis(2 4-di" ,etl ,ylindenyl)di" ,etl ,~kirconium dimethylsilanediylbis(2-ethylindenyl)di" ,e~l ,yl~ir~nium dimethylsilanediylbis(2-ethyl4-ethylindenyl)dimethyl~ir~nium dimethylsilaneJiylbis(2-ethyl-4-phenylindenyl)dimethyl~i, conium dimethylsilaned;ybis(2-methyl4 5-be"~oindenyl)dimetl,ykirconium 25 di",etl ,yl~ilanediylbis(2-methyl4 6-diisopropylindenyl)dil "eth~l~irconium dimethylsilaneJiylbis(2-methyl45~iisopropylindenyl)di,netl,yl irconium di. "etl ,ylsilanediylbis(2 4 6-t, i,netl ,ylindenyl)dimethykirconium dimethylsilanediylbis(2 5 6-l,imetl,ylindenyl)dimethylzirconium dimethylsilanediylbis(2 4 7-l, i."ethylindenyl)dimeth~l~irconium 30 dimethylsilaneJiylbis(2-methyl-5-isobutylindenyl)dirnethylzirconium dimethylsilanediylbis(2-methyl-5-t-butylindenyl)dimethykirconium dimethylsilanediylbis(2-methyl4-phenanlhl ylindenyl)dimethylzirconium dimethylsilanediylbis(2-ethyl4-phe"anll ,rylindenyl)dimethykirconium methyl(phenyl)silan6Jiylbis(2-methyl4-phenylindenyl)dimethykir~"ium methyl(phenyl)silanediylbis(2-methyl4 6- diisopropylinJenyl)dimethylzirconium methyl(phenyl)silanediyll,is(2-methyl4-isopropyli. ,de,)yl)dimethyl~irco"ium methyl(phenyl)silanedi~lbis(2-methyl-4 5-benzoindenyl)dimethykircol ,ium 5 methyl(phenyl)sila"eJ;~ll,is(2-methyl4 5-(methylbenzo)indenyl)dirnell,ykirconium methyl(phenyl)silaneJiylbis(2-methyl-4 Sttet, ar"ell "~I~"~o)indenyl)-dimethylzirconium methyl(phenyl)sila"6Jiyll,is(2-methyl-4~-acenaphtl ,indenyl)d,. "ethyl~ir~. ,iummethyl(phenyl)silanediylbis(2-methylir,-Jenyl).li",ethykir~nium 10 methyl(phenyl)silane.Jiylbis(2-methyl-5-isobutylindenyl)dimethyki, conium methyl(phenyl)silan6diylbis(2-methyl-4-phenanthrylindenyl)dimethyl- ~ircol ,ium methyl(phenyl)silanediylbis(2-ethyl4-~1 ,enan U "ylindenyl)dimethyl~irconium 1 2~U,aneJiyll,is(2-methyl4-pheny,i. ,Jenyl)dimethykirconium 1 4-butan~ lbis(2-methyl4-phenylindenyl)dimethykirconi~m 1 2~th 2. aJ;ylbis(2-methyl4 6-diisop, opylindenyl)dimethyki, conium 1 4but ,~Ji~1L.is(2-methyl q iso~ropylindenyl)dimethyl~irconium 1 4-butan~iylbis(2-methyl4 5-benzoindenyl)dimethyl~irconium 1 2~U ,~n~liylL.is(2-methyl4 5-benzoindenyl)dimethykirconium 1 2~U,aneJi~lbis(2 4 7-~,i",etl"~lindenyl)dimethyl,irconium 20 1 2~U ,a"eJ;yll,is(2-methylindenyl)dimeU ,ykir~"ium 1 4-butaneJ;ylbis(2-methylindenyl)dimethykir~nium Particular pr~ference is given to:
dimethylsil~nediylbis(2-methylinden~l)zirconium dichloride 25 dimethylsila"eJiylbis(2-methyl4-(1-naphthyl)indenyl)zirconium dichloride dimethylsilanediylbis(2-methyl4-phenylindenyl)~irconium dichloride dimethylsilanediylbis(2-methyl44~-acenaphthindenyl)zirconium dichloride dimetl,ylsilanediylbis(2-ethyl4-phenylindenyl)zirconium dichloride dimethylsilaned;ybis(2-methyl4 5-benzoindenyl)zirconium dichloride 30 dimethylsila"ediylbis(2-methyl4 6-diisop,opylindenyl)zirconium dichloride di. "etl ,ylsilanediylbis(2-methyl4-phenanthrylindenyl)zirconium dichloride dimethylsilanediylbis(2-ethyl4-pl)e"a, IU " ylindenyl)zirconium dichloride 2 1 933 1 ~
methyl(phenyl)silanediylbis(2-methyl4~henar,ll"ylindenyl)~ir~"ium dichloride methyl(phenyl)silaneJiylbis(2-ethyl4-pl ,ena. ni llyli"denyl)~irconium dichloride Methods of ~,r~paring metallocenes of the formula I are des~ibed for example in S Joumal of O(gano",etallic Chem. 288 (1985) 63 - 67 and the documents cited tl,erei.~.
The catalyst system of the invention preferably further comprises at least one ~ yst.
The cocatalyst c~mpGI ,ent which can according to the invention be present in the catalyst system is at least one co",pound selscted from the group consisting of aluminoAanes or Lewis acids or ionic co",pounds which react with a met~llocene to convert the latter into a calionic co",pound.
Aluminoxanes which are preferably used are co",pounds of the formula ll (R Al)n (Il) Alumir,oxanes can for example be cyclic as in formula lll --O A I
-- _ or linear as in formula IV
R\ R /R
A I--O A I O " A I ~ I V ) R/ \R
or of the cluster type as in formula V, as are desa ibed in recent literature; cf. JACS
117 (1995), 6485-74, OrganG",et~lics 13 (1994), 2957-2969.
I~
~ "~ t ~l ) 1~
The radicals R in the formulae (Il), (Ill), (IV) and (V) can be identical or dirrerenl and each be a C1-C20-hydlo~,bon group such as a C1-C6-alkyl group, a C6-C18-aryl group, benzyl or hydl ogen, and p is an integer from 2 to 50, preferably from 10 to 35.
The radicals R are preferably identical and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly prererably methyl.
If the radicals R are difreren~, they are prererably methyl and hydlogen, methyl and isobutyl or methyl and n-butyl, with hyd~gen, isobutyl or n-butyl preferably being pr~sent in a propG, lion of 0.01 - 40% (number of rrdic~ls R).
25 The aluminoxane can be prepared in various ways by known methods. One of the melhod~ is, for exd"~ple, reacting an aluminum hydrocarbon compound and/or a hydlidoaluminum hydlocarl,on cG",,,~ound with water (grseous, solid, liquid or bound - for example as water of cryslr'li~lion) in an inert solvent (e.g. toluene). Toprepare an alum noxane having difrerent alkyl groups R, two difrerenl 30 trialkylaluminums (AIR3 + AIR'3) corresponding to the desired composition andreactivity are reacled with water (cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424).
2 1 933 1 ~
_ Regardless of the ~ tl)od of preparation, all aluminoxane solutions have in cGi"r.,on a varying cGntent of unreacled aluminum slal ling cornpound which is present in free form or as ~duct 5 As Lewis acid, pre~er~nce is given to using at least one Grganoboron or or~,anoaluminum cGr"~ound containing C1-C20-groups such as L ranched or unL,an.;l.~.J alkyl or haloalkyl, e.g. methyl, propyl, isopropyl, isobutyl and trifluor~.,etl,yl or unsaturated groups such as aryl or haloaryl, e.g. phenyl, tolyl, benzyl, p-fluorophenyl, 3,5-difluGru~Jhe"~l, ~.lta*.loropî,enyl, pentalluoropl,enyl, 3,4,5-trifluoropl,ei"~l and 3,5-di(trifluo~o.netl ,yl)phenyl.
Particular preference is given to o(ga.,oboron cG.."~ounds.
Examples of Lewis acids are trifluoroborane, triphenyll,orane, 15 tris(4-fluoro~l ,enyl)l,ora. .e, tris(3,5-difluoropl ,enyl)l,orane, tris(4-fluor~..,etl .yl~hel ,yl)boral .e, tris(pentt~nuorophenyl)borane, tris(tolyl)l,Gr~.,e, tris(3,5-dimethylphenyl)borane, tris(3,5-difluoro~l .enyl)borane and/or tris(3,4,5-trifluoropl ,enyl)borane.
In particular, pr~ference is given to tris(penlalluoropl)enyl)bo~ne.
lonic co,~r'~lysts which are preferably used are cGmpounds containing a non-coordinating anion, for example tetrakis(pentan.lorophenyl)borates, tet~,cl .enylL,orales, SbF6-, CF3S03- or Cl04-. As cationic counterion, use is made of Lewis bases such as methylamine, aniline, dimethylamine, diethylamine, N-25 methylaniline, diphenylamine, N,N~i."ethylaniline, l,i",ethylamine, triethylamine, tri-n-butyla"~ine, methyldiphenylamine, pyridine, p-bromo-N,N~i,.,etl,ylaniline, p-nitro-N,N-dimethyla"iline, triethylphosphine, triphenylphos~l,ine, diphenylphospl)ine,tetrahydrothiophene and triphenyl~lbenium.
30 Examples of such ionic compounds according to the present invention are:
triethylal, .r. IGnium tetra(phenyl)borate, tributyla,.".,oni ~m tetra(phenyl)borate, l, i..,etl ,yla,nmonium tetra(tolyl)borate, tributyla"",~onium tetra(tolyl)borale tributyla"""onium tetra(~,enldlluoropl ,enyl)borate tributyl8,."~0nium tetra(penldlluoropl ,ei .yl)aluminate lripr~pyl~,..,.~onium tstra(dimethylphenyl)borate 5 tributyla" " "onium tetra(trifluoror"ell ,ylphenyl)borale tributyl~r"",onium tetra(4-fluorophenyl)borale N N-dimethylanilinium tetra(phenyl)borale N N-diethylanilinium tetra(phenyl)borale N N-dimethylanilinium tetrakis(pentafluorophenyl)borate 10 N N-dimethylanilinium tetrakis(pentdlluorophenyl)aluminate di(propyl)ammonium tetrakis(,l~entdlluorophel~yl)borate di(cyclol ,exyl)ammonium tetrakis(penlanuorophenyl)bor~le t, i~l ,enylpl ,ospl onium tetrakis(phenyl)borate triethyl~l os~l ,onium tetrakis(phenyl)bora~e 15 diphenylpl)ospl.o,nium tetrakis(phenyl)borate tri(methyl~ "yl)pl .ospl .onium t~trakis(phenyl)borate tri(dimethylphenyl)~l .os~l ,onium tetrakis(phenyl)borale l, i~l ,enylc~- ~nium tetrakis(pe, tdlluorophenyl)borate l ,enyl~, t,enium tetrakis(pentanuoropl)enyl)aluminate 20 b ipl .enyl~, Len. un tetrakis(phenyl)aluminate fe"~c~nium tetrakis(penldlluorophenyl)borate and/or fe"oeenium tetrakis(pentdiluoropl,e"yl)aluminate.
rre~ere"ce is given to lri,c I ,enylcarbenium tetrakis(pentafluorophenyl)borate and/or N N-dimethylanilinium tetrakis(~,e, .tdlluo, o~l ,enyl)borate.
25 It is also possible to use mixtures of at least one Lewis acid and at least one ionic cGI"pound.
Also illl~lldl)t as cocAI~lyst col"ponents are borane or ca,l,orane co""~ounds such as 7 8-dicarbaunde~ rane(13) 30 undeca~,ydrido-7 8~ir"etl,yl-7 8-dicarbaunde~Ahorane d~le¢~hydrido-1-phenyl-1 3-dicarbanonaborane tri(butyl)a",-noniumundecahydrido-8-ethyl-7,9-dicarbaundec~horate, 4~rl,~nona~orane( 1 4)-bis(tri(butyl)a" ,r"onium) nonaborate bis(tri(butyl)ammonium) u.,dec~l~orate bis(tri(butyl)ammonium) d~JecAhorate bis(tri(butyl)a..,..,onhm) decacl1lorodecaborale tri(butyl)ammonium 1~,bAclecAhorates 5 tri(butyl)ammonium 1~.bAdoJe~horates tri(butyl)ammonium 1 -b imdt h~lsilyl-1~, b~decAhorates tri(buyl)ammonium bis(nonahydrido-1 3-dica. L,onnonal~rate)cob~t~te(lll) Tri(butyl)ammonium bis(u..~ecal)ydrido-7 8-dicarbaunde-~horate)-fer,dle(lll).
10 The support co",ponenl of the catalyst system of the invention can be any Grga"i~
or inor~anic inert solid in particular a porous support such as talc inorganic oxides and finely di~ided polymer powders (e.g. polyolefins).
Suitable inorganic oxides are those of elem6nts of groups 2 3 4 5 13 14 15 and 15 16 of the Periodic Table of the Elements. Examples of oxides prefer,ed as supports include silicon dioxide aluminum oxide and also mixed oxides of the two ele,.,ents and cor, e5PGI .ding oxide mixtures. Other inorganic oxides which can be used alone or in combination with the last-named prefer, ed oxidic supports are for exampleMgO ZrO2 TiO2 or B2O3 to name only a few.
The support ,.,aterials used have a specir,c surface area in the range from 10 to 1000 m2/g a pore volume in the range from 0.1 to 5 ml/g and a mean particle size of from 1 to 500 IJm. P~eference is given to supports having a specir,c surface area in the range from 50 to 500 m2/g a pore volume in the range between 0.5 and 3.5 ml/g 25 and a mean particle size in the range from 5 to 350 um. Particular preferel)ce is given to supports having a specific surface area in the range from 200 to 400 m2/g a pore volume in the range from 0.8 to 3.0 ml/g and a mean particle size of from 10 to 200 ~m.
30 If the support material used naturally has a low moisture contenl or residual solvent cGnlent dehydration or drying before use can be omitted. If this is not the case as when using silica gel as support material dehydration or drying is advisable. The weight loss on ignition (LOI) should be 1% or less. The thermal dehydration or drying of the support ",alerial can be carried out under rerluced pressure and simultaneous ~lanl;eting with inert gas (e.g. nilrogen). The drying te"~peralure is in the range between 100 and 1000C preferably between 200 and 800C. In this case the pressure is not decisive. The duration of the drying process can be 5 between 1 and 24 hours. Shorter or longer drying times are possible provided that under the cG-~-liliGns selected e~ librium can be established with the hydroxyl groups on the support surface which normally requires betwocn 4 and 8 hours.
Dehyd~dliG., or drying of the support ",aterial can also be achieved by chemical10 metl l~ds by r~acting the adsG, Led water and the hydroxyl groups on the surface with suitable s~ sl~)ces for making the surface inert. The reaclion with the reagent for making the surface inert can convert the hydroxyl groups completely or partially into a form which does not lead to any adverse inlera.tion with the catalytically active cen~ers. Suitable s~ nces for making the surface inert are for example 15 silicon halides and silanes e.g. silicon teba~;l.loride chlorol,i"~ethylsilane dimethylaminotrichlorosilane and o~anometallic cG"")ounds of aluminum boron and "~s~ esium e.g. I,i",~ll"~laluminum triethylaluminum triisobutylaluminum triethyll,orane dibutyl~"agnesium. The chemical dehydration or making inert of the support ",at6(ial is carried out for example by reac~ing with exclusion of air and 20 moisture a suspension of the support material in a sl~-t~h!e solvent with the reagent for makin~ the surface inert in pure form or dissolved in a suitable solvent. Suitable solvents are for example alipha~ic or aro",atic hydrocarl.ons such as penlane I ,exane heptane toluene or xylene. The reaclion for making the surface inert iscarried out at tel"peratures between 25 C and 120 C preferably between 50 and 25 70C. Higher and lower tel"peral-Jres are possible. The reaction time is between 30 minutes and 20 hours preferably from 1 to 5 hours. After the chemical dehydl alio"
has proceeded to completion the support material is isolated by filtration under inert condiliGns, washed one or more times with suitable inert solvents as have been desu ib~J above and finally dried in a stream of inert gas or under reduced 30 pressure.
Organic support materials such as finely divided polyolefin powders (e.g.
polyethylene polypropylene or polystyrene) can also be used and should likewise 219331~
be freed of a~ . ing moisture, residu~l solvent or other impurities by appropri~le pUIifiC~tiGn and drying operatiG,.s before use.
To prepar~ the SlJ~JpGI led catalyst system, at least one of the above- des~ ibed S mePIloc~.,e cG",ponenls is brought into contact with the coc~PIyst cG""~onenl in a suitable solvent so as to obtain a soluble reaction product.
The soluble r eactiG" product is then added to the support material which has been dehyJ~ ated or made inert, the solvent is removed and the resulting SUp,)GI l~d ."ct-'lcc~ catalyst system is dried to ensure that all or most of the solvent isremoved from the pores of the support material. The SUppGI led catalyst is ol,tained as a froe flowing powder.
A process for prepdri,~ a free-flowing and, if desired, prepolym6ri~6.J SUppGI led catalyst system comprises the following steps:
a) pre~J~IdtiGll of a preacti.lated met~llocene/cocA~A~yst mixture in a suitable solvent, where the metallocene con"~onent has one of the structures desu ibeJ above, b) ~p~ ion of the preacli~ated met~llocene/co~lalyst solution to a porous, generally inorganic dehydrated support, c) removal of the major part of solvent from the resulting mixture, d) isol-tion of the suppo. led catalyst system, e) if desi~d, a prepoly",eri~alion of the resulting supported catalyst system using one or more olefinic monomer(s), in order to obtain a prepoly",~ri~ed SUppGI l~d catalyst system.
Plefer.ed solvents for the preparalion of the preactivated metallocene/coc~l~lyst mixture are hydrocarl,ons and hydrocarL,on mixtures which are liquid at the selected - - 21 q331 9 reaction te",~rat.lre and in which the individual co,nponents preferably dissolve.
However the solubility of the individual COrnpGI ,enls is not a prerequisite if it is ensured that the rea-tiGn product of met~llocene and co~l~lyst COmpGi ,ent is soluble in the sale~t6J solvent. Examples of suitable solvents include alkanes such aspenlane isopenta"e l,exane hep~ane octaneandnG,)ane;cycloalkanessuch as cyclopenlane and cyclohexane; and arol"dtics such as ber,~el,e toluene ethyl~n~ne and diethyll~"~ene. It is also possible to use halogel)ate-i hydroca,L.ons such as methylene chloride or ar~",atics such as fluorobe"~ene or o-dichlor~ , .e. Very particular preference is given to toluene.
The amounts of alu."ino~cane and metallocene used in the preparalion of the suppGIt~d catalyst system can be varied over a wide range. r~ference is given tousing a molar ratio of aluminum to the transition metal in the metallocene of from 10:1 to 1000:1 very particularly prererably a ratio of from 50:1 to 500:1.
In the case of methylaluminoxane preferel)ce is given to using 30% sll en~tl, solutions in toluene but the use of 10% strength solutions is also possi~le.
For the preacli~ation the metallocene in the form of a solid is dissolved in a solution of the aluminoxane in a suit~'e solvent. It is also possible to dissolve the ",et~'l~ne separalely in a suitable solvent and s~hse~uently to col,lbil,e this solution with the aluminoxane solution. rleference is given to using toluene.
EP-A 0302424 des~ ibes the preacti-/ation of metallocenes for use in unsupportedform in poly",eri~tiol,s. The preactivation time is from 5 minutes to 100 hours preferably from 5 to 60 minutes in particular from 10 to 20 minutes. A significantly longer prea~ /ation is possible but it normally neither increases the activity nor Je~eases the activity although it can be quite useful for storage pu".oses. Theprea~i-/ation is carried out at a temperalure of from -78 to 1 00C preferal)ly from 0 to 70C.
Sul ~risi, Igly it has now been found that in the case of sterically demanding metallocenes such as rac-dimethylsilanediylbis(2-methyl4-phenylindenyl)zirconiumdichloride a distinctly longer preactivation time leads to a significant increase in .
activity. In the case of sterically demanding met~locenes the preactivation time is pr~fo, aL,ly from 30 minutes to 200 hours in particular from 1 to 50 hours especi~'ly from 5 to 20 hours.
5 The preacti~ation can take place at room te,nperal-Jre (25 C). The use of higher te",~eratures can in some cases shG, ~n the time necess~y for preactivation and effect an ~ tional inc(ease in activity. In this case Uhigher tel"peraluren means a ran~e between 50 and 1 00C. Even at higher temperatures the prefer,ed ,~,rea~ti~ation time in the case of the metr"ccenes prefer,ed accordi,1g to the 10 invention is d;slinctly above the preacti.ration time known from the prior art.
The preacti-/ated solution is s~hse~uently combined with an inert support ",ale,ial usually silica gel which is in the form of a dry powder or as a suspe"sio" in one of the abov~",enlioned solvents. The powder used is preferably silica gel. Any order of 15 addition can be used. The preactivated met~llocene/coc~'AIyst solution can be the support ",alerial or else the support ",aterial can be introd~Ged into the solution.
The volume of the preacli~ated solution can exceed 100% of the total pore volumeof the support ",alerial used or else can be up to 100% of the total pore volume.
20 The te",perat~lre at which the preactivated solution is brought into cGnlac~ with the support ",alerial can vary in the range between 0 and 1 00C. However lower or higher temperat.lres are also possible. After co",b..)ing the support material and solution the mixture is maintained at this te",peral-Jre for a further period of from about 1 minute to 1 hour prereral,ly 5 minutes.
All or most of the solvent is suhse~uently removed from the suppol led catalyst system; for this procedure the mixture can be stirred and if desired also heated.
rl~erably both the visible propo, lion of solvent and also the solvent in the pores of the support material are removed. The removal of the solvent can be carried out in a 30 conventional ",a"ner using reduced pressure and/or flushing with inert gas. During the drying procedure the mixture can be heated until the free solvent has been removed which usually takes from 1 to 3 hours at a telnperalure which is pre~erably selected so as to be between 30 and 60C. The free solvent is the visible proportion of solvent in the mixture. For the pl" ~,oses of the present invention, residual solvent is the propG, liGI ~ which is ~, Iclosed in the pores. As an allel "ali~/e to complete removal of the solvent, the SUIJpGl led catalyst system can also be dried only to a certain r~sid~' solvent contenl, with the free solvent having been completely 5 removed. The SU,upGI led catalyst system can subsequently be washed with a low-boiling hyd~ l l,on such as penlane or I ,exane and dried again.
The SU~pGI t~i catalyst system prepared according to the invention can either beused directly for the poly-"eri~-dlion of olefins or be prepoly"~eri~ed with one or more 10 olefinic ~G~GI~ers before use in a poly..,eri~dlion process. The procedure for prepoly..~ri~atio.. of suppG-led catalyst systems is described, for example, in WO 94/28034.
The prese. It invention also provides a process for preparing a polyolefin by polymeri~tion of one or more olefins in the presence of the catalyst system of the invention colr~prisin~ at least one l-~nsilion metal col.,pG.,ent of the formula 1. For the pu.~oses of the presenl invention, the term poly",eri~3tion refers to either a l,G",opoly"~eri~dtion or a copoly",eri~alion.
Preference is given to polymerizing olefins of the formula Rm-CH=CH-Rn, where Rmand Rn are iJ6ntical or Jif~renl and are each a h~JI ogen atom or a carL,on-containin~ radical having from 1 to 20 carbon atoms, in particular from 1 to 10 cal bGI I atoms and Rm and Rn to~ether with the atoms connectin~ them can form one or more rings. Examples of such olefins are 1-olefins having 2 - 40, preferably from 2 to 10 ca. I,Gn atoms, for example ethene, p~pene, 1 -butena, 1 -pentene, 1 -hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1,3-but~diene, 1 ,4-hexadiene, vinylnorbG. "ene, no, bG" ,adiene, ethylnorbor"adiene and cyclicolefins such as no, bor"ene, tetracyclododecene or methylnorbornene. In the p~cess of the invention, preference is given to ho",Gpoly")eri~i"g ethene or ~ rop~ne, or copoly",eri~in~ ethene with one or more 1-olefins having from 3 to 20 carbon atoms, e.g. propene, and/or one or more dienes having from 4 to 20 carbonatoms, e.g. 1,4-butadiene, nGrbG",adiene or ethylno,l,Grnadiene. Examples of such copolymers are ethene-propene-copolymers or ethene-propene-1,4-hexadiene terpolymers.
The poly",eri~atiG" is ca"ieJ out at a te",perature of from ~0 to 300 C preferably from 50 to 200C. The pressure is from 0.5 to 2000 bar pre~erably from 5 to 64 bar.
The poly",eri~dtion can be carried out in solution in bulk in suspension or in the gas phase continuously or batchwise in one or more stages.
The ca~alyst system prepared according to the invention can be used as sole 10 catalyst CGlllpGI ,ent for the polymeri~a~iGn of olefins having from 2 to 20 ca, l,on atoms or pre~erably in combi. IdtiG, I with an aluminum alkyl or an alu",inoxane. The soluble aluminum celllpGnent is added to the ,nonomer and serves to free the mG,)G,ner of s~ lA~s which can impair the catalyst activity. The amount of aluminum cefi,pon6nt added .lepe"ds on the quality of the ",onor"el:i used.
If, .ec~ss~ hyJ~ o9el l can be added as mcl~c~ weight regul~'or and/or to inerease the activity.
The invention is illusba~ed by the following exa",ples.
Examples General The preparation and handling of the organGI"etallic cG",pounds were carried out with excl- ~siQn of air and moisture under argon (Schlenk technique). All necess~ry solvents were freed of air and moisture before use by boiling for a number of nours over a suitable desiccant and s~ ~hse~uent distillation under argon.
The met~locenes used were charactel i~ed by 1 H-NMR 1 3C-NMR and IR
spe-;t~oscopy.
D~rl,~ilions;
PP = polypropylene MC = ",et~'lc~ne cat = SUppG~ catalyst system h= hour VN = viscosity number in cm3/g Mw = weight average molar mass in g/mol M~JMn = molar mass distribution deter",ined by gel per",edliGn chromatoy,d~l,y BD = bulk density in g/dm3 and mp. = ",elt;ng point in C deter"~ined by dirrere,ltial scanning calorimetry (DSC 2ndl,eatiny) Example 1 Prepa~tion of the SU~JpGI led catalyst system 444 mg (0.71 mmol) of rac~li",etl,ylsilanediylbis(2-methyl4-phenylindenyl)~i,~i,ium dichloride were dissolved at room te",perature in 35.5 ml (128 mmol of Al) of 30%
st,e,.yth methylaluminoxane solution in toluene1). For the prea.;ti~ation the mixture was allowed to stand at 25C for 18 h while being prote~;ted from light. The mePIlocene/MAO solution thus prepareJ was s~ ~hse~uently diluted with 86.9 ml oftoluene to a total volume of 122.4 ml. 30.6 9 of SiO22) were slowly introd~ ~ced into this solution. The ratio of the volume of the solution to the total pore volume of the support material was 2.5. After ~ddi~i~n was cG"~plete the mixture was stirred for 5 minutes at room ~e",perat.lre. Subsegl~ently the mixture was evaporaled to dryness under red~ pressure at 40C over a period of 2 h and the residue was dried for 5h at 25C and 10~3 mbar. This gave 39.5 9 of a free-flowing pink powder which according to ~le."enlal analysis conlained 0.15% by weight of Zr and 8.0% by weight of Al.
Poly" ,~ri~dtion A dry 16 dm3 reactor which had been flushed first with nil,ogen and s~lhse~uently with pr~p~ne was filled with 10 L of liquid propene. 8 ml of 20% strength triethylaluminum sol! ~tion in Varsol (Witco) were added as scavenger and the mixture was stirred for 15 minutes at 30 C. S! ~hse~uently a suspension of 1.2 9 of the su~ J ",et~llocene catalyst in 20 ml of a dearomatized petroleum fraction having a boiling point range from 100C to 120C was added to the reactor the mixture was heated to the poly"~eri~alion temperature of 65 C and the poly",eri~ation system was held at 65C for 1 h. The poly",eri~ation was sl~pped by addition of 20 ml of isGpropanol the excess monomer was vented and the polymer obtained was dried under reduce~ pressure. This resulted in 2.4 kg of polypropylene powder.
The catalyst activity was 193 kg of PP/(g of MC x h) or 2 kg PP/(g of cat x h) The isot~tic polypropylene prepared had the following prope"ies:
mp. 147C; Mw = 901,000 g/mol, MW/Mn = 2.3, VN = 603 ml/g, BD = 370 g/dm3 5 CG",parati~e Example 1 r, epar~tion of the S~lppGI le.J catalyst system 460 mg (0.73 mmol) of rac-dimethylsilanediylbis(2-methyl-4-10 phenylin~l~"yl)~i,cGnium dichloride were dissolved at room te",pera~ure in 36.8 ml (133 mmol of Al) of 30% sll enytl l methylaluminoxane solution in toluene1). Themixture was diluted with 93 ml of toluene and stirred for 10 min at 25C. 33.2 9 of SiO22) were slowly introdt~ced into this solution. The ratio of the volume of the solution to the tobl pore volume of the support ",alerial was 2.5. After addition was 15 complete, the mixture was stirred for 5 minutes at room tei"perature. S! Ihseg~ ~ently, the mixture was evaporaled to dryness under reduced pressure at 40C over a period of 2 h and the residue was dried for 5 h at 25C at 10~3 mbar. This gave 44 9 of a free-flowing, pink powder which, according to ele,~enl31 analysis, contained 0.16% by weight of Zr and 8.0% by weight of Al.
Poly",eri~ation The poly",eri~atiGn was carried out using a Ille~llod similar to Example 1. Thisresulted in 1.4 kg of polypropylene powder.
The catalyst activity was 109 kg of PP/(g of MC x h) or 1.2 kg PP/(g of cat x h) The isot~ctic polypropylene prepared had the following properties:
mp. 146C; Mw = 1,010,000 g/mol, MW/Mn = 2.3, VN = 643 mllg, BD = 380 g/dm3 1) AlL,e",arle CGr~,oration, Baton Rouge, l oui~i^na, USA
2) Silica grade MS 948, W.R. Grace, Davison Chemical Division, Baltimore, Maryland, USA, pore volume 1.6 ml/g, calcined at 800 C.
.
Example 2 r, eparaliG" of the SUppG~ ~ed catalyst system 198 mg (0.31 mmol) of rac~imethylsilanediylbis(2-methyl4-phenylindenyl)~ircG"iumdichloride were ~issolvcd at room te""~erature in 17.4 ml (68 mmol of Al) of 30%st~r,.Jtl, methylalumir,oxane sol~ ~tion in toluene3). For the preacti~/ation the mixture was allow~d to stand at 25C for 18 h while being prot~ct~d from light. The met^'lcc~ne/MAO solution was s~hse~uently diluted with 44.6 ml of toluene to total volume of 62 ml. 15.5 9 of sio24) were slowly intro~uce~ into this solution. The ratio of the volume of the soMtion to the total pore volume of the support material was 2.5. After A-l~lition was complete the mixture was stirred for 5 minutes at roomt6",~rature. S! Ihse~l ~ently the mixture was evaporaled to dryness under re~luce~l pressure at 40C over a period of 2 h and the residue was dried for 5 h at 25 C and 10~3 mbar. This gave 20.2 9 of a free-flowing pink powder which accord;ng to cle."ental analysis contained 0.12% by weight of Zr and 7.9% by weight of Al.
Poly",~ ation The poly",6ri~tion was carried out under the same conditions as in Example 1 butusing 1.6 9 of catalyst and 8 ml of 20% stren!Jtl, triethylaluminum in Varsol (Witco).
This res~lte~ in 1.7 kg of polypropylene powder.
The catalyst activity was 128 kg of PP/(g of MC x h) or 1.06 kg of PP/(g of cat x h) Th~ isot~ctic polypropylene prepared had the following properties:
mp. 148 C; Mw = 1.300.000 g/mol M~,JMn = 2.8 VN = 762 ml/g BD = 290 g/dm3 Co""~arati~e Example 2 PreparatiG" of the supported catalyst system 203 mg (0.32 mmol) of rac-dimethylsilanediylbis(2-methyl4-phenylindenyl)~i,cGnium dichloride were d;ssolvcd at room te",peralure in 17.8 ml (70 mmol of Al) of 30%ab~rl!Jtll methylalumir,oxane solution in toluene3). The mixture was diluted with 45 ml of toluene and stirred for 10 minutes at room te",perat, re.15.7 9 of SiO2~) were slowly intro~l~c~ into this solution. The ratio of the volume of the solution to the total pore volume of the support material was 2.5. After addition was complete, the mixture was stirred for 5 minutes at room te",peral,Jre. Subsequently, the mixture was evaporated to dryness under red~ ~ced pressure at 40 C over a t,eriod of 2 h and the residue was dried for 5h at 25C and 10-3 mbar. This gave 20.0 9 of a free-flowing, pink powder which, according to elen,enlal analysis, contained 0.12% byweight of Zr and 8.0% by weight of Al.
Poly"~e, i~lion The poly.,~eri~tion was car- ied out under the same conditions as in Example 1, but using 2.2 9 of catalyst and 8 ml of 20% strength triethylaluminum in Varsol (Witco).
This res~ ~lted in 0.8 kg of polypropylene powder.
The catalyst activity was 60 kg of PP/(g of MC x h) or 0.5 kg of PP/(g of cat x h) The iSQt~CtiC polypropylene prepared had the following prope, lies:
mp. 148C; MW = 1,300,000 g/mol, MW/Mn = 3.0, VN =698 mllg, BD = 310 g/dm3 3) Witco GmbH, Bergkamen, Federal Republic of Germany 4) Silica grade MS 948, W.R. Grace, Davison Chemical Division, Baltimore, Maryland, USA, pore volume 1.6 mllg, calcined at 600C
Exa",ple 3 r, eparatiGn of the SUppOI led catalyst system 23 mg (0.040 mmol) of rac-di",etl,ylsilanediylbis(2-methyl4,5-ben7r..)denyl)~ir~i)ium dichloride were dissolved in 1.8 ml (7.1 mmol of Al) of 30%
-~;tlt:lnJtll methylaluminoxane solution in toluene3) and the mixture was allowed to stand at 25C for 18 h while being prote~;ted from light. S~ ~hseg! ~ently the metallocene/MA0 solution thus prepared was diluted with toluene to a total volume of 4 ml. 6.5 9 of PP powder5) were then slowly introd~ ~ce~ into this solution. A
vacuum (0.1 mbar) was briefly applied to remove the gas prese"l in the pores of the support and the solution was thus completely soaked up. After slir~ing inlensively for a further 10 minutes a l,G",ogeneous finely divided and free-flowing powder was obtained.
Poly",eri~ation The poly",eri~ation was carried out under the same conditions as in Example 1 but using the total amount of catalyst powder from Example 3 and 10 ml of 20% slren.Jtl, triisobutylaluminum in Varsol (Witco). This resulted in 2.5 kg of polypropylene powder.
The ~talyst activity was 110 kg of PP/(g of MC x h) The isot~-~1ic polypropylene prepared had the following properties:
mp. 146 C; Mw = 350.000 g/mol MWJMn = 2.2 VN = 250 ml/g BD = 280 g/dm3 5) AccurellD -PP (sieve h~-;tion ~ 200 ,um) from Akzo, freed of impurities by exl,detion with toluene in a Soxhlet exl, actor under inert conditions s~ ~hse~uently dried for 5 h at 25C and 2 x 104 mbar and flushed with argon CG"~parati~e Exslllple 3 Preparation of the su~,po, led catalyst system 23 mg (0.040 mmol) of rac-d;metl ,~lsilanediylbis(2-methyl4 5-benzoindenyl)~irconium dichloride were dissolved in 1.8 ml (7.1 mmol of Al) of 30%
-~l, er,!Jth methylaluminoxa"e solution in toluene3) and diluted with toluene to a total volume of 4 ml. This mixture was stirred for 10 minutes at 25C. 6.5 g of PP
powder5) were slowly introduced into the metallocene/MA0 solution thus prepared.
A vacuum (0.1 mbar) was briefly applied to remove the gas present in the pores of the support and the solution was thus completely soaked up. After stirring intensively for a further 10 minutes, a hG"~Ggeneous, finely divided and free-flowing powder was ol)tained.
Poly,Y)eri~ation The polyll,eri~dliG" was csr.ied out under the same conditions as in Exa",ple 1, but using the total amount of the catalyst powder from Col"parali~e Exal.,~le 3 and 10 ml of 20% st~n~tl) triisobutylaluminum in Varsol (Witco). This resulted in 1.8 kg of polypropylene powder.
The catalyst activity was 78 kg of PP/(g of MC x h) The i50~iC polypropylene prepared had the following properties:
mp. 146C; Mw = 330.000 g/mol, Mw/Mn = 2.3, VN = 244 ml/g, BD = 290 g/dm3 5) Accurell -PP (sieve f~ dCliOn < 200 ,um) from Akzo, freed of impurities by e~ ~-,tion with toluene in a Soxhlet e,~l, actor under inert conditions, sl ~hse~uently dried for 5 h at 25 C and 2 x 10~ mbar and flushed with argon Example 4 rl eparalion of the suppo-led catalyst system 200 mg (0.32 mmol) of rac~;,netl,~lsilanediylbis(2-methyl4-phenylindenyl)zirconium dichloride were dissolved at room temperature in 17.6 ml (69 mmol of Al) of 30%
sl,eny~l, methylalumir,oxa,)e solution in toluene3). For the preactivation, the mixture was allowed to stand at 25C for 18 h while being protected from light. The 30 metallocene/MAO solution thus prepared was s~lhse~uently diluted with 103 ml of toluene to a total volume of 120.6 ml. 16.1 9 of SiO26) were slowly introduced into this solution. The ratio of the volume of the solution to the total pore volume of the support male,ial was 2.5. After addition was complete, the mixture was stirred for 5 minutes at room te")perature. Subsequently, the mixture was evaporaled to dryness under redl ~c~ pressure at 40 C over a period of 2 h and the residue was dried for 5 h at 25C and 10~3 mbar. This gave 21.1 9 of a free-flowing, pink powder which, according to elefi,en~al analysis, contained 0.14% by weight of Zr and 8.6% by 5 weight of Al.
HOECHSTAKTIENGESELLSCHAFT HOE 95/F 314 DR.LV/as 5 Das~ i~tiGI I
Suppo, l6d catalyst system a process for itS preparation and its use for the poly",eri~tion of olefins 10 The pres~n~ invention relates to a SUppGI led catalyst system having a high activity and to an economical and enviro. ""entally friendly process for pr~paring the catalyst system and also to the use of the catalyst system for poly",eri~dlion.
rr~c~sses for prepari.)g polyolefins with the aid of soluble ho-nogenous catalyst 15 systems cGI~ risi~9 a lfansiliGn metal col"ponent of the met~llocene type and a yst col;"~onent seleGled from the group consisting of alumir,oxanes Lewis acids or ionic cGI"pounds have been des~ ibed. These catalysts have a high activity and give ho."opolymers and copolymers having a narrow molerul^- weight distribution.
When soluble (hol"Ggeneous) met~locene/methylaluminoxane catalyst systems are used in processes in which the polymer for",ed is obtained as a solid heavy deposits on the reactor walls and agiL~lor are frequently formed. These deposits are fol",ed by agglomeration (Polymer Commun. (1991) 32 58) of the polymer particles25 when the metallocene or alu",i"oxane or both are presenl in solution in the suspensio. . medium. Such deposits in the rea~tor systems have to be removed regularly since they rapidly reach considerable thicknesses have a high al(en~Jth and hinder heat ll ansrer to the cooling medium.
30 To prevent these deposits it is advant~geous to use metallocenes in suppol led form.
WO-A 94/28034 discloses a supported catalyst system in which a preactivated (at room te"~peralure) solution of metallocene and the coc~t~lyst methylaluminoxane (MAO) is applied to a porous support material (preferably silica gel). The preliminary r~a~ti~n l~tween MAO and metallocene takes between 1 and 60 minutes pr~fetably 10 minutes.
EP-A 0 518 092 ~isclQses a suppo, led catalyst system in which the prea~;tivatedmetallocene/MAO solution is al.plied to porous polymers as support ",alerials. The preactivation take~ from 1 to 120 minutes preferably from 10 to 100 minutes. Thepreacti~ation takes place at te,.,peralures betwecn 0 and 50C.
The catalyst systems des~ ibed have a low productivity based on the suppo, led system in kg of polymer per g of catalyst when compared with cl ~ssi~l Ziegler-Natta systems.
The catalyst systems les~ il,ecJ also have high catalysts costs which are esse, Itially ~us~ by the fact that the e~e"sive co~t~lyst c~",ponent methylaluminoxane has to be used in excess.
It is an object of the prese- Il invention to provide a SUppGI led catalyst system having a high activity and an econG"~ical and envi~..."entally friendly process for prepa.ing the catalyst system.
The object of the present invention is achieved by a SUppGI led catalyst system having a high activity which is obtainable by a) bringing at least one met- 'locene com~onent in at least one solvent into conlact with at least one cocPt~lyst w",pone"t b) adding the soluble product to the support material and c) removing the solvent.
The advantage of the catalyst system of the invention is a significant increase in the activity and the productivity for the same co,l,posilion of the catalyst system where in particular the ratio of cocAt~lyst to metallocene is not altered.
A prefer.ed e,nbodiment of the invention is a supported catalyst system where -d) the SUppGi led catalyst system is isolated and e) prepoly",eri~ed with at least one olefinic ",G"G,oer.
The metalloce"e cG~"~Gnenl of the catalyst system of the invention can in principle 5 be any metallocene. The metallocene can be either l ridged or u,)bridgeJ and have identical or Ji~rent ii,~dl nls. Preference is given to mePIloc6l ,es of group IVb of the Periodic Table of the El~lllents, for example titanium, zirconium or hafnium.
The metallocene is prdferably a met-'locene of the formula (I) below. Particular10 prefarence is given to ~i, conocel ,es which bear indenyl and tetrah~Jro.ndenyl derivatives as ligands.
R3~ 6 ~ ~R I ( I ) R \ R
~ ~
/ B >--6~
Rs~ R4 25 where M1 is a metal of group IVb of the Periodic Table of the Elements, R1 and R2 are ideutical or dirrerent and are each a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C20-aryl group, a C6-C10-aryloxygroup, a C2-C10-alkenyl group, an OH group, an NR122 group, where R12 is a C1- to 30 C2-alkyl group or a C6-C14-aryl group, or a halogen atom, R3 to R8 and R3 to R8 are identical or dirrere"t and are each a hyJ~-,ge" atom, a C1-C40-hyd~ocarL,on group which may be linear, cyclic or bré."~;l,eJ, e.g. a C1-C10-alkyl group, a C2-C10-alkenyl group, a C6-C20-aryl group, a -C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, or c~, It radicals R4 to R8 and/oder R4 to R8 togetl ,er with the atoms con- ,~clin~ them form a ring system, R9 is a bridge, preferal,ly s R10 R10 R10 R10 R1o _ o _ ~2_ O-- --C-- --o_ ~2-- --C--~2_ R1o Rl Rl R10 R10 Rl Rl Rl _ ~,~2_ --C--C_ _ ~t C ~,~2_ R l ' , R l ~ R l l , R l l R l l , R ' l R l l R l l , -- -- x R10 R10 Rl --C--C--C--~ ~10, >~ . - G ~ - . - O - . - S - . ~5 0, ~5 0 ~ , ~C O . ~ or ~11 ( 0 ) ~ ~ , where R10 and R11 are iWentical or differenl and are each a hydroge" atom, a halogen atom or a C1-C40-group such as a C1-C20-alkyl group, a C1-C10-fluoroalkyl group, a C1-C10-. 'koxy group, a C6-C14-aryl group, a C6-C10-fluoroaryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, or R10 and R1 1 together with theatoms co, In6~Ain!3 them form in each case one or more rings, and x is an integer from zero to 18, M2 is silicon, ger")anium or tin and the rings A and B are identical or difrerent, saturated or unsaturated.
R9 can also link two units of the formula I to one another.
219331~
In formula 1 it is particularly pr~fer,~d that M1 is zirconium or hafnium R1 and R2 are idel ltical and are methyl or chlorine in particular chlorine and R9 =
M2R10R11, where M2 is silicon or germanium and R10 and R11 are each a C1-C20-hydloc~ ol~ group such as C1-C10-alkyl or C6-C14 aryl The indenyl or tetrahydroindenyl ligands of the met-llQcenes of the formula I are ~,r~rer~ly substituted in the 2 2 4 4 7 2 6 2 4 6 2 5 6 2 4 5 6 or 2 4 5 6 7 posilions in particular in the 2 4 positions. Pleferled substituents are C1-C4-alkyl groups such as methyl ethyl or isopropyl or C6-C10-aryl groups such as phenyl naphtl ,yl or mesityl. The 2 position is preferably s~ ~hstit~n~d by a C1-C4-alkyl group such as methyl or ethyl.
If the 2 and 4 positions are s~ ~hstihlted then R5 and R5 are preferably ide"tical or difrerent and are each a C6-C10-aryl group a C7-C10-arylalkyl group a C7-C40-alkylaryl group or a C8-C40- arylalkenyl group.
The following numb~ri,)g is used here for the substitution position:
5~
25 Of particular i,npG"ance are also metallocenes of the formula I in which the substituents in the 4 and 5 positions of the indenyl radicals (R5 and R6 as well as R5 and R6 ) tog~tl .er with the atoms cc"necting them form a ring system pre~erably a six~"e"~bered ring. This condensed ring system can likewise be substituted by radicals having the ,..eanings of R3 - R3. An example which may be mentioned of 30 such cGI"~ounds I is din.etl,ylsilanediylbis(2-methyl4 5-benzoindenyl)zirconium dichloride.
Particular pr~fere"ce is given to those compounds of the formula I which bear a C6--C20-aryl group in the 4 positiGn and a C1-C4-alkyl group in the 2 position. An example of such a cGn"~ound of the formula I is dimetl,ylsilanediylbis(2-methyl4-phenylindenyl)zirconium dichloride.
5 Examples of the met~'locene cori"~onenl of the catalyst system of the invention are:
dimethylsilanediylbis(indenyl)zirconium di~l,loride dimethylsilan~li~rlLis(4~aph~1,ylindenyl)zirconium dichloride dimethylsilan~diylbis(2-methyl~"~oindenyl)zirconium dichloride dimethylsilanediylbis(2-methy,indenyl)~irconium dichloride 10 dimethylsilan~i~lLis(2-methyl4-(1~,aphthyl)indenyl)~irconium dichloride dimethylsilanediylbis(2-methyl4-(2-"aphthyl)indenyl)zirconium dichloride dim~th~lsilanediylbis(2-methyl4-phenylindenyl)zirconium dichloride dirnethylsila"~liylbis(2-methyl4-t-butylindenyl)zirconium dichloride dimethylsilanediyll.is(2-methyl4-isol~ropylindenyl)zirconium dichlorid 15 dimethylsilan~diylbis(2-methyl-4-ethyli"denyl)~ircG"ium dichloride dimethylsilanediylbis(2-methyl4ff-acena~htl,indenyl)zirconium dichloride dimethyl ~ nediylLis(2 4-dimethylindenyl)zirconium dichloride dimethylsilanediylLis(2-ethylindenyl)zirconium dichloride dimethylsil~"ediylbis(2-ethyl4-ethylindenyl)zirconium di~,loride 20 dimethylsil~ lbis(2-ethyl4-phenylindenyl)~i,wnium dichloride dimethylsilanedi~bis(2-methyl4 5-benzoindenyl)zirconium dichloride dimethylsila"ediylbis(2-methyl4 6-diisopropylindenyl)~ ium dichloride dimethylsilaneJi~lbis(2-methyl4 5-diisop,opylindenyl)zirconium dichloride dil "etl ,ylsilanediylbis(2 4 6-l, i" ,e~l ,ylindenyl)~i, conium dichloride 25 dimethylsilanediylbis(2 5 6-t,i"~e~lIylindenyl)zirconium dichloride dimethylsilanedi~lbis(2 4 7-trimethylindenyl)zirconium dichloride dimethylsilanediylbis(2-methyl-5-isobutylindenyl)zirconium dichloride dimethylsilanediylbis(2-methyl-5-t-butylindenyl)zirconium dichloride dimethylsilanediylbis(2-methyl4-,c 1 ,enantl u ylindenyl)~irconium dichloride 30 dimethylsilanediylbis(2-ethyl4-phenanthrylindenyl)zirconium dichloride methyl(phenyl)silanediylbis(2-methyl4-phenylindenyl)zirconiumdichlorid methyl(phenyl)silanediylbis(2-methyl4 6-diisopropylindenyl)zirconium dichloride methyl(phenyl)silanediylbis(2-methyl4-isopropylindenyl)zirconium dichloride -methyl(phenyl)sila"edi~lbis(2-methyl-4 S-l,en~oindenyl)~i,conium dichloride methyl(phenyl)silanediylbis(2-methyl-4 5-(methyll.e"~o)-indenyl)~irconium dichloride methyl(phenyl)sil~,)edi~lbis(2-methyl4 5-(tetr~" ,eli ,ylL,er,~o)indenyl)zirco-nium dichloride methyl(phenyl)silanediylbis(2-methyl-4-a-acenaphtl ,i"clenyl)zirconium dichloride methyl(phenyl)sila"eJ;ylL,is(2-methylindenyl)~irconilJm dichloride methyl(phenyl)sila"eJiylbis(2-methyl-5-isobutylindenyl)zirconium dichloride methyl(phenyl)silanedi~lbis(2-methyl4-pl)enarltl " yl;ndenyl)~irconium dichloride methyl(phenyl)silanediylbis(2-ethyl4-phena, Ithlylindenyl)zirconium dichloride 1 2~th~n~i~1bis(2-methyl-4~henylindenyl)~ircon. ~m dichloride 1 4-bulanediylbis(2-methyl-4-phenylindenyl)zirconium dichloride 1 2 eti .aneJi~lbis(2-methyl-4 6-diisopropylindenyl)~irconium dichloride 1 4-butan~d;ylbis(2-methyl-4-isopr~pylindel "~ ir~n ~rn dichloride 1 4-butsinedi~rlbis(2-methyl-4 5-beri~oindenyl)~irconium dichloride 1 2~ti.~.)eJiylbis(2-methyl-4 5-benzoindenyl)zirconium dichloride 1 2~tl.a,leJiylbis(2 4 7-tri",eU,ylindenyl)zirconium dichloride 1 2~hanedi~1bis(2-methylindenyl)~irconium dichloride 1 4-butanedi~rlbis(2-methylindenyl)~irconium dichloride bis(butylcyclo,.)entadienyl)Zr+CH2CHCHCH2B~(C6F5)3 bis(methylindenyl)Zr+CH2CHCHCH2B~(C6F5)3 dimethylsilal ,e Jiybis(2-methyl4,5-benzoindenyl)Zr+CH2CHCHCH2B~(C6F5)3 1 2~tl,anediylbis(2-methyli"denyl)Zr+CH2CHCHCH2B~(C6F5)3 1 ,4-butaned;~lL,is(2-methylindenyl)Zr+CH2CHCHCH2B~(C6F5)3 dimethylsilanediylbis(2-methyl-4 6~iisopropylindenyl)-Zr+CH2CHCHcH2B (C6F5)3 dimethylsilaneJi~ll,is(2-ethyl-4-phenylindenyl)Zr+CH2CHCHCH2B~(C6F5)3 dimethylsilanediylbis(2-methyl-4-phenylindenyl)Zr+CH2CHCHCH2B~(C6F5)3 methyl(phenyl)silandiylbis(2-methyl-4-phenylindenyl)-Zr+cH2cHcHcH2B (C6F5)3 dimethylsilanedi~rlbis(2-methylindenyl)Zr+CH2CHCHCH2B~(C6F5)3 dimethylsilanediylbis(indenyl)Zr+CH2CHCHCH2B~(C6F5)3 dimethylsilandiyl(tert-butylamido)(tetramethylcyclopentadienyl)-zirconium dichloride [tris(p6, Itanuoro~l ,eny-l)(cyclopenladienylidene)L,orateo](cyclopenladienyl)-1 2 3 4-tetra~l ,e"ylbuta-1 3-dienyl ~i, conium dimethylsilanJiyl [tris(penldlluoropl)eny-l)(2-methyl-4-phenylindenylidene)-boraleo](2-methyl4-phenylindenyl)-1 2 3 4-tetra~l,enylbuta-1 3-dienyl zirconium 5 dimethylsilandiyl-[tris(trifluoromethyl)(2-methylber,~indenylidene)-borateo](2-methyl~,kindenyl-)-1 2 3 4-tet, apl ,eny-lbuta-1 3-dienyl~irconium dimethylsilan~iyl [tris(pent~lluoropl)el,y-l)(2-methylindenylidene)boraleo]
(2-methylindenyl)-1 2,3 4-tetra,c l ,enylbuta-1 3-dienyl ~ircGI)ium dimethylsila. ,eJiylbis(indenyl)dimethyl~ircG"ium 1 0 dimethylsilaneJiylbis(4-naphlhylindenyl)dimethylzirconium dimethylsila"ediylbis(2-methylLe, I~Gil ,Jenyl)dimethykirconium dimethylsilan~Jiylbis(2-methylindenyl)dimethyl~ircGnium dimethylsilaned;ylbis(2-methyl-4-(1 -naphll ,yl)indenyl)di,nethykirconium dimethylsilaneJiylbis(2-methyl-4-(2-nap ht hy-l)indenyl)dimeth-ykirco~ ,ium 15 dimethylsilanediylbis(2-methyl4-phenylindenyl)di",ell,ykirconium dimethylsilan6Jiylbis(2-methyl-4-t-butylinJenyl)dimethykirconium dimethylsilanedi~lbis(2-methyl-4-isopropylindenyl)dir"etl ,ykirconium dimethylsilanediylbis(2-methyl-4-ethylindeny-l)dimethyl~irconium dimethylsilaneJiylbis(2-methyl-4~-acena,chtl ,indenyl)dimethyl~i, cGnium 20 dimethylsilan~Jiylbis(2 4-di" ,etl ,ylindenyl)di" ,etl ,~kirconium dimethylsilanediylbis(2-ethylindenyl)di" ,e~l ,yl~ir~nium dimethylsilanediylbis(2-ethyl4-ethylindenyl)dimethyl~ir~nium dimethylsilaneJiylbis(2-ethyl-4-phenylindenyl)dimethyl~i, conium dimethylsilaned;ybis(2-methyl4 5-be"~oindenyl)dimetl,ykirconium 25 di",etl ,yl~ilanediylbis(2-methyl4 6-diisopropylindenyl)dil "eth~l~irconium dimethylsilaneJiylbis(2-methyl45~iisopropylindenyl)di,netl,yl irconium di. "etl ,ylsilanediylbis(2 4 6-t, i,netl ,ylindenyl)dimethykirconium dimethylsilanediylbis(2 5 6-l,imetl,ylindenyl)dimethylzirconium dimethylsilanediylbis(2 4 7-l, i."ethylindenyl)dimeth~l~irconium 30 dimethylsilaneJiylbis(2-methyl-5-isobutylindenyl)dirnethylzirconium dimethylsilanediylbis(2-methyl-5-t-butylindenyl)dimethykirconium dimethylsilanediylbis(2-methyl4-phenanlhl ylindenyl)dimethylzirconium dimethylsilanediylbis(2-ethyl4-phe"anll ,rylindenyl)dimethykirconium methyl(phenyl)silan6Jiylbis(2-methyl4-phenylindenyl)dimethykir~"ium methyl(phenyl)silanediylbis(2-methyl4 6- diisopropylinJenyl)dimethylzirconium methyl(phenyl)silanediyll,is(2-methyl4-isopropyli. ,de,)yl)dimethyl~irco"ium methyl(phenyl)silanedi~lbis(2-methyl-4 5-benzoindenyl)dimethykircol ,ium 5 methyl(phenyl)sila"eJ;~ll,is(2-methyl4 5-(methylbenzo)indenyl)dirnell,ykirconium methyl(phenyl)silaneJiylbis(2-methyl-4 Sttet, ar"ell "~I~"~o)indenyl)-dimethylzirconium methyl(phenyl)sila"6Jiyll,is(2-methyl-4~-acenaphtl ,indenyl)d,. "ethyl~ir~. ,iummethyl(phenyl)silanediylbis(2-methylir,-Jenyl).li",ethykir~nium 10 methyl(phenyl)silane.Jiylbis(2-methyl-5-isobutylindenyl)dimethyki, conium methyl(phenyl)silan6diylbis(2-methyl-4-phenanthrylindenyl)dimethyl- ~ircol ,ium methyl(phenyl)silanediylbis(2-ethyl4-~1 ,enan U "ylindenyl)dimethyl~irconium 1 2~U,aneJiyll,is(2-methyl4-pheny,i. ,Jenyl)dimethykirconium 1 4-butan~ lbis(2-methyl4-phenylindenyl)dimethykirconi~m 1 2~th 2. aJ;ylbis(2-methyl4 6-diisop, opylindenyl)dimethyki, conium 1 4but ,~Ji~1L.is(2-methyl q iso~ropylindenyl)dimethyl~irconium 1 4-butan~iylbis(2-methyl4 5-benzoindenyl)dimethyl~irconium 1 2~U ,~n~liylL.is(2-methyl4 5-benzoindenyl)dimethykirconium 1 2~U,aneJi~lbis(2 4 7-~,i",etl"~lindenyl)dimethyl,irconium 20 1 2~U ,a"eJ;yll,is(2-methylindenyl)dimeU ,ykir~"ium 1 4-butaneJ;ylbis(2-methylindenyl)dimethykir~nium Particular pr~ference is given to:
dimethylsil~nediylbis(2-methylinden~l)zirconium dichloride 25 dimethylsila"eJiylbis(2-methyl4-(1-naphthyl)indenyl)zirconium dichloride dimethylsilanediylbis(2-methyl4-phenylindenyl)~irconium dichloride dimethylsilanediylbis(2-methyl44~-acenaphthindenyl)zirconium dichloride dimetl,ylsilanediylbis(2-ethyl4-phenylindenyl)zirconium dichloride dimethylsilaned;ybis(2-methyl4 5-benzoindenyl)zirconium dichloride 30 dimethylsila"ediylbis(2-methyl4 6-diisop,opylindenyl)zirconium dichloride di. "etl ,ylsilanediylbis(2-methyl4-phenanthrylindenyl)zirconium dichloride dimethylsilanediylbis(2-ethyl4-pl)e"a, IU " ylindenyl)zirconium dichloride 2 1 933 1 ~
methyl(phenyl)silanediylbis(2-methyl4~henar,ll"ylindenyl)~ir~"ium dichloride methyl(phenyl)silaneJiylbis(2-ethyl4-pl ,ena. ni llyli"denyl)~irconium dichloride Methods of ~,r~paring metallocenes of the formula I are des~ibed for example in S Joumal of O(gano",etallic Chem. 288 (1985) 63 - 67 and the documents cited tl,erei.~.
The catalyst system of the invention preferably further comprises at least one ~ yst.
The cocatalyst c~mpGI ,ent which can according to the invention be present in the catalyst system is at least one co",pound selscted from the group consisting of aluminoAanes or Lewis acids or ionic co",pounds which react with a met~llocene to convert the latter into a calionic co",pound.
Aluminoxanes which are preferably used are co",pounds of the formula ll (R Al)n (Il) Alumir,oxanes can for example be cyclic as in formula lll --O A I
-- _ or linear as in formula IV
R\ R /R
A I--O A I O " A I ~ I V ) R/ \R
or of the cluster type as in formula V, as are desa ibed in recent literature; cf. JACS
117 (1995), 6485-74, OrganG",et~lics 13 (1994), 2957-2969.
I~
~ "~ t ~l ) 1~
The radicals R in the formulae (Il), (Ill), (IV) and (V) can be identical or dirrerenl and each be a C1-C20-hydlo~,bon group such as a C1-C6-alkyl group, a C6-C18-aryl group, benzyl or hydl ogen, and p is an integer from 2 to 50, preferably from 10 to 35.
The radicals R are preferably identical and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly prererably methyl.
If the radicals R are difreren~, they are prererably methyl and hydlogen, methyl and isobutyl or methyl and n-butyl, with hyd~gen, isobutyl or n-butyl preferably being pr~sent in a propG, lion of 0.01 - 40% (number of rrdic~ls R).
25 The aluminoxane can be prepared in various ways by known methods. One of the melhod~ is, for exd"~ple, reacting an aluminum hydrocarbon compound and/or a hydlidoaluminum hydlocarl,on cG",,,~ound with water (grseous, solid, liquid or bound - for example as water of cryslr'li~lion) in an inert solvent (e.g. toluene). Toprepare an alum noxane having difrerent alkyl groups R, two difrerenl 30 trialkylaluminums (AIR3 + AIR'3) corresponding to the desired composition andreactivity are reacled with water (cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424).
2 1 933 1 ~
_ Regardless of the ~ tl)od of preparation, all aluminoxane solutions have in cGi"r.,on a varying cGntent of unreacled aluminum slal ling cornpound which is present in free form or as ~duct 5 As Lewis acid, pre~er~nce is given to using at least one Grganoboron or or~,anoaluminum cGr"~ound containing C1-C20-groups such as L ranched or unL,an.;l.~.J alkyl or haloalkyl, e.g. methyl, propyl, isopropyl, isobutyl and trifluor~.,etl,yl or unsaturated groups such as aryl or haloaryl, e.g. phenyl, tolyl, benzyl, p-fluorophenyl, 3,5-difluGru~Jhe"~l, ~.lta*.loropî,enyl, pentalluoropl,enyl, 3,4,5-trifluoropl,ei"~l and 3,5-di(trifluo~o.netl ,yl)phenyl.
Particular preference is given to o(ga.,oboron cG.."~ounds.
Examples of Lewis acids are trifluoroborane, triphenyll,orane, 15 tris(4-fluoro~l ,enyl)l,ora. .e, tris(3,5-difluoropl ,enyl)l,orane, tris(4-fluor~..,etl .yl~hel ,yl)boral .e, tris(pentt~nuorophenyl)borane, tris(tolyl)l,Gr~.,e, tris(3,5-dimethylphenyl)borane, tris(3,5-difluoro~l .enyl)borane and/or tris(3,4,5-trifluoropl ,enyl)borane.
In particular, pr~ference is given to tris(penlalluoropl)enyl)bo~ne.
lonic co,~r'~lysts which are preferably used are cGmpounds containing a non-coordinating anion, for example tetrakis(pentan.lorophenyl)borates, tet~,cl .enylL,orales, SbF6-, CF3S03- or Cl04-. As cationic counterion, use is made of Lewis bases such as methylamine, aniline, dimethylamine, diethylamine, N-25 methylaniline, diphenylamine, N,N~i."ethylaniline, l,i",ethylamine, triethylamine, tri-n-butyla"~ine, methyldiphenylamine, pyridine, p-bromo-N,N~i,.,etl,ylaniline, p-nitro-N,N-dimethyla"iline, triethylphosphine, triphenylphos~l,ine, diphenylphospl)ine,tetrahydrothiophene and triphenyl~lbenium.
30 Examples of such ionic compounds according to the present invention are:
triethylal, .r. IGnium tetra(phenyl)borate, tributyla,.".,oni ~m tetra(phenyl)borate, l, i..,etl ,yla,nmonium tetra(tolyl)borate, tributyla"",~onium tetra(tolyl)borale tributyla"""onium tetra(~,enldlluoropl ,enyl)borate tributyl8,."~0nium tetra(penldlluoropl ,ei .yl)aluminate lripr~pyl~,..,.~onium tstra(dimethylphenyl)borate 5 tributyla" " "onium tetra(trifluoror"ell ,ylphenyl)borale tributyl~r"",onium tetra(4-fluorophenyl)borale N N-dimethylanilinium tetra(phenyl)borale N N-diethylanilinium tetra(phenyl)borale N N-dimethylanilinium tetrakis(pentafluorophenyl)borate 10 N N-dimethylanilinium tetrakis(pentdlluorophenyl)aluminate di(propyl)ammonium tetrakis(,l~entdlluorophel~yl)borate di(cyclol ,exyl)ammonium tetrakis(penlanuorophenyl)bor~le t, i~l ,enylpl ,ospl onium tetrakis(phenyl)borate triethyl~l os~l ,onium tetrakis(phenyl)bora~e 15 diphenylpl)ospl.o,nium tetrakis(phenyl)borate tri(methyl~ "yl)pl .ospl .onium t~trakis(phenyl)borate tri(dimethylphenyl)~l .os~l ,onium tetrakis(phenyl)borale l, i~l ,enylc~- ~nium tetrakis(pe, tdlluorophenyl)borate l ,enyl~, t,enium tetrakis(pentanuoropl)enyl)aluminate 20 b ipl .enyl~, Len. un tetrakis(phenyl)aluminate fe"~c~nium tetrakis(penldlluorophenyl)borate and/or fe"oeenium tetrakis(pentdiluoropl,e"yl)aluminate.
rre~ere"ce is given to lri,c I ,enylcarbenium tetrakis(pentafluorophenyl)borate and/or N N-dimethylanilinium tetrakis(~,e, .tdlluo, o~l ,enyl)borate.
25 It is also possible to use mixtures of at least one Lewis acid and at least one ionic cGI"pound.
Also illl~lldl)t as cocAI~lyst col"ponents are borane or ca,l,orane co""~ounds such as 7 8-dicarbaunde~ rane(13) 30 undeca~,ydrido-7 8~ir"etl,yl-7 8-dicarbaunde~Ahorane d~le¢~hydrido-1-phenyl-1 3-dicarbanonaborane tri(butyl)a",-noniumundecahydrido-8-ethyl-7,9-dicarbaundec~horate, 4~rl,~nona~orane( 1 4)-bis(tri(butyl)a" ,r"onium) nonaborate bis(tri(butyl)ammonium) u.,dec~l~orate bis(tri(butyl)ammonium) d~JecAhorate bis(tri(butyl)a..,..,onhm) decacl1lorodecaborale tri(butyl)ammonium 1~,bAclecAhorates 5 tri(butyl)ammonium 1~.bAdoJe~horates tri(butyl)ammonium 1 -b imdt h~lsilyl-1~, b~decAhorates tri(buyl)ammonium bis(nonahydrido-1 3-dica. L,onnonal~rate)cob~t~te(lll) Tri(butyl)ammonium bis(u..~ecal)ydrido-7 8-dicarbaunde-~horate)-fer,dle(lll).
10 The support co",ponenl of the catalyst system of the invention can be any Grga"i~
or inor~anic inert solid in particular a porous support such as talc inorganic oxides and finely di~ided polymer powders (e.g. polyolefins).
Suitable inorganic oxides are those of elem6nts of groups 2 3 4 5 13 14 15 and 15 16 of the Periodic Table of the Elements. Examples of oxides prefer,ed as supports include silicon dioxide aluminum oxide and also mixed oxides of the two ele,.,ents and cor, e5PGI .ding oxide mixtures. Other inorganic oxides which can be used alone or in combination with the last-named prefer, ed oxidic supports are for exampleMgO ZrO2 TiO2 or B2O3 to name only a few.
The support ,.,aterials used have a specir,c surface area in the range from 10 to 1000 m2/g a pore volume in the range from 0.1 to 5 ml/g and a mean particle size of from 1 to 500 IJm. P~eference is given to supports having a specir,c surface area in the range from 50 to 500 m2/g a pore volume in the range between 0.5 and 3.5 ml/g 25 and a mean particle size in the range from 5 to 350 um. Particular preferel)ce is given to supports having a specific surface area in the range from 200 to 400 m2/g a pore volume in the range from 0.8 to 3.0 ml/g and a mean particle size of from 10 to 200 ~m.
30 If the support material used naturally has a low moisture contenl or residual solvent cGnlent dehydration or drying before use can be omitted. If this is not the case as when using silica gel as support material dehydration or drying is advisable. The weight loss on ignition (LOI) should be 1% or less. The thermal dehydration or drying of the support ",alerial can be carried out under rerluced pressure and simultaneous ~lanl;eting with inert gas (e.g. nilrogen). The drying te"~peralure is in the range between 100 and 1000C preferably between 200 and 800C. In this case the pressure is not decisive. The duration of the drying process can be 5 between 1 and 24 hours. Shorter or longer drying times are possible provided that under the cG-~-liliGns selected e~ librium can be established with the hydroxyl groups on the support surface which normally requires betwocn 4 and 8 hours.
Dehyd~dliG., or drying of the support ",aterial can also be achieved by chemical10 metl l~ds by r~acting the adsG, Led water and the hydroxyl groups on the surface with suitable s~ sl~)ces for making the surface inert. The reaclion with the reagent for making the surface inert can convert the hydroxyl groups completely or partially into a form which does not lead to any adverse inlera.tion with the catalytically active cen~ers. Suitable s~ nces for making the surface inert are for example 15 silicon halides and silanes e.g. silicon teba~;l.loride chlorol,i"~ethylsilane dimethylaminotrichlorosilane and o~anometallic cG"")ounds of aluminum boron and "~s~ esium e.g. I,i",~ll"~laluminum triethylaluminum triisobutylaluminum triethyll,orane dibutyl~"agnesium. The chemical dehydration or making inert of the support ",at6(ial is carried out for example by reac~ing with exclusion of air and 20 moisture a suspension of the support material in a sl~-t~h!e solvent with the reagent for makin~ the surface inert in pure form or dissolved in a suitable solvent. Suitable solvents are for example alipha~ic or aro",atic hydrocarl.ons such as penlane I ,exane heptane toluene or xylene. The reaclion for making the surface inert iscarried out at tel"peratures between 25 C and 120 C preferably between 50 and 25 70C. Higher and lower tel"peral-Jres are possible. The reaction time is between 30 minutes and 20 hours preferably from 1 to 5 hours. After the chemical dehydl alio"
has proceeded to completion the support material is isolated by filtration under inert condiliGns, washed one or more times with suitable inert solvents as have been desu ib~J above and finally dried in a stream of inert gas or under reduced 30 pressure.
Organic support materials such as finely divided polyolefin powders (e.g.
polyethylene polypropylene or polystyrene) can also be used and should likewise 219331~
be freed of a~ . ing moisture, residu~l solvent or other impurities by appropri~le pUIifiC~tiGn and drying operatiG,.s before use.
To prepar~ the SlJ~JpGI led catalyst system, at least one of the above- des~ ibed S mePIloc~.,e cG",ponenls is brought into contact with the coc~PIyst cG""~onenl in a suitable solvent so as to obtain a soluble reaction product.
The soluble r eactiG" product is then added to the support material which has been dehyJ~ ated or made inert, the solvent is removed and the resulting SUp,)GI l~d ."ct-'lcc~ catalyst system is dried to ensure that all or most of the solvent isremoved from the pores of the support material. The SUppGI led catalyst is ol,tained as a froe flowing powder.
A process for prepdri,~ a free-flowing and, if desired, prepolym6ri~6.J SUppGI led catalyst system comprises the following steps:
a) pre~J~IdtiGll of a preacti.lated met~llocene/cocA~A~yst mixture in a suitable solvent, where the metallocene con"~onent has one of the structures desu ibeJ above, b) ~p~ ion of the preacli~ated met~llocene/co~lalyst solution to a porous, generally inorganic dehydrated support, c) removal of the major part of solvent from the resulting mixture, d) isol-tion of the suppo. led catalyst system, e) if desi~d, a prepoly",eri~alion of the resulting supported catalyst system using one or more olefinic monomer(s), in order to obtain a prepoly",~ri~ed SUppGI l~d catalyst system.
Plefer.ed solvents for the preparalion of the preactivated metallocene/coc~l~lyst mixture are hydrocarl,ons and hydrocarL,on mixtures which are liquid at the selected - - 21 q331 9 reaction te",~rat.lre and in which the individual co,nponents preferably dissolve.
However the solubility of the individual COrnpGI ,enls is not a prerequisite if it is ensured that the rea-tiGn product of met~llocene and co~l~lyst COmpGi ,ent is soluble in the sale~t6J solvent. Examples of suitable solvents include alkanes such aspenlane isopenta"e l,exane hep~ane octaneandnG,)ane;cycloalkanessuch as cyclopenlane and cyclohexane; and arol"dtics such as ber,~el,e toluene ethyl~n~ne and diethyll~"~ene. It is also possible to use halogel)ate-i hydroca,L.ons such as methylene chloride or ar~",atics such as fluorobe"~ene or o-dichlor~ , .e. Very particular preference is given to toluene.
The amounts of alu."ino~cane and metallocene used in the preparalion of the suppGIt~d catalyst system can be varied over a wide range. r~ference is given tousing a molar ratio of aluminum to the transition metal in the metallocene of from 10:1 to 1000:1 very particularly prererably a ratio of from 50:1 to 500:1.
In the case of methylaluminoxane preferel)ce is given to using 30% sll en~tl, solutions in toluene but the use of 10% strength solutions is also possi~le.
For the preacli~ation the metallocene in the form of a solid is dissolved in a solution of the aluminoxane in a suit~'e solvent. It is also possible to dissolve the ",et~'l~ne separalely in a suitable solvent and s~hse~uently to col,lbil,e this solution with the aluminoxane solution. rleference is given to using toluene.
EP-A 0302424 des~ ibes the preacti-/ation of metallocenes for use in unsupportedform in poly",eri~tiol,s. The preactivation time is from 5 minutes to 100 hours preferably from 5 to 60 minutes in particular from 10 to 20 minutes. A significantly longer prea~ /ation is possible but it normally neither increases the activity nor Je~eases the activity although it can be quite useful for storage pu".oses. Theprea~i-/ation is carried out at a temperalure of from -78 to 1 00C preferal)ly from 0 to 70C.
Sul ~risi, Igly it has now been found that in the case of sterically demanding metallocenes such as rac-dimethylsilanediylbis(2-methyl4-phenylindenyl)zirconiumdichloride a distinctly longer preactivation time leads to a significant increase in .
activity. In the case of sterically demanding met~locenes the preactivation time is pr~fo, aL,ly from 30 minutes to 200 hours in particular from 1 to 50 hours especi~'ly from 5 to 20 hours.
5 The preacti~ation can take place at room te,nperal-Jre (25 C). The use of higher te",~eratures can in some cases shG, ~n the time necess~y for preactivation and effect an ~ tional inc(ease in activity. In this case Uhigher tel"peraluren means a ran~e between 50 and 1 00C. Even at higher temperatures the prefer,ed ,~,rea~ti~ation time in the case of the metr"ccenes prefer,ed accordi,1g to the 10 invention is d;slinctly above the preacti.ration time known from the prior art.
The preacti-/ated solution is s~hse~uently combined with an inert support ",ale,ial usually silica gel which is in the form of a dry powder or as a suspe"sio" in one of the abov~",enlioned solvents. The powder used is preferably silica gel. Any order of 15 addition can be used. The preactivated met~llocene/coc~'AIyst solution can be the support ",alerial or else the support ",aterial can be introd~Ged into the solution.
The volume of the preacli~ated solution can exceed 100% of the total pore volumeof the support ",alerial used or else can be up to 100% of the total pore volume.
20 The te",perat~lre at which the preactivated solution is brought into cGnlac~ with the support ",alerial can vary in the range between 0 and 1 00C. However lower or higher temperat.lres are also possible. After co",b..)ing the support material and solution the mixture is maintained at this te",peral-Jre for a further period of from about 1 minute to 1 hour prereral,ly 5 minutes.
All or most of the solvent is suhse~uently removed from the suppol led catalyst system; for this procedure the mixture can be stirred and if desired also heated.
rl~erably both the visible propo, lion of solvent and also the solvent in the pores of the support material are removed. The removal of the solvent can be carried out in a 30 conventional ",a"ner using reduced pressure and/or flushing with inert gas. During the drying procedure the mixture can be heated until the free solvent has been removed which usually takes from 1 to 3 hours at a telnperalure which is pre~erably selected so as to be between 30 and 60C. The free solvent is the visible proportion of solvent in the mixture. For the pl" ~,oses of the present invention, residual solvent is the propG, liGI ~ which is ~, Iclosed in the pores. As an allel "ali~/e to complete removal of the solvent, the SUIJpGl led catalyst system can also be dried only to a certain r~sid~' solvent contenl, with the free solvent having been completely 5 removed. The SU,upGI led catalyst system can subsequently be washed with a low-boiling hyd~ l l,on such as penlane or I ,exane and dried again.
The SU~pGI t~i catalyst system prepared according to the invention can either beused directly for the poly-"eri~-dlion of olefins or be prepoly"~eri~ed with one or more 10 olefinic ~G~GI~ers before use in a poly..,eri~dlion process. The procedure for prepoly..~ri~atio.. of suppG-led catalyst systems is described, for example, in WO 94/28034.
The prese. It invention also provides a process for preparing a polyolefin by polymeri~tion of one or more olefins in the presence of the catalyst system of the invention colr~prisin~ at least one l-~nsilion metal col.,pG.,ent of the formula 1. For the pu.~oses of the presenl invention, the term poly",eri~3tion refers to either a l,G",opoly"~eri~dtion or a copoly",eri~alion.
Preference is given to polymerizing olefins of the formula Rm-CH=CH-Rn, where Rmand Rn are iJ6ntical or Jif~renl and are each a h~JI ogen atom or a carL,on-containin~ radical having from 1 to 20 carbon atoms, in particular from 1 to 10 cal bGI I atoms and Rm and Rn to~ether with the atoms connectin~ them can form one or more rings. Examples of such olefins are 1-olefins having 2 - 40, preferably from 2 to 10 ca. I,Gn atoms, for example ethene, p~pene, 1 -butena, 1 -pentene, 1 -hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1,3-but~diene, 1 ,4-hexadiene, vinylnorbG. "ene, no, bG" ,adiene, ethylnorbor"adiene and cyclicolefins such as no, bor"ene, tetracyclododecene or methylnorbornene. In the p~cess of the invention, preference is given to ho",Gpoly")eri~i"g ethene or ~ rop~ne, or copoly",eri~in~ ethene with one or more 1-olefins having from 3 to 20 carbon atoms, e.g. propene, and/or one or more dienes having from 4 to 20 carbonatoms, e.g. 1,4-butadiene, nGrbG",adiene or ethylno,l,Grnadiene. Examples of such copolymers are ethene-propene-copolymers or ethene-propene-1,4-hexadiene terpolymers.
The poly",eri~atiG" is ca"ieJ out at a te",perature of from ~0 to 300 C preferably from 50 to 200C. The pressure is from 0.5 to 2000 bar pre~erably from 5 to 64 bar.
The poly",eri~dtion can be carried out in solution in bulk in suspension or in the gas phase continuously or batchwise in one or more stages.
The ca~alyst system prepared according to the invention can be used as sole 10 catalyst CGlllpGI ,ent for the polymeri~a~iGn of olefins having from 2 to 20 ca, l,on atoms or pre~erably in combi. IdtiG, I with an aluminum alkyl or an alu",inoxane. The soluble aluminum celllpGnent is added to the ,nonomer and serves to free the mG,)G,ner of s~ lA~s which can impair the catalyst activity. The amount of aluminum cefi,pon6nt added .lepe"ds on the quality of the ",onor"el:i used.
If, .ec~ss~ hyJ~ o9el l can be added as mcl~c~ weight regul~'or and/or to inerease the activity.
The invention is illusba~ed by the following exa",ples.
Examples General The preparation and handling of the organGI"etallic cG",pounds were carried out with excl- ~siQn of air and moisture under argon (Schlenk technique). All necess~ry solvents were freed of air and moisture before use by boiling for a number of nours over a suitable desiccant and s~ ~hse~uent distillation under argon.
The met~locenes used were charactel i~ed by 1 H-NMR 1 3C-NMR and IR
spe-;t~oscopy.
D~rl,~ilions;
PP = polypropylene MC = ",et~'lc~ne cat = SUppG~ catalyst system h= hour VN = viscosity number in cm3/g Mw = weight average molar mass in g/mol M~JMn = molar mass distribution deter",ined by gel per",edliGn chromatoy,d~l,y BD = bulk density in g/dm3 and mp. = ",elt;ng point in C deter"~ined by dirrere,ltial scanning calorimetry (DSC 2ndl,eatiny) Example 1 Prepa~tion of the SU~JpGI led catalyst system 444 mg (0.71 mmol) of rac~li",etl,ylsilanediylbis(2-methyl4-phenylindenyl)~i,~i,ium dichloride were dissolved at room te",perature in 35.5 ml (128 mmol of Al) of 30%
st,e,.yth methylaluminoxane solution in toluene1). For the prea.;ti~ation the mixture was allowed to stand at 25C for 18 h while being prote~;ted from light. The mePIlocene/MAO solution thus prepareJ was s~ ~hse~uently diluted with 86.9 ml oftoluene to a total volume of 122.4 ml. 30.6 9 of SiO22) were slowly introd~ ~ced into this solution. The ratio of the volume of the solution to the total pore volume of the support material was 2.5. After ~ddi~i~n was cG"~plete the mixture was stirred for 5 minutes at room ~e",perat.lre. Subsegl~ently the mixture was evaporaled to dryness under red~ pressure at 40C over a period of 2 h and the residue was dried for 5h at 25C and 10~3 mbar. This gave 39.5 9 of a free-flowing pink powder which according to ~le."enlal analysis conlained 0.15% by weight of Zr and 8.0% by weight of Al.
Poly" ,~ri~dtion A dry 16 dm3 reactor which had been flushed first with nil,ogen and s~lhse~uently with pr~p~ne was filled with 10 L of liquid propene. 8 ml of 20% strength triethylaluminum sol! ~tion in Varsol (Witco) were added as scavenger and the mixture was stirred for 15 minutes at 30 C. S! ~hse~uently a suspension of 1.2 9 of the su~ J ",et~llocene catalyst in 20 ml of a dearomatized petroleum fraction having a boiling point range from 100C to 120C was added to the reactor the mixture was heated to the poly"~eri~alion temperature of 65 C and the poly",eri~ation system was held at 65C for 1 h. The poly",eri~ation was sl~pped by addition of 20 ml of isGpropanol the excess monomer was vented and the polymer obtained was dried under reduce~ pressure. This resulted in 2.4 kg of polypropylene powder.
The catalyst activity was 193 kg of PP/(g of MC x h) or 2 kg PP/(g of cat x h) The isot~tic polypropylene prepared had the following prope"ies:
mp. 147C; Mw = 901,000 g/mol, MW/Mn = 2.3, VN = 603 ml/g, BD = 370 g/dm3 5 CG",parati~e Example 1 r, epar~tion of the S~lppGI le.J catalyst system 460 mg (0.73 mmol) of rac-dimethylsilanediylbis(2-methyl-4-10 phenylin~l~"yl)~i,cGnium dichloride were dissolved at room te",pera~ure in 36.8 ml (133 mmol of Al) of 30% sll enytl l methylaluminoxane solution in toluene1). Themixture was diluted with 93 ml of toluene and stirred for 10 min at 25C. 33.2 9 of SiO22) were slowly introdt~ced into this solution. The ratio of the volume of the solution to the tobl pore volume of the support ",alerial was 2.5. After addition was 15 complete, the mixture was stirred for 5 minutes at room tei"perature. S! Ihseg~ ~ently, the mixture was evaporaled to dryness under reduced pressure at 40C over a period of 2 h and the residue was dried for 5 h at 25C at 10~3 mbar. This gave 44 9 of a free-flowing, pink powder which, according to ele,~enl31 analysis, contained 0.16% by weight of Zr and 8.0% by weight of Al.
Poly",eri~ation The poly",eri~atiGn was carried out using a Ille~llod similar to Example 1. Thisresulted in 1.4 kg of polypropylene powder.
The catalyst activity was 109 kg of PP/(g of MC x h) or 1.2 kg PP/(g of cat x h) The isot~ctic polypropylene prepared had the following properties:
mp. 146C; Mw = 1,010,000 g/mol, MW/Mn = 2.3, VN = 643 mllg, BD = 380 g/dm3 1) AlL,e",arle CGr~,oration, Baton Rouge, l oui~i^na, USA
2) Silica grade MS 948, W.R. Grace, Davison Chemical Division, Baltimore, Maryland, USA, pore volume 1.6 ml/g, calcined at 800 C.
.
Example 2 r, eparaliG" of the SUppG~ ~ed catalyst system 198 mg (0.31 mmol) of rac~imethylsilanediylbis(2-methyl4-phenylindenyl)~ircG"iumdichloride were ~issolvcd at room te""~erature in 17.4 ml (68 mmol of Al) of 30%st~r,.Jtl, methylalumir,oxane sol~ ~tion in toluene3). For the preacti~/ation the mixture was allow~d to stand at 25C for 18 h while being prot~ct~d from light. The met^'lcc~ne/MAO solution was s~hse~uently diluted with 44.6 ml of toluene to total volume of 62 ml. 15.5 9 of sio24) were slowly intro~uce~ into this solution. The ratio of the volume of the soMtion to the total pore volume of the support material was 2.5. After A-l~lition was complete the mixture was stirred for 5 minutes at roomt6",~rature. S! Ihse~l ~ently the mixture was evaporaled to dryness under re~luce~l pressure at 40C over a period of 2 h and the residue was dried for 5 h at 25 C and 10~3 mbar. This gave 20.2 9 of a free-flowing pink powder which accord;ng to cle."ental analysis contained 0.12% by weight of Zr and 7.9% by weight of Al.
Poly",~ ation The poly",6ri~tion was carried out under the same conditions as in Example 1 butusing 1.6 9 of catalyst and 8 ml of 20% stren!Jtl, triethylaluminum in Varsol (Witco).
This res~lte~ in 1.7 kg of polypropylene powder.
The catalyst activity was 128 kg of PP/(g of MC x h) or 1.06 kg of PP/(g of cat x h) Th~ isot~ctic polypropylene prepared had the following properties:
mp. 148 C; Mw = 1.300.000 g/mol M~,JMn = 2.8 VN = 762 ml/g BD = 290 g/dm3 Co""~arati~e Example 2 PreparatiG" of the supported catalyst system 203 mg (0.32 mmol) of rac-dimethylsilanediylbis(2-methyl4-phenylindenyl)~i,cGnium dichloride were d;ssolvcd at room te",peralure in 17.8 ml (70 mmol of Al) of 30%ab~rl!Jtll methylalumir,oxane solution in toluene3). The mixture was diluted with 45 ml of toluene and stirred for 10 minutes at room te",perat, re.15.7 9 of SiO2~) were slowly intro~l~c~ into this solution. The ratio of the volume of the solution to the total pore volume of the support material was 2.5. After addition was complete, the mixture was stirred for 5 minutes at room te",peral,Jre. Subsequently, the mixture was evaporated to dryness under red~ ~ced pressure at 40 C over a t,eriod of 2 h and the residue was dried for 5h at 25C and 10-3 mbar. This gave 20.0 9 of a free-flowing, pink powder which, according to elen,enlal analysis, contained 0.12% byweight of Zr and 8.0% by weight of Al.
Poly"~e, i~lion The poly.,~eri~tion was car- ied out under the same conditions as in Example 1, but using 2.2 9 of catalyst and 8 ml of 20% strength triethylaluminum in Varsol (Witco).
This res~ ~lted in 0.8 kg of polypropylene powder.
The catalyst activity was 60 kg of PP/(g of MC x h) or 0.5 kg of PP/(g of cat x h) The iSQt~CtiC polypropylene prepared had the following prope, lies:
mp. 148C; MW = 1,300,000 g/mol, MW/Mn = 3.0, VN =698 mllg, BD = 310 g/dm3 3) Witco GmbH, Bergkamen, Federal Republic of Germany 4) Silica grade MS 948, W.R. Grace, Davison Chemical Division, Baltimore, Maryland, USA, pore volume 1.6 mllg, calcined at 600C
Exa",ple 3 r, eparatiGn of the SUppOI led catalyst system 23 mg (0.040 mmol) of rac-di",etl,ylsilanediylbis(2-methyl4,5-ben7r..)denyl)~ir~i)ium dichloride were dissolved in 1.8 ml (7.1 mmol of Al) of 30%
-~;tlt:lnJtll methylaluminoxane solution in toluene3) and the mixture was allowed to stand at 25C for 18 h while being prote~;ted from light. S~ ~hseg! ~ently the metallocene/MA0 solution thus prepared was diluted with toluene to a total volume of 4 ml. 6.5 9 of PP powder5) were then slowly introd~ ~ce~ into this solution. A
vacuum (0.1 mbar) was briefly applied to remove the gas prese"l in the pores of the support and the solution was thus completely soaked up. After slir~ing inlensively for a further 10 minutes a l,G",ogeneous finely divided and free-flowing powder was obtained.
Poly",eri~ation The poly",eri~ation was carried out under the same conditions as in Example 1 but using the total amount of catalyst powder from Example 3 and 10 ml of 20% slren.Jtl, triisobutylaluminum in Varsol (Witco). This resulted in 2.5 kg of polypropylene powder.
The ~talyst activity was 110 kg of PP/(g of MC x h) The isot~-~1ic polypropylene prepared had the following properties:
mp. 146 C; Mw = 350.000 g/mol MWJMn = 2.2 VN = 250 ml/g BD = 280 g/dm3 5) AccurellD -PP (sieve h~-;tion ~ 200 ,um) from Akzo, freed of impurities by exl,detion with toluene in a Soxhlet exl, actor under inert conditions s~ ~hse~uently dried for 5 h at 25C and 2 x 104 mbar and flushed with argon CG"~parati~e Exslllple 3 Preparation of the su~,po, led catalyst system 23 mg (0.040 mmol) of rac-d;metl ,~lsilanediylbis(2-methyl4 5-benzoindenyl)~irconium dichloride were dissolved in 1.8 ml (7.1 mmol of Al) of 30%
-~l, er,!Jth methylaluminoxa"e solution in toluene3) and diluted with toluene to a total volume of 4 ml. This mixture was stirred for 10 minutes at 25C. 6.5 g of PP
powder5) were slowly introduced into the metallocene/MA0 solution thus prepared.
A vacuum (0.1 mbar) was briefly applied to remove the gas present in the pores of the support and the solution was thus completely soaked up. After stirring intensively for a further 10 minutes, a hG"~Ggeneous, finely divided and free-flowing powder was ol)tained.
Poly,Y)eri~ation The polyll,eri~dliG" was csr.ied out under the same conditions as in Exa",ple 1, but using the total amount of the catalyst powder from Col"parali~e Exal.,~le 3 and 10 ml of 20% st~n~tl) triisobutylaluminum in Varsol (Witco). This resulted in 1.8 kg of polypropylene powder.
The catalyst activity was 78 kg of PP/(g of MC x h) The i50~iC polypropylene prepared had the following properties:
mp. 146C; Mw = 330.000 g/mol, Mw/Mn = 2.3, VN = 244 ml/g, BD = 290 g/dm3 5) Accurell -PP (sieve f~ dCliOn < 200 ,um) from Akzo, freed of impurities by e~ ~-,tion with toluene in a Soxhlet e,~l, actor under inert conditions, sl ~hse~uently dried for 5 h at 25 C and 2 x 10~ mbar and flushed with argon Example 4 rl eparalion of the suppo-led catalyst system 200 mg (0.32 mmol) of rac~;,netl,~lsilanediylbis(2-methyl4-phenylindenyl)zirconium dichloride were dissolved at room temperature in 17.6 ml (69 mmol of Al) of 30%
sl,eny~l, methylalumir,oxa,)e solution in toluene3). For the preactivation, the mixture was allowed to stand at 25C for 18 h while being protected from light. The 30 metallocene/MAO solution thus prepared was s~lhse~uently diluted with 103 ml of toluene to a total volume of 120.6 ml. 16.1 9 of SiO26) were slowly introduced into this solution. The ratio of the volume of the solution to the total pore volume of the support male,ial was 2.5. After addition was complete, the mixture was stirred for 5 minutes at room te")perature. Subsequently, the mixture was evaporaled to dryness under redl ~c~ pressure at 40 C over a period of 2 h and the residue was dried for 5 h at 25C and 10~3 mbar. This gave 21.1 9 of a free-flowing, pink powder which, according to elefi,en~al analysis, contained 0.14% by weight of Zr and 8.6% by 5 weight of Al.
6) Grade MS 3030 manuf^~tllred by PQ Cor~ oration, Valley Forge, Pennsylvania, USA, pore volume: 3 ml/g, calcined at 300 C
10 Poly"~e,i~lion The polyn,eri~tio" was cs"ied out under the same conditions as in Example 1, butusing 1.6 9 of catalyst and 8 ml of 20% triethylaluminum in Varsol (Witco). Thisresulted in 1.3 kg of polypropylene powder.
The catalyst activity was 83 kg of PP/(g of MC x h) or 0.8 kg of PP/(g of cat x h) The isot~ic polypropylene pr~parad had the following prope, lies:
mp. 147C; Mw = 910,000 g/mol, MW/Mn = 2.3, VN = 610 ml/g, BD = 380 g/dm3 Co"",a(ali~e Exsr"ple 4 rl apar~tion of the sL~ Jo~ led catalyst system 198 mg (0.31 mmol) of rac-dimethylsilanediylbis(2-methyl4-phenylindenyl)zirconium dichloride were dissolved at room temperature in 17.6 ml (69 mmol of Al) of 30%
s~ra"5Jtl, methylal~""i.,o~ane solution in toluene3) The mixture was diluted witn 106 ml of toluene and stirred for 10 minutes at 25C.16.5 9 of SiO26) were slowly 30 introduced into this solution. The ratio of the volume of the solution to the total pore volume of the support material was 2.5. After addition was complete, the mixturewas stirred for 5 minutes at room te",,l~eral.lre. Subsequently, the mixture wasevaporated to dryness under red~ ~ced pressure at 40C over a period of 2 h and the residue was dried for 5 h at 25C and 10-3 mbar. This gave 21.3 9 of a free-flowing pink powder which according to ele",ental analysis contained 0.13 % by weight ofZr and 8.7% by weight of Al.
Poly",eri~alion The polyn,ericalion was ca"ied out using a method similar to Example 1 but using1.6 9 of the catalyst from CG",,,~ara~i~e Example 4. This resulted in 0.8 kg of polypropylene powder.
The catalyst activity was 56 kg of PP/(g of MC x h) or 0.5 kg of PP/(g of cat x h) The isol~ic polypropylene prepared had the following prope, lies:
mp. 147C; Mw = 1 000 000 g/mol MW/Mn = 2.2 VN = 640 ml/g BD = 390 g/dm3 Example 5 r~pa~atiG" of the suppo, led catalyst system 109 mg (0.17 mmol) of rac4i",ethylsilanediylbis(2-methyl4-phenylindenyl)~irconium dichloride were dissolved in 9.7 ml (38 mmol of Al) of 30% sllenylil methylalumir,oxane solution in toluene3) and the mixture was stirred for 5 h at 60C.
The metallocene/MAO solution was s~ ~hsequently cooled to 25C and diluted with 55.6 ml of toluene to a total volume of 65.3 ml. 8.7 9 of sio27) were slowly introduced into the solution thus prepared. The ratio of the volume of the solution to the total pore volume of the support material was 2.5. After addition was complete the mixture was stirred for 5 minutes at room temperalure. Subsequently the mixture was evaporaled to dryness under reduced pressure at 40 C over a period of 2 h and the residue was dried for 5 h at 25C and 10-3 mbar. This gave 12.8 g of a free-flowing pink powder which according to ele,nental analysis contained 0.12%
by weight or Zr and 8.0% by weight of Al.
21933t9 7) Grade MS 3030 manuf~ctl~red by PQ CGr~,oralion, Valley Forge, Pennsylvania, USA, pore volume: 3 ml/g, calcined at 400 C
Poly",~, i~alion The poly",6ri~aliG" was cslli~J out under the same conditions as in Example 1, but using 1.6 9 of the catalyst from Example 5 and 8 ml of 20% triethylaluminum in Varsol (Witco). This res~ ~ted in 1.8 kg of polypropylene powder.
The catalyst activity was 133 kg of PP/(g of MC x h) or 1.1 kg of PP/(g of cat x h) The isot~ctic polypropylene prepared had the following prope, lies:
mp. 148C, Mw = 1,200,000 g/mol; MW/Mn = 2.4; VN = 680 ml/g, BD = 390 gldm3 Co."pdr~ti./e Example 5 rreparalion of the suppo. leJ catalyst system 123 mg (0.20 mmol) of rac-dimethylsilanediylbis(2-methyl-4-phenylindenyl)~irconium dichloride were dissolved in 10.9 ml (43 mmol of Al) of a 30% strength methylaluminoxane solution in toluene3) and the mixture was stirred for 5 h at 25C.
The ",dl^'lccene/MAO solution was s~ ~hse~uently diluted with 65 ml of toluene to a total volume of 75.9 ml. 10.1 9 of sio27) were slowly introduGed into the solution thus pre~ared. The ratio of the volume of the solution to the total pore volume of the support ",ale,ial was 2.5. After addi~iG" was complete, the mixture was stirred for a further 5 minutes at 25C. Sl ~hseguently, the mixture was evaporaled to drynessunder re~hlced pressure at 40C over a period of 2 h and the residue was dried for 5 h at 25C and 10~3 mbar. This gave 14.8 9 of a free-flowing, pink powder which, according to ele."ental analysis, contained 0.12% by weight of Zr and 7.8% by weight of Al.
Poly" ,~ri~dtiG, ~
The poly-.,eri~alion was carried out using a ",eU,od similar to Example 1 but using 1.6 9 of the catalyst from Col"parali~/e Example 5. This resulted in 1.1 kg of 5 polypropylene powder.
The catalyst activity was 85 kg of PP/(g of MC x h) or 0.7 kg of PP/(g of cat x h) The isQl^clic polypropylene prepareJ had the following propel lies:
mp. 149C; Mw = 1 250 000 g/mol MW/Mn = 2.3 VN = 678 mllg BD = 380 g/dm3 The chara~t6ri~tic data of the respective catalyst systems and the polymers obtained measured in the Exampl~s and Co",parali~/e Examples 1 to 5 are to 15 provide a better overview sullllllali~ed in Tables 1 and 2 below.
Table 1 Catalyst system E~)C#) Metallocene T i m e T e m p . %Zr %AI Acta) lminl rcl E1 I*) 1080 25 0.15 8.0 193 C1 I*) 10 25 0.16 8.0 109 E2 I*) 1080 25 0.12 7.9 128 C2 I*) 10 25 0.12 8.0 60 E3 Il**) 1080 25 n.d. n.b. 110 C3 Il**) 10 25 n.d. n.b. 78 E4 I~) 1080 25 0.14 8.6 83 C4 I*) 10 25 0.13 8.7 56 E5 I*) 300 60 0.12 8.0 133 C5 I*) 300 25 0.12 7.8 85 15 +) Examples #) C~.""~ara~i~/e examples a) Catalyst activity in kg of PP/(g of MC x h) *) rac~imethylsilanediylbis(2-methyl4-phenylindenyl)zirconium dichloride **) rac~imethylsilanediylbis(2-methyl-4,5-benzoindenyl)zirconium dichloride Table 2 Polymers E~l C#) mp. Mw Mw/Mn VN BD
r~ [gmol] lmlg1l[gldm3]
E1 147901,000 2.3 603 370 C1 1461,010,000 2.3 643 380 E2 1481,300,000 2.8 762 290 C2 1481,300,000 3.0 698 310 E3 146350,000 2.2 250 280 C3 146330,000 2.3 244 290 E4 147910,000 2.3 610 380 C4 1471,000,000 2.2 640 390 E5 1481,200,000 2.4 680 390 C5 1491,250,000 2.3 678 380
10 Poly"~e,i~lion The polyn,eri~tio" was cs"ied out under the same conditions as in Example 1, butusing 1.6 9 of catalyst and 8 ml of 20% triethylaluminum in Varsol (Witco). Thisresulted in 1.3 kg of polypropylene powder.
The catalyst activity was 83 kg of PP/(g of MC x h) or 0.8 kg of PP/(g of cat x h) The isot~ic polypropylene pr~parad had the following prope, lies:
mp. 147C; Mw = 910,000 g/mol, MW/Mn = 2.3, VN = 610 ml/g, BD = 380 g/dm3 Co"",a(ali~e Exsr"ple 4 rl apar~tion of the sL~ Jo~ led catalyst system 198 mg (0.31 mmol) of rac-dimethylsilanediylbis(2-methyl4-phenylindenyl)zirconium dichloride were dissolved at room temperature in 17.6 ml (69 mmol of Al) of 30%
s~ra"5Jtl, methylal~""i.,o~ane solution in toluene3) The mixture was diluted witn 106 ml of toluene and stirred for 10 minutes at 25C.16.5 9 of SiO26) were slowly 30 introduced into this solution. The ratio of the volume of the solution to the total pore volume of the support material was 2.5. After addition was complete, the mixturewas stirred for 5 minutes at room te",,l~eral.lre. Subsequently, the mixture wasevaporated to dryness under red~ ~ced pressure at 40C over a period of 2 h and the residue was dried for 5 h at 25C and 10-3 mbar. This gave 21.3 9 of a free-flowing pink powder which according to ele",ental analysis contained 0.13 % by weight ofZr and 8.7% by weight of Al.
Poly",eri~alion The polyn,ericalion was ca"ied out using a method similar to Example 1 but using1.6 9 of the catalyst from CG",,,~ara~i~e Example 4. This resulted in 0.8 kg of polypropylene powder.
The catalyst activity was 56 kg of PP/(g of MC x h) or 0.5 kg of PP/(g of cat x h) The isol~ic polypropylene prepared had the following prope, lies:
mp. 147C; Mw = 1 000 000 g/mol MW/Mn = 2.2 VN = 640 ml/g BD = 390 g/dm3 Example 5 r~pa~atiG" of the suppo, led catalyst system 109 mg (0.17 mmol) of rac4i",ethylsilanediylbis(2-methyl4-phenylindenyl)~irconium dichloride were dissolved in 9.7 ml (38 mmol of Al) of 30% sllenylil methylalumir,oxane solution in toluene3) and the mixture was stirred for 5 h at 60C.
The metallocene/MAO solution was s~ ~hsequently cooled to 25C and diluted with 55.6 ml of toluene to a total volume of 65.3 ml. 8.7 9 of sio27) were slowly introduced into the solution thus prepared. The ratio of the volume of the solution to the total pore volume of the support material was 2.5. After addition was complete the mixture was stirred for 5 minutes at room temperalure. Subsequently the mixture was evaporaled to dryness under reduced pressure at 40 C over a period of 2 h and the residue was dried for 5 h at 25C and 10-3 mbar. This gave 12.8 g of a free-flowing pink powder which according to ele,nental analysis contained 0.12%
by weight or Zr and 8.0% by weight of Al.
21933t9 7) Grade MS 3030 manuf~ctl~red by PQ CGr~,oralion, Valley Forge, Pennsylvania, USA, pore volume: 3 ml/g, calcined at 400 C
Poly",~, i~alion The poly",6ri~aliG" was cslli~J out under the same conditions as in Example 1, but using 1.6 9 of the catalyst from Example 5 and 8 ml of 20% triethylaluminum in Varsol (Witco). This res~ ~ted in 1.8 kg of polypropylene powder.
The catalyst activity was 133 kg of PP/(g of MC x h) or 1.1 kg of PP/(g of cat x h) The isot~ctic polypropylene prepared had the following prope, lies:
mp. 148C, Mw = 1,200,000 g/mol; MW/Mn = 2.4; VN = 680 ml/g, BD = 390 gldm3 Co."pdr~ti./e Example 5 rreparalion of the suppo. leJ catalyst system 123 mg (0.20 mmol) of rac-dimethylsilanediylbis(2-methyl-4-phenylindenyl)~irconium dichloride were dissolved in 10.9 ml (43 mmol of Al) of a 30% strength methylaluminoxane solution in toluene3) and the mixture was stirred for 5 h at 25C.
The ",dl^'lccene/MAO solution was s~ ~hse~uently diluted with 65 ml of toluene to a total volume of 75.9 ml. 10.1 9 of sio27) were slowly introduGed into the solution thus pre~ared. The ratio of the volume of the solution to the total pore volume of the support ",ale,ial was 2.5. After addi~iG" was complete, the mixture was stirred for a further 5 minutes at 25C. Sl ~hseguently, the mixture was evaporaled to drynessunder re~hlced pressure at 40C over a period of 2 h and the residue was dried for 5 h at 25C and 10~3 mbar. This gave 14.8 9 of a free-flowing, pink powder which, according to ele."ental analysis, contained 0.12% by weight of Zr and 7.8% by weight of Al.
Poly" ,~ri~dtiG, ~
The poly-.,eri~alion was carried out using a ",eU,od similar to Example 1 but using 1.6 9 of the catalyst from Col"parali~/e Example 5. This resulted in 1.1 kg of 5 polypropylene powder.
The catalyst activity was 85 kg of PP/(g of MC x h) or 0.7 kg of PP/(g of cat x h) The isQl^clic polypropylene prepareJ had the following propel lies:
mp. 149C; Mw = 1 250 000 g/mol MW/Mn = 2.3 VN = 678 mllg BD = 380 g/dm3 The chara~t6ri~tic data of the respective catalyst systems and the polymers obtained measured in the Exampl~s and Co",parali~/e Examples 1 to 5 are to 15 provide a better overview sullllllali~ed in Tables 1 and 2 below.
Table 1 Catalyst system E~)C#) Metallocene T i m e T e m p . %Zr %AI Acta) lminl rcl E1 I*) 1080 25 0.15 8.0 193 C1 I*) 10 25 0.16 8.0 109 E2 I*) 1080 25 0.12 7.9 128 C2 I*) 10 25 0.12 8.0 60 E3 Il**) 1080 25 n.d. n.b. 110 C3 Il**) 10 25 n.d. n.b. 78 E4 I~) 1080 25 0.14 8.6 83 C4 I*) 10 25 0.13 8.7 56 E5 I*) 300 60 0.12 8.0 133 C5 I*) 300 25 0.12 7.8 85 15 +) Examples #) C~.""~ara~i~/e examples a) Catalyst activity in kg of PP/(g of MC x h) *) rac~imethylsilanediylbis(2-methyl4-phenylindenyl)zirconium dichloride **) rac~imethylsilanediylbis(2-methyl-4,5-benzoindenyl)zirconium dichloride Table 2 Polymers E~l C#) mp. Mw Mw/Mn VN BD
r~ [gmol] lmlg1l[gldm3]
E1 147901,000 2.3 603 370 C1 1461,010,000 2.3 643 380 E2 1481,300,000 2.8 762 290 C2 1481,300,000 3.0 698 310 E3 146350,000 2.2 250 280 C3 146330,000 2.3 244 290 E4 147910,000 2.3 610 380 C4 1471,000,000 2.2 640 390 E5 1481,200,000 2.4 680 390 C5 1491,250,000 2.3 678 380
Claims (17)
1. A supported catalyst system having a high activity, obtainable by a) bringing at least one metallocene component in at least one solvent into contact with at least one cocatalyst component, b) adding the soluble product to the support material and c) removing the solvent.
2. A supported catalyst system as claimed in claim 1, wherein d) the supported catalyst system is isolated and e) prepolymerized with at least one olefinic monomer.
3. A supported catalyst system as claimed in claim 1 or 2, wherein the metallocene component is a compound having the formula (I) (I) wherein M1 is a metal of group IVb of the Periodic Table of the Elements, R1 and R2 are identical or different and are each a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C20-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, an OH group, an NR12 2 group, where R12 is a C1-C2-alkyl group or a C6-C14-aryl group, or a halogen atom, R3 to R8 and R3' to R8' are identical or different and are each a hydrogen atom, a C1-C40-hydrocarbon group which may be linear, cyclic or branched, e.g. a C1-C10-alkyl group, a C2-C10-alkenyl group, a C6-C20-aryl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, or adjacent radicals R4 to R8 and/or R4' to R8' together with the atoms connecting them form a ring system, R9 is a bridge, preferably , , , , , , , , , .
where R10 and R11 are identical or different and are each a hydrogen atom, a halogen atom or a C1-C40-group such as a C1-C20-alkyl group, a C1-C10-fluoroalkyl group, a C1-C10-alkoxy group, a C6-C14-aryl group, a C6-C10-fluororyl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, or R10 and R11 together with the atoms connecting them form one or more rings, and x is an integer from zero to 18, M2 is silicon, germanium or tin and the rings A and B are identical or different, saturated or unsaturated.
R9 can also link two units of the formula I to one another.
where R10 and R11 are identical or different and are each a hydrogen atom, a halogen atom or a C1-C40-group such as a C1-C20-alkyl group, a C1-C10-fluoroalkyl group, a C1-C10-alkoxy group, a C6-C14-aryl group, a C6-C10-fluororyl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, or R10 and R11 together with the atoms connecting them form one or more rings, and x is an integer from zero to 18, M2 is silicon, germanium or tin and the rings A and B are identical or different, saturated or unsaturated.
R9 can also link two units of the formula I to one another.
4. A supported catalyst system as claimed in one or more of claims 1 to 3, wherein M1 is zirconium or hafnium.
5. A supported catalyst system as claimed in one or more of claims 1 to 4, wherein R1 and R2 are identical and are methyl or chlorine, in particular chlorine, and R9 = M2R10R11, where M2 is silicon or germanium and R10 and R11 are each a C1-C20-hydrocarbon group such as C1-C10-alkyl or C6-C14-aryl.
6. A supported catalyst system as claimed in one or more of claims 1 to 5, wherein the cocatalyst component is at least one compound selected from the group consisting of aluminoxanes or Lewis acids or ionic compounds which react with a metallocene to convert the latter into a cationic compound.
7. A supported catalyst system as claimed in one or more of claims 1 to 6, wherein the solvent is a hydrocarbon or hydrocarbon mixture.
8. A supported catalyst system as claimed in claim 7, wherein the solvent is at least one hydrocarbon such as pentane, isopentane, hexane, heptane, octane, nonane; cyclopentane, cyclohexane or aromatics such as benzene, toluene, ethylbenzene and diethylbenzene or halogenated hydrocarbons such as methylene chloride or halogenated aromatics such as fluorobenzene or o-dichlorobenzene.
9. A supported catalyst system as claimed in one or more of claims 1 to 8, wherein the metallocene component and the cocatalyst component are used in a molar ratio of aluminum to the transition metal in the metallocene of from
10:1 to 1000:1.
10. A supported catalyst system as claimed in one or more of claims 1 to 9, wherein the time for process step (a) is from 30 minutes to 200 hours.
10. A supported catalyst system as claimed in one or more of claims 1 to 9, wherein the time for process step (a) is from 30 minutes to 200 hours.
11. A supported catalyst system as claimed in one or more of claims 1 to 10, wherein the time is from 1 to 50 hours, in particular from 5 to 20 hours.
12. A supported catalyst system as claimed in one or more of claims 1 to 11, wherein the support material used is silica gel as powder.
13. A process for preparing the supported catalyst system having a high activity as claimed in one or more of claims 1 to 12, which comprises a) bringing at least one metallocene component in at least one solvent into contact with at least one cocatalyst component, b) adding the soluble product to the support material and c) removing the solvent.
14. The process as claimed in claim 13, wherein d) the supported catalyst system is isolated and e) prepolymerized with at least one olefinic monomer.
15. A process for preparing a polyolefin by polymerization of one or more olefins in the presence of at least one catalyst system as claimed in one or more of claims 1 to 12.
16. The process as claimed in claim 15, wherein at least one olefin having the formula Rm-CH=CH-Rn is polymerized, where Rm and Rn are identical or different and are each a hydrogen atom or a carbon-containing radical having from 1 to 20 carbon atoms and Rm and Rn together with the atoms connecting them can form one or more rings.
17. Use of at least one catalyst system as claimed in one or more of claims 1 to 12 for preparing a polyolefin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19548288A DE19548288A1 (en) | 1995-12-22 | 1995-12-22 | Supported catalyst system, process for its preparation and its use for the polymerization of olefins |
| DE19548288.3 | 1995-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2193319A1 true CA2193319A1 (en) | 1997-06-23 |
Family
ID=7781116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002193319A Abandoned CA2193319A1 (en) | 1995-12-22 | 1996-12-18 | Supported catalyst system, a process for its preparation and its use for the polymerization of olefins |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0780402B1 (en) |
| JP (1) | JP4445044B2 (en) |
| AT (1) | ATE238355T1 (en) |
| BR (1) | BR9606095A (en) |
| CA (1) | CA2193319A1 (en) |
| DE (2) | DE19548288A1 (en) |
| ES (1) | ES2197933T3 (en) |
| NO (1) | NO965501L (en) |
| TW (1) | TW374772B (en) |
| ZA (1) | ZA9610688B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU8647898A (en) * | 1997-08-12 | 1999-03-01 | Chisso Corporation | Process for the preparation of olefin (co)polymers, olefin copolymers, and application thereof |
| RU2348653C2 (en) | 2003-02-21 | 2009-03-10 | Дау Глобал Текнолоджиз Инк. | Method of homo- or copolymerisation of conjugated olefins |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3726067A1 (en) * | 1987-08-06 | 1989-02-16 | Hoechst Ag | METHOD FOR PRODUCING 1-OLEFIN POLYMERS |
| DE4119343A1 (en) * | 1991-06-12 | 1992-12-17 | Basf Ag | INSULATED, SUPPORTED CATALYST SYSTEM FOR THE POLYMERIZATION OF C (DOWN ARROW) 2 (DOWN ARROW) - TO C (DOWN ARROW) 1 (DOWN ARROW) (DOWN ARROW) 0 (DOWN ARROW) -ALK-1-END |
| FI112233B (en) * | 1992-04-01 | 2003-11-14 | Basell Polyolefine Gmbh | Catalyst for olefin polymerization, process for its preparation and its use |
| US5240894A (en) * | 1992-05-18 | 1993-08-31 | Exxon Chemical Patents Inc. | Method for making and using a supported metallocene catalyst system |
| US5238892A (en) * | 1992-06-15 | 1993-08-24 | Exxon Chemical Patents Inc. | Supported catalyst for 1-olefin(s) (co)polymerization |
| WO1994028034A1 (en) | 1993-05-25 | 1994-12-08 | Exxon Chemical Patents Inc. | Supported metallocene catalyst systems for the polymerization of olefins, preparation and use thereof |
| DE4333569A1 (en) * | 1993-10-01 | 1995-04-06 | Hoechst Ag | Process for olefin polymerization |
| FI96866C (en) * | 1993-11-05 | 1996-09-10 | Borealis As | Support olefin polymerization catalyst, its preparation and use |
| DE4344688A1 (en) * | 1993-12-27 | 1995-06-29 | Hoechst Ag | Metallocene compound |
| DE4344689A1 (en) * | 1993-12-27 | 1995-06-29 | Hoechst Ag | Metallocene compound |
-
1995
- 1995-12-22 DE DE19548288A patent/DE19548288A1/en not_active Withdrawn
-
1996
- 1996-12-18 DE DE59610373T patent/DE59610373D1/en not_active Expired - Lifetime
- 1996-12-18 CA CA002193319A patent/CA2193319A1/en not_active Abandoned
- 1996-12-18 ES ES96120354T patent/ES2197933T3/en not_active Expired - Lifetime
- 1996-12-18 EP EP96120354A patent/EP0780402B1/en not_active Expired - Lifetime
- 1996-12-18 AT AT96120354T patent/ATE238355T1/en not_active IP Right Cessation
- 1996-12-19 ZA ZA9610688A patent/ZA9610688B/en unknown
- 1996-12-19 BR BR9606095A patent/BR9606095A/en not_active Application Discontinuation
- 1996-12-20 NO NO965501A patent/NO965501L/en not_active Application Discontinuation
- 1996-12-20 TW TW085115774A patent/TW374772B/en active
- 1996-12-24 JP JP34301896A patent/JP4445044B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE59610373D1 (en) | 2003-05-28 |
| NO965501L (en) | 1997-06-23 |
| BR9606095A (en) | 1998-11-03 |
| ATE238355T1 (en) | 2003-05-15 |
| JPH09188712A (en) | 1997-07-22 |
| TW374772B (en) | 1999-11-21 |
| NO965501D0 (en) | 1996-12-20 |
| EP0780402B1 (en) | 2003-04-23 |
| ZA9610688B (en) | 1997-06-23 |
| ES2197933T3 (en) | 2004-01-16 |
| DE19548288A1 (en) | 1997-06-26 |
| EP0780402A1 (en) | 1997-06-25 |
| JP4445044B2 (en) | 2010-04-07 |
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