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NO178891B - Metallocenforbindelser - Google Patents

Metallocenforbindelser Download PDF

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NO178891B
NO178891B NO903928A NO903928A NO178891B NO 178891 B NO178891 B NO 178891B NO 903928 A NO903928 A NO 903928A NO 903928 A NO903928 A NO 903928A NO 178891 B NO178891 B NO 178891B
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hydrocarbyl
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radicals
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Jo Ann Marie Canich
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Exxon Chemical Patents Inc
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Priority to NO953466A priority Critical patent/NO309657B1/no
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Publication of NO178891C publication Critical patent/NO178891C/no

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Description

Foreliggende oppfinnelse vedrører nye metallocenforbindelser og nærmere bestemt visse overgangsmetallforbindelser fra gruppe IVB i det periodiske system. Disse forbindelsene kan anvendes i et katalysatorsystem sammen med en alumoksanforbindelse for fremstilling av polyolefiner, spesielt polyetylen, polypropylen og a-olefin-kopolymerer av etylen og propylen som har en høy molekylvekt. Katalysatorsystemet er meget aktivt ved lave forhold for aluminium til gruppe IVB-overgangsmetallet, og katalyserer således fremstillingen av et polyolefinprodukt som inneholder lave nivåer av kataly-satorrest.
Som velkjent eksisterer det forskjellige prosesser og katalysatorer for homopolymerisasjon eller kopolymerisasjon av olefiner. For mange anvendelser er det av største viktighet for et polyolefin å ha en høy vektmidlere molekylvekt samtidig som det har en relativt snever molekylvektfordeling. En høy vektmidlere molekylvekt gir når den er ledsaget av en snever molekylvektfordeling, et polyolefin eller en etylen-a-olefin-kopolymer med høye styrkeegenskaper.
Tradisjonelle Ziegler-Natta-katalysatorsystemer - en overgangsmetallforbindelse som er kokatalysert med en aluminiumalkylforbindelse - er i stand til å produsere polyolef iner som har en høy molekylvekt, men en bred molekylvektfordeling.
I den senere tid har det blitt utviklet et katalysatorsystem hvori overgangsmetallforbindelsen har to eller flere cyklopentadienylring-ligander, hvor en slik metallforbindelse er betegnet en metallocen, som katalyserer fremstillingen av olefinmonomerer til polyolefiner. Følgelig har metallocenforbindelser av gruppe IVB-metaller, spesielt titanocen og zirkonocen, blitt benyttet som overgangsmetallkomponenten i et slikt "metallocen"-holdig katalysatorsystem for fremstilling av polyolefiner og etylen-a-olefin-kopolymerer. Når slike metallocener kokatalysseres med en aluminiumalkyl-slik tilfellet er med et Ziegler-Natta-katalysatorsystem av tradisjonell type - er den katalytiske aktiviteten til et slikt metallocen-katalysatorsystem vanligvis for lav til å være av noen kommersiell interesse.
Det har siden blitt kjent at slike metallocener kan kokataly-seres med en alumoksanforbindelse, istedenfor en aluminiumalkylforbindelse, for å tilveiebringe et metallocen-katalysatorsystem av høy aktivitet som katalyserer fremstillingen av polyolefiner.
En rekke forskjellige gruppe IVB-overgangsmetallforbindelser av metallocentypen har blitt angitt som mulige kandidater for et alumoksan-kokatalysert katalysatorsystem. Selv om bis(cyklopentadienyl)-gruppe IVB-overgangsmetallforbindelser har vært den mest foretrukne og omfattende undersøkte type av metallocener for bruk i metallocen/alumoksan-katalysator for polyolefinfremstilling, så har det fremkommet forslag om at mono- og tris(cyklopentadienyl)-overgangsmetallforbindelser også kan være nyttige. Se, f.eks. US-patenter 4 522 982, 4 530 914 og 4 701 431. Slike mono(cyklopentadienyl)-overgangsmetallforbindelser som hittil har vært foreslått som kandidater for en metallocen/alumoksan-katalysator er mono(cyklopentadienyl)-overgangsmetalltrihalogenider og
-trialkyler.
Mer nylig har publikasjonen WO 87/03887 beskrevet bruken av en sammensetning som omfatter et overgangsmetall som er koordinert til i det minste en cyklopentadienyl- og minst en heteroatomligand som en komponent av metallocentypen for bruk i et metallocen/alumoksan-katalysatorsystem for a-olefin-polymerisasjon. Sammensetningen er bredt definert som et overgangsmetall, fortrinnsvis i gruppe IVB i det periodiske system som er koordinert med minst en cyklopentadienylligand og en til tre hetereoligander, idet resten av koordinasjons-behovet er tilfredsstilt med cyklopentadienyl- eller hydrokarbylligander. Det beskrevne metallocen/alumoksan-katalysatorsystemet er Illustrert utelukkende under hen-visning til overgangsmetallforbindelser som er bis(cyklopentadienyl)-gruppe IVB-overgangsmetallforbindelser.
Videre, ved den tredje kjemiske kongress i Nord-Amerika holdt i Toronto, Canada, juni 1988, rapporterte John Bercaw forsøk på å benytte en forbindelse av et gruppe IIIB-overgangsmetall koordinert til en enkel cyklopentadienyl-heteroatombrodannet ligand som et katalysatorsystem for polymerisasjon av olefiner. Selv om en viss katalytisk aktivitet ble observert under de benyttede betingelser, så var aktivltetsgraden og de egenskaper som ble observert i det resulterende polymer-produkt nedslående for en oppfatning at en slik overgangs-metallforblndelse på nyttig måte kunne anvendes for kommer-sielle polymerisasjonsprosesser.
Det eksisterer fremdeles et behov for katalysatorsystemer som tillater fremstilling av polyolefiner av høyere molekylvekt og ønskelig med en snevrere molekylvektfordeling.
I tråd med dette er det ifølge foreliggende oppfinnelse tilveiebragt en metallocenforbindelse, som er kjennetegnet ved at den har den generelle formel:
hvor:
M og M' er Zr, Hf eller Tl;
(C5H4_XRX) er en cyklopentadienylring som er substituert med fra 0 til 4 grupper R, <M>x<H> er 0, 1, 2, 3 eller 4 som betegner substitusjonsgraden, og hver substituentgruppe R er uavhengig et radikal valgt fra C]—C2o-nydroliarDylradikaler, substituerte Ci-^o-hydro^rbylradikaler hvor ett eller flere hydrogenatomer er erstattet med et halogenatom, C^—C20-hydrokarbylsubstituerte metalloidradikaler hvor metalloidet er valgt fra gruppe IVA i det periodiske system, og halogen-radikaler, eller (C5H4_XRX) er en cyklopentadienylring hvori to tilstøtende R-grupper er sammenføyet fra en C4-C2o_ring-struktur slik at det oppnås en mettet eller umettet polycyklisk cyklopentadienylligand;
(JR<*>Z_2) er en heteroatomligand hvor J er et element med koordinasjonstall 3 fra gruppe VA eller et element med koordinasjonstall 2 fra gruppe VIA i det periodiske system, og hver R' er uavhengig et radikal valgt fra C]— C2o~hydrokarbylradikaler, substituerte Cj—C2o~nydrokarbylradikaler hvor ett eller flere hydrogenatomer er erstattet med et halogenatom, og "z" er koordinasjonstallet til elementet J;
hver Q er uavhengig en hvilken som helst enverdig, anionisk ligand eller to 0'er er et toverdig, anionisk chelaterings-middel;
B er en kovalent brodannende gruppe inneholdende et element fra gruppe IVA eller VA i det periodiske system, valgt fra dialkyl-, alkyl-, aryl- eller diarylsilisium- eller-germaniumradikal, eller fenylamido, t-butylamido, metylamido, t-butylfosfido, etylfosfido, fenylfosfido, metylen, dimetylmetylen, dietylmetylen, etylen, dimetyletylen, dietyletylen, dipropyletylen; og
L er en Lewis-base hvor "w" betegner et tall fra 0 til 3, men unntatt forbindelser av den generelle formel:
hvor M har den ovenfor angitte betydning, (C5H4_X»R<2>X») er en cyklopentadienylring som er substituert med fra 0 til 4 R<2->grupper, x' er 1, 2, 3 eller 4, og hvor R<2> og de i gruppene Si(R<2>)2 og YR<2> er uavhengig valgt fra hydrogen, silyl, alkyl, aryl og kombinasjoner derav med opptil 10 karbonatomer,
Q' er uavhengig valgt fra halogen, alkyl, aryl, fenoksy, alkoksy med opptil 10 karbonatomer eller -NR<2> hvor R<2> har den ovenfor angitte betydning, idet n er 1 eller 2 avhengig av valensen til M, og Y er nitrogen eller fosfor.
Det er foretrukket heteroatomet i ligander JR *z_2 er nitrogen, fosfor, oksygen eller svovel. Videre er det foretrukket at M og/eller M' er zirkonium eller hafnium.
Det foretrekkes at gruppen Q er et hydrid-, halogen- eller hydrokarbylradlkal som er forskjellig fra en cykllsk cyklopentadienylgruppe. Videre er det ytterligere foretrukket at gruppen Q er substituert eller usubstituert Cj-C2o-hyclro-karbyl, alkoksyd, aryloksyd, amid, arylamid, fosfid eller arylfosfid, forutsatt at når en hvilken som helst av Q er en hydrokarbylgruppe, så er en slik Q-gruppe forskjellig fra (C5H4_XRX), eller begge er sammen en alkylidengruppe eller en hydrokarbylmetallocykelgruppe.
Eksempler på nevnte polycykliske cyklopentadienylligand er lndenyl, tetrahydroindenyl, fluorenyl eller oktahydro-fluorenyl.
Nevnte Lewis-base kan f.eks. være dietyleter, tetraetyl-ammoniumklorid, tetrahydrofuran, dimetylanilin, anilin, trimetylfosfin, n-butylamin og lignende.
Eksempler på B-gruppen er identifisert i kolonne 1 i nedenstående tabell 1 under overskriften "B".
Eksempler på hydrokarbylradikaler for Q er metyl, etyl, propyl, butyl, amyl, isoamyl, heksyl, isobutyl, heptyl, oktyl, nonyl, decyl, cetyl, 2-etylheksyl, fenyl og lignende, idet metyl er foretrukket. Eksempler på halogenatomer for 0 innbefatter klor, brom, fluor og jod, idet klor er foretrukket. Eksempler på alkoksyder og aryloksyder for Q er metoksyd, fenoksyd og substituerte fenoksyder slik som 4—metylfenoksyd. Eksempler på amider for Q er dimetylamid, dietylamid, metyletylamid, di-t-butylamid, diisopropylamid og lignende. Eksempler på arylamider er difenylamid og hvilke som helst andre substituerte fenylamider. Eksempler på fosfider for 0 er difenylfosfid, dicykloheksylfosfid, dietylfosfid, dimetylfosfid og lignende. Eksempler på alkyldienradikaler for begge 0 sammen er metyliden, etyliden og propyliden. Eksempler på Q-gruppen som er egnet som en bestanddelgruppe eller element i gruppe IVB-overgangsmetallkomponenten i katalysatorsystemet er identifisert i kolonne 4 i tabell 1 under overskriften "Q".
Egnede hydrokarbyl- og substituert hydrokarbylradikaler som, som en R-gruppe, kan være benyttet istedenfor minst ett hydrogenatom i cyklopentadienylringen, vil inneholde fra 1 til 20 karbonatomer og innbefatte rette og forgrenede alkylradikaler, cykliske hydrokarbonradikaler, alkylsubstituerte. cykliske hydrokarbonradikaler, aromatiske radikaler, alkylsubstituerte aromatiske radikaler og cyklopentadienyl-dienyl-p-n-butylfenylamidozirkoniumdiklorid, dimetylsilyl-te trame tyl cyklopent adieny 1 -p-n-butylf enyl aml dohafnium-diklorid. For illustrerende formål vil de ovenfor angitte forbindelser og de som er permutert fra tabell 1 ikke innbefatte Lewis-baseliganden (L). Betingelsene under hvilke komplekser inneholdende Lewls-baseligander slik som eter eller de som danner dimerer oppnås, bestemmes av den sterlske massen til ligandene omkring metallsenteret. For eksempel har t-butylgruppen i Me2Si(Me4C5)(N-t-Bu)ZrCl2 større steriske behov enn fenylgruppen i Me2Si(Me4C5)(NPh)ZrCl2<*>Et20 hvorved eterkoordinasjon i førstnevnte forbindelse ikke tillates. Likeledes, på grunn av den nedsatte steriske massen til trimetylsilylcyklopentadienylgruppen i [Me2Si(Me3SiC5H3)-(N-t-Bu)ZrCl2]2 1 forhold til den til tetrametylcyklopenta-dienylgruppen i Me2Si(Me4C5)(N-t-Bu)ZrCl2, så er førstnevnte forbindelse dimerisk og sistnevnte ikke.
ringer inneholdende en eller flere kondenserte, mettede eller umettede ringer. Egnede organometalliske radikaler som, som en R-gruppe, kan være benyttet istedenfor minst ett hydrogenatom i cyklopentadienylringen, innbefatter trimetylsilyl, trietylsilyl, etyldimetylsilyl, metyldietylsilyl, trifenyl-germyl, trimetylgermyl og lignende. Eksempler på cyklopentadienyl r inggrupper (C5H4_XRX) som er egnet i foreliggende metallocenforbindelser er identifisert i kolonne 2 i tabell 1 under overskriften (C5H4_XRX).
Egnede hydrokarbyl- og substituerte hydrokarbylradikaler som, som en R'-gruppe, kan være benyttet istedenfor minst ett hydrogenatom i heteroatom-J-ligandgruppen, vil inneholde fra 1 til 20 karbonatomer og innbefatte rette og forgrenede alkylradikaler, cykliske hydrokarbonradikaler, alkylsubstituerte cykliske hydrokarbonradikaler, aromatiske radikaler og alkylsubstituerte aromatiske radikaler. Eksempler på heteroatom-ligandgrupper (JR'Z_2) som egnet er identifisert i kolonne 3 i tabell 1 under overskriften (JR'Z_2).
Tabell 1 viser representative bestanddelgrupper og en
rekke sluttkomponenter kan dannes ved å permutere alle mulige kombinasjoner av de nevnte bestanddelgruppene med hverandre. Illustrerende forbindelser er: dimetylsilyltetrametyl-cyklopentadienyl-tert-butylamidozirkoniumdiklorid, dimetyl-s i ly1 tet rame tylcyklopentadienyl-tert-butylamidohafnium-diklorid, dimetylsilyl-tert-butylcyklopentadienyl-tert-butylamido-zirkoniumdiklorid, dimetylsilyl-tert-butyl-cyklopentadienyl-tert-butylamido-hafniumdiklorld, dimetylsilyl tr imetylsilylcyklopentadienyl-tert-butylamidozirkonium-diklorid, dimetylsilyltrimetylcyklopentadienylfenylamido-zirkoniumdiklorid, dimetylsilyltetrametylcyklopentadienyl-fenylamidohafniumdiklorid, metylfenylsilyltetrametylcyklo-pentadienyl-tert-butylamidozirkoniumdiklorid, metylfenyl-s i ly1 tet r ame ty 1cyklopentadienyl-tert-butylamidohafnium-diklorid, metylfenylsilyltetrametylcyklopentadienyl-tert-butylamldohafniumdimetyl, dimetylsilyltetrametylcyklopenta-
Forbindelsene kan fremstilles ved omsetning av en cyklopenta-dienyllitiumforbindelse med en dihalogenforbindelse hvorved et lltiumhalogenidsalt frigjøres og en monohalogensubstituent blir kovalent bundet til cyklopentadienylforbindelseh. Det således substituerte cyklopentadlenylreaksjonsproduktet blir deretter omsatt med et litiumsalt av et fosfid, oksyd, sulfid eller amid (for illustrasjonsformål et litiumamid) hvorved halogenelementet i monohalogensubstituentgruppen i reaksjons-produktet reagerer slik at det frigjøres et lltiumhalogenidsalt og amindelen i litlumamidsaltet blir kovalent bundet til substituenten i cyklopentadienylreaksjonsproduktet. Det resulterende aminderivatet av cyklopentadienylproduktet blir deretter omsatt med en alkyllitiumreagens hvorved de labile hydrogenatomene, ved karbonatomet i cyklopentadienylforbin-delsén og ved nitrogenatoinet i amindelen som er kovalent bundet til substituentgruppen, reagerer med alkylgruppen i 11tiumalkylreagensen til frigjøring av alkanen og dannelse av et litiumsalt av cyklopentadienylforbindelsen. Deretter fremstilles foreliggende metallocenforbindelser ved omsetning av dilitiumsalt-cyklopentadienylforbindelsen med et av gruppe IVB-overgangsmetallene, Zr, Hf eller Ti, fortrinnsvis et halogenid derav.
Fordelaktige forbindelser er de hvor B—gruppebroen er en dialkyl-, diaryl- eller alkylarylsilan, eller metylen eller etylen. Eksempler på de mer foretrukne typer av brodannede grupper er dimetylsilyl-, metylfenylsilyl-, dietylsilyl-, etylfenylsilyl-, difenylsilyl-, etylen- eller metylen-brodannede forbindelser. Mest foretrukket av de brodannede forbindelsene er dimetylsilyl-, dietylsilyl- og metylfenylsilyl -brodannede forbindelser.
For å illustrere typer av metallocenforbindelser kan en hvilken som helst kombinasjon av gruppene i tabell 1 velges. Et eksempel på en forbindelse ville være dimetylsilyl-cyklopentadienyl-t-butylamidodiklorzirkonium.
Foreliggende metallocener kan som nevnt anvendes sammen med alumoksanforbindelser i katalysatorsystemer. Alumoksankomponenten 1 slike katalysatorsystemer er en ollgomer-forbindelse som kan representeres ved den generelle formel (R<2->Al-0)m som er en cyklisk forbindelse, eller kan være R<3>(R<4->Al-0-)m-AlR<5>2 som er en lineær forbindelse. En alumoksan er generelt en blanding av både den lineære og den cykliske forbindelsen. I den generelle alumoksanformelen er R2, R<3>, r<4> og R<5> uavhengig en enverdig anionisk ligand slik som et Cj—Cs-alkylradikal, f.eks. metyl, etyl, propyl, butyl, pentyl eller halogenid og "m" er et helt tall fra 1 til 50. Mest foretrukket er R<2>, R<3>, R<4> og R5 hver metyl og "m" er minst 4. Når et alkylaluminiumhalogenid anvendes i fremstillingen av alumoksan, så kan en eller flere av R<2->R^ være halogenid.
Anvendelse av foreliggende metallocenforbindelse i katalysatorsystemer for fremstilling av polyolefiner skal omtales i det nedenstående. Således kan et katalysatorsystem omfattende foreliggende metallocenforbindelse hensiktsmessig fremstilles ved å anbringe en utvalgt metallocenforbindelse og en utvalgt alumoksanforbindelse, i en hvilken som helst rekkefølge, i et alkan- eller aromatisk hydrokarbonoppløsningsmiddel, fortrinnsvis et som også er egnet for bruk som et polymerisa-sjonsfortynningsmiddel. Når hydrokarbonoppløsningsmldlet som benyttes også er egnet for bruk som et polymerisasjons-fortynningsmiddel, så kan katalysatorsystemet fremstilles in situ i polymerisasjonsreaktoren. Alternativt kan katalysatorsystemet fremstilles separat, i konsentrert form, og tilsettes til polymerisasjonsfortynningsmidlet i en reaktor. På den annen side kan, om ønsket, komponentene i katalysatorsystemet fremstilles som separate oppløsningsmidler og tilsettes til polymerlsasjonsfortynningsmidlet i en reaktor, i passende forhold, slik det er egnet for en kontinuerlig væskepolymerisasjonsreaksjonsmetode. Alkan og aromatiske hydrokarboner egnet som oppløsningsmidler for dannelse av katalysatorsystemet og også som et polymerisasjons-fortynningsmiddel er eksemplifisert ved rette og forgrenede hydrokarboner slik som isobutan, butan, pentan, heksan, heptan, oktan og lignende, cykliske og alicykliske hydrokarboner slik som cykloheksan, cykloheptan, metylcykloheksan, metylcykloheptan og lignende, og aromatiske og alkylsubstituerte aromatiske forbindelser slik som benzen, toluen, xylen og lignende. Egnede oppløsningsmidler innbefatter også flytende olefiner som kan virke som monomerer eller komono-merer inkludert etylen, propylen, 1-buten, 1-heksen og lignende.
Det oppnås vanligvis optimale resultater når metallocen-forbindelsen er til stede i polymeriasjonsfortynningsmidlet i en konsentrasjon fra 0,0001 til 1,0 mmol/liter fortynnings-middel og alumoksankomponenten er til stede i en mengde for tilveiebringelse av et molarforhold for aluminium til overgangsmetall på fra 1:1 til 20 000:1. Tilstrekkelig oppløsningsmiddel bør benyttes for derved å tilveiebringe tilstrekkelig varmeoverføring bort fra katalysatorkomponentene under reaksjonen og for å oppnå god blanding.
Katalysatorsystembestanddelene, dvs. metallocenforbindelsene, alumoksanforbindelsen og polymerisasjonsfortynningsmidlet kan tilsettes til reaksjonsbeholderen på hurtig eller langsom måte. Temperaturen som holdes under kontrakten mellom katalysatorkomponentene kan variere sterkt, slik som f.eks. fra -10 til 300°C. Høyere eller lavere temperaturer kan også benyttes. Under dannelsen av katalysatorsystemet blir reaksjonsblandingen fortrinnsvis holdt innenfor en temperatur fra 25 til 100°C, mest foretrukket ca. 25°C.
Til enhver tid blir de individuelle katalysatorsystemkompo-nenter samt katalysatorsystemet når dette først er dannet, beskyttet overfor oksygen og fuktighet. Reaksjonene blir derfor utført i en oksygen- og fuktighetsfri atmosfære og, når katalysatorsystemet utvinnes separat, blir det utvunnet i en oksygen- og fuktighetsfri atmosfære. Reaksjonene blir derfor fortrinnsvis utført i nærvær av en inert tørr gass slik som f.eks. helium og nitrogen.
Når det gjelder anvendelse av foreliggende metallocenforbindelser i et katalysatorsystem for polymerisasjons-formål, vises det til NO-patentsøknad 920971 og den der angitte omtale og eksemplifisering.
Følgende eksempler illustrerer fremstilling av spesielle metallocenforbindelser ifølge oppfinnelsen.
Alle fremgangsmåter ble foretatt under en inert atmosfære av helium eller nitrogen. Valg av oppløsningsmiddel er ofte valgfrie, og f.eks. i de fleste tilfeller kan enten pentan eller 30-60 petroleumeter benyttes om hverandre. De litium-holdige amidene ble fremstilt fra tilsvarende aminer og enten n-BuLi eller MeLi. Publiserte metoder for fremstilling av LiHC5Me4 innbefatter CM. Fendrick et al., Organometallics, 3. 819, (1984) og F.H. Kohler og K.H. Doll, Z. Naturforsch., 376, 144 (1982). Andre litierte substituerte cyklopenta-dienylforbindelser fremstilles typisk fra den tilsvarende cyklopentadienylligand og n-BuLi eller MeLi, eller ved omsetning av MeLi med den passende fulvenforbindelsen. ZrCl4 og HfCl4 ble innkjøpt fra enten Aldrich Chemical Company eller Cerac. Aminer, silaner og litiumreagenser ble innkjøpt fra Aldrich Chemical Company eller Petrarch Systems. Metylalumoksan ble levert av enten Sherring eller Ethyl Corp.
"BTksempel
Forbindelse A:
Del 1. Me4HC5Li (10,0 g, 0,078 mol) ble langsomt tilsatt til en Me2SiCl2 (11,5 ml, 0,095, i 225 ml tetrahydrofuran (THF)-oppløsning). Oppløsningen ble omrørt i en time for å sikre fullstendig reaksjon. THF-oppløsnings-midlet ble deretter fjernet via et vakuum til en kald felle holdt ved -196°C. Pentan ble tilsatt for å utfelle L1C1. Blandingen ble filtrert gjennom Celite. Oppløsningsmidlet ble fjernet fra filtratet. Me4HC5SiMe2Cl (15,34 g, 0,071 mol) ble utvunnet som en blekgul væske.
Del 2. Me4HC5SiMe2Cl (10,0 g, 0,047 mol) ble langsomt tilsatt til en suspensjon av LiHN-t-Bu (3,68 g, 0,047 mol, a:100 ml TET). Blandingen ble omrørt natten over. TET ble deretter fjernet via et vakuum til en kald felle holdt ved -196'C. Petroleumeter (xlOO ml) ble tilsatt for å utfelle L1C1. Blandingen ble filtrert gjennom Celite. Oppløsningsmidlet ble fjernet fra filtratet. Me2Si(Me4HC5)(HN-t-Bu) (11,14 g, 0,044 mol) ble Isolert som en blekgul væske.
Del 3. Me2Si(Me4HC5)(HN-t-Bu) (11,14 g, 0,044 mol) ble fortynnet med 2:100 ml Et20. MeLi (1,4 M, 64 ml, 0,090 mol) ble langsomt tilsatt. Blandingen fikk omrøres i % time etter den sluttelige tilsetning av MeLi. Eteren ble redusert i volum før fraflltrering av produktet. Produktet, [Me2Si(Me4C5)(N-t-Bu)]Li2, ble vasket med flere små porsjoner av eter og deretter vakuumtørket.
Del 4. [Me2Si(Me4C5)(N-t-Bu)]Li2 (3,0 g, 0,011 mol) ble suspendert i %150 ml Et20. ZrCl4 (2,65 g, 0,011 mol) ble langsomt tilsatt og den resulterende blanding ble omrørt natten over. Eteren ble fjernet via et vakuum til en kald felle holdt ved -196°C. Pentan ble tilsatt for å utfelle LiCl. Blandingen ble filtrert gjennom Celite to ganger. Pentanen ble betydelig redusert i volum og det blekgule, faste stoffet ble frafUtrert og vasket med oppløsningsmiddel.
Me2Si(Me4C5)(N-t-Bu)ZrCl2 (1,07 g, 0,0026 mol) ble utvunnet. Ytterligere Me2Si(Me4C5)(N-t-Bu )ZrCl2 ble utvunnet fra filtratet ved gjentagelse av omkrystalii-sasjonsmetoden. Totalt utbytte, 1,94 g (0,0047 mol).
Eksempel B
Forbindelse B:
Den samme fremgangsmåten som 1 eksempel A for fremstilling av forbindelse A ble fulgt med unntagelse for buk av HfCl4 Istedenfor ZrCl4 i del 4. Således, når [Me2Si(Me4C5)-(N-t-Bu)]Ll2 (2,13 g, 0,0081 mol) og HfCl4 (2,59 g, 0,0081 mol) ble benyttet, så ble Me2Sl(Me4C5) (N-t-Bu)HfCl2 (0,98 g, 0,0020 mol) fremstilt.
Eksempel C
Forbindelse C:
Del 1. Me2SiCl2 (7,5 ml, 0,062 mol) ble fortynnet med «30 ml THF. En t-BuH4C5Li-oppløsning (7,29 g, 0,056 mol, slOO ml THF) ble langsomt tilsatt og den resulterende blandingen ble omrørt natten over. THF ble fjernet via en vakuum til en felle holdt ved -196°C. Pentan ble tilsatt for å utfelle LiCl og blandingen ble filtrert gjennom Celite. Pentanen ble fjernet fra filtratet
hvilket etterlot en blekgul væske, t-BuH4C5SiMe2Cl (10,4 g, 0,048 mol).
Del 2. Til en THF-oppløsning av LiHN-t-Bu (3,83 g, 0,048 mol,
2:125 ml) ble T-BuH4C5SiMe2Cl (10,4 g, 0,048 mol)
tilsatt dråpevis. Den resulterende oppløsningen ble <;> omrørt natten over. THF ble fjernet via et vakuum til en felle holdt ved -196°C. Pentan ble tilsatt for å utfelle LiCl og blandingen ble filtrert gjennom Celite. Pentanen ble fjernet fra filtratet, hvilket
etterlot en blekgul væske, Me2Si(t-BuH4C5)(NH-t-Bu) ) (11,4 g, 0,045 mol).
Del 3. MeSi(t-BuH4C5)(NH-t-Bu) (11,4 g, 0,045 mol) ble fortynnet med slOO ml Et20. MeLi (1,4 M, 70 ml, 0,098
mol) ble langsomt tilsatt. Blandingen ble omrørt natten over. Eteren ble fjernet via et vakuum til en felle holdt ved -196°C hvilket etterlot et blekgult
faststoff, [Me2Si(t-BuH3C5)(N-t-Bu)]Li2 (11,9 g, 0,045 mol).
Del 4. [Me2Si(t-BuH3C5)(N-t-Bu)]L12 (3,39 g, 0,013 mol) ble suspendert 1 slOO ml Et20. ZrCl4 (3,0 g, 0,013 mol) ble langsomt tilsatt. Blandingen ble omrørt natten over. Eteren ble fjernet og pentan ble tilsatt for å utfelle LiCl. Blandingen ble filtrert gjennom Celite. Pentanoppløsningen ble redusert i volum og det lysebrune faste stoffet ble frafiltrert og vasket flere ganger med små mengder pentan. Produktet med empirisk formel Me2Si(t-BuH3C5)(N-t-Bu)ZrCl2 (2,43 g, 0,0059 mol) ble isolert.
Eksempel D
Forbindelse D:
Samme fremgangsmåte som i eksempel C for fremstilling av forbindelse C ble fulgt med unntagelse for bruk av HfCl4 i del 4. Således, da [Me2Si(t-BuH3C5)(N-t-Bu)]Li2 (3,29 g, 0,012 mol) og HfCl4 (4,0 g, 0,012 mol) ble benyttet, ble produktet med den empiriske formel Me2Si(t-BuH3C5)(N-t-Bu )HfCl2 (1,86 g, 0,037 mol) fremstilt.
Eksempel E
Forbindelse E:
Del 1. Me2SiCl2 (7,0 g, 0,054 mol) ble fortynnet med *100 ml eter. Me3SiC5H4Li (5,9 g, 0,041 mol) ble langsomt tilsatt. Omkring 75 ml THF ble tilsatt og blandingen ble omrørt natten over. Oppløsningsmidlet ble fjernet via et . vakuum til en kald felle holdt ved -196°C. Pentan ble tilsatt for å utfelle LiCl. Blandingen ble filtrert gjennom Celite. Oppløsningsmidlet ble fjernet fra filtratet hvilket ga Me2Si(Me3SiC5H4)C1 (8,1 g, 0,035 mol) som en blekgul væske.
Del 2. Me2Si(Me3SiC5H4)Cl (3,96 g, 0,017 mol) ble fortynnet med x50 ml eter. LiHN-t-Bu (1,36 g, 0,017 mol) ble langsomt tilsatt og blandingen ble omrørt natten over. Eteren ble fjernet via et vakuum og pentan ble tilsatt for å utfelle LiCl. Blandingen ble filtrert gjennom Celite og pentanen ble fjernet fra filtratet. Me2Si(Me3SiC5B:4 )(NH-t-Bu) (3,7 g, 0,014 mol) ble isolert som en blekgul væske.
Del 3. Me2Si(Me3SiC5H4 )(NH-t-Bu) (3,7 g, 0,014 mol) ble fortynnet med eter. MeLi (25 ml, 1,4M i eter, 0,035 mol) ble langsomt tilsatt. Blandingen ble omrørt i 1,5 timer etter den sluttelige tilsetning av MeLi. Eteren ble fjernet via vakuum hvilket ga 4,6 g av et hvitt, fast stoff formulert som Li2[Me2Si(Me3SiC5H3)-(N-t-Bu)]]*34Et20 og uomsatt MeLi som ikke ble fjernet fra det faste stoffet.
Del 4. Li2[Me2Si(Me3SiC5H3)(N-t-Bu)]'3/4Et20 (1,44 g, 0,043
mol) ble suspendert i x50 ml eter. ZrCl4 (1,0 g, 0,0043 mol) ble langsomt tilsatt og reaksjonsblandingen ble omrørt i noen timer. Oppløsningsmidlet ble fjernet via vakuum og pentan ble tilsatt for å utfelle LiCl. Blandingen ble filtrert gjennom Celite og filtratet ble redusert i volum. Kolben ble anbragt i fryseren (-40°C) for å maksimere utfelling av produktet. Det faste stoffet ble frafUtrert hvilket ga 0,273 av et gråhvitt, fast stoff. Filtratet ble igjen redusert i volum, bunnfallet frafiltrert for å oppnå ytterligere 0,345 g for en total mengde på 0,62 g av forbindelsen med empirisk formel Me2Si-(Me3SiCgH3)(N-t-Bu)ZrCl2. Røntgenkrystallstrukturen for dette produktet viser at forbindelsen er dimerisk av natur.
Eksempel F
Forbindelse F:
Del 1. Me4HC5SiMe2Cl ble fremstilt som beskrevet i eksempel A
for fremstilling av forbindelse A, del 1.
Del 2. LiHNPh (4,6 g, 0,0462 mol) ble oppløst i slOO ml THF.
Me4HC5SiMe2Cl (10,0 g, 0,0466 mol) ble langsomt tilsatt. Blandingen ble omrørt natten over. THF ble fjernet via et vakuum. Petroleumeter og toluen ble tilsatt for å utfelle LiCl og blandingen ble filtrert gjennom Celite. Oppløsningsmidlet ble fjernet hvilket etterlot en mørkegul væske, Me2Si(Me4HC5)(NHPh) (10,5 g, 0,0387 mol).
Del 3. Me2Si(Me4HC5)(NHPh) (10,5 g, 0,0387 mol) ble fortynnet med x60 ml eter. MeLi (1,4 M i eter, 56 ml, 0,0784 mol) ble langsomt tilsatt og reaksjonsblandingen ble omrørt natten over. Det resulterende, hvite faste stoff, Li2[Me2Si(Me4C5)(NPh)*3/4Et20 (11,0 g) ble f raf Utrert og vasket med eter.
Del 4. Li2[Me2Si(Me4C5)(NPh)-3/4Et20 (2,81 g, 0,083 mol) ble suspendert i *40 ml eter. ZrCl4 (1,92 g, 0,0082 mol) ble langsomt tilsatt og blandingen ble omrørt natten over. Eteren ble fjernet via et vakuum og en blanding av petroleumeter og toluen ble tilsatt for å utfelle LiCl. Blandingen ble filtrert gjennom Celite, oppløsningsmiddelblandingen ble fjernet via vakuum, og pentan ble tilsatt. Blandingen ble anbragt i fryseren ved —40°C for å maksimere utfelling av produktet. Det faste stoffet ble deretter frafiltrert og vasket med pentan. Me2Si(Me4C5)(NPh)ZrCl2'Et20 ble utvunnet som et blekgult, fast stoff (1,89 g).
Eksempel G
Forbindelse G:
Samme fremgangsmåte som den i eksempel F for fremstilling av forbindelse F ble fulgt med unntagelse for bruk av HfCl4 isteden for ZrCl4 i del 4. Således, da Li2[Me2Si(Me4C5)-(NPh)]'3/4Et20 (2,0 g, 0,0059 mol)og HfCl4 (1,89 g, 0,0059 mol) ble benyttet, så ble Me2Si(Me4C5)(NPh)HfCl2-fcEt20 (,170
g) fremstilt.
"Eksempel
Forbindelse H;
Del 1. MePhSiCl2 (14,9 g, 0,078 mol) ble fortynnet med 2=250
ml THF. Me4C5HLi (10,0 g, 0,078 mol) ble langsomt tilsatt som et fast stoff. Reaksjonsoppløsnlngen ble omrørt natten over. Oppløsningsmidlet ble fjernet via et vakuum til en kald felle holdt ved -196° C. Petroleumeter ble tilsatt for å utfelle LiCl. Blandingen ble filtrert gjennom Celite og pentanen ble fjernet fra filtratet. MePhSi(Me4C5H)Cl (20,8 g, 0,075 mol) ble isolert som en gul, viskøs væske.
Del 2. LiHN-t-Bu (4,28 g, 0,054 mol) ble oppløst i slOO ml THF. MePhSi(Me4C5H)Cl (15,0 g, 0,054 mol) ble tilsatt dråpevis. Den gule oppløsningen ble omrørt natten over. Oppløsningsmidlet ble fjernet via vakuum. Petroleumeter ble tilsatt for å utfelle LiCl. Blandingen ble filtrert gjennom Celite og filtratet ble inndampet. MePhSi(Me4C5H)(NH-t-Bu) (16,6 g, 0,053 mol) ble utvunnet som en ekstremt viskøs væske.
Del 3. MePhSi(Me4C5H)(NH-t-Bu) (16,6 g, 0,053 mol) ble fortynnet med slOO ml eter. MeLi (76 ml, 0,106 mol, 1,4 M) ble langsomt tilsatt og reaksjonsblandingen ble omrørt i £3 timer. Eteren ble redusert i volum og litiumsaltet ble frafiltrert og vasket med pentan hvilket ga 20,0 g av et blekgult, fast stoff formulert som Li2[MePhSi(Me4C5)(N-t-Bu)]-3/4Et20.
Del 4. Li2[MePhSi(Me4C5)(N-t-Bu)]-3/4Et20 (5,0 g, 0,0131 mol)
ble suspendert i xlOO ml Et20. ZrCl4 (3,06 g, 0,0131 mol) ble langsomt tilsatt. Reaksjonsblandingen ble omrørt ved romtemperatur i sl,5 timer og reaksjons-blandingens farve mørknet svakt i løpet av denne tiden. Oppløsningsmidlet ble fjernet via vakuum og en blanding av petroleumeter og toluen ble tilsatt. Blandingen ble filtrert gjennom Celite for å fjerne
LiCl. Filtratet ble inndampet til nesten tørrhet og frafUtrert. Det gråhvite faste stoffet ble vasket med petroleumeter. Utbyttet av produkt, MePhSiCMe^s )-(N-t-Bu)ZrCl2, var 3,82 g (0,0081 mol).
TiTcgftm pftl T
Forbindelse I;
Li2[MePhSi(Me4C5 )(N-t-Bu)]-3/4Et20 ble fremstilt som beskrevet i eksempel H for fremstilling av forbindelse H, del 3.
Del 4. Li2[MePhSi(Me4C5)(N-t-Bu)]*3/4Et20 (5,00 g, 0,0131
mol) ble suspendert i xlOO ml Et20. HfCl4 (4,20 g, 0,0131 mol) ble langsomt tilsatt og reaksjonsblandingen ble omrørt natten over. Oppløsningsmidlet ble fjernet via vakuum og petroleumeter ble tilsatt for å utfelle LiCl. Blandingen ble filtrert gjennom Celite. Filtratet ble inndampet til nesten tørrhet og frafUtrert. Det gråhvite, faste stoffet ble vasket med petroleumeter. MePhSi(Me4C5)(N-t-Bu)HfCl2 ble utvunnet (3,54 g, 0,0058 mol).
Eksempel J
Forbindelse J:
MePhSi(Me4C5)(N-t-Bu)HfMe2 ble fremstilt ved tilsetning av en støkiometrisk mengde av MeLi (1,4 M i eter) til MePhSi-(Me4C5)(N-t-Bu)EfCl2 suspendert i eter. Det hvite, faste stoffet kunne isoleres i et nesten kvantitativt utbytte.
Eksempel K
Forbindelse K:
Del 1. Me4C5SiMe2Cl ble fremstilt som beskrevet i eksempel A
for fremstilling av forbindelse A, del 1.
Del 2. Me4C5SiMe2Cl (10,0 g, 0,047 mol) ble fortynnet med x25
ml Et20. LiHNC5H4-p-n-Bu-l/10Et20 (7,57 g, 0,047 mol) ble langsomt tilsatt. Blandingen ble omrørt i ~3
timer. Oppløsningsmidlet ble fjernet via vakuum. Petroleumeter ble tilsatt for å utfelle LiCl, og blandingen ble filtrert gjennom Celite. Oppløsnings-midlet ble fjernet hvilket etterlot en oransjefarvet, viskøs væske, Me2Si(Me4C5H)(HNC6H4-p-n-Bu) (12,7 g, 0,039 mol).
Del 3. Me2Si(Me4C5H((HNC6H4-p-n-Bu) (12,7 g, 0,039 mol) ble fortynnet med 350 ml Et20. MeLi (1,4 M, 55 ml, 0,077 mol) ble langsomt tilsatt. Blandingen ble omrørt i 3:3 timer. Produktet ble f raf Utrert og vasket med Et20 hvilket ga Li2[Me2Si(Me4C5)(NC^B^-p-n-Bu)[•3/4Et20 som et hvitt, fast stoff (13,1 g, 0,033 mol).
Del 4. Li2[Me2Si(Me4C5)(NC6H4-p-n-Bu)]'3/4Et20 (3,45 g,
0,0087 mol) ble suspendert i s:50 ml Et20. ZrCl4 (2,0 g, 0,0086 mol) ble langsomt tilsatt og blandingen ble omrørt natten over. Eteren ble fjernet via vakuum og petroleumeter ble tilsatt for å utfelle LiCl. Blandingen ble filtrert gjennom Celite. Filtratet ble inndampet til tørrhet til oppnåelse av et gult, fast stoff som ble omkrystallisert fra pentan og identifisert som Me2Si(Me4C5)(NC6H4-p-n-Bu)ZrCl2'2/3Et20 (4,2
g)<.>
Eksempel L
Forbindelse L:
Li2[Me2Si(Me4C5)(NCcfH4-p-n-Bu)]'3/4Et20 ble fremstilt som
beskrevet i eksempel K for fremstilling av forbindelse K, del i 3.
Del 4. Li2[Me2Si(Me4C5)(NC6H4-p-n-Bu)]'3/4Et20 (3,77 g,
0,0095 mol) ble suspendert i 3:50 ml Et20. HfCl4 (3,0
g, 0,0094 mol) ble langsomt tilsatt som et fast stoff og blandingen ble omrørt natten over. Eteren ble fjernet via vakuum og petroleumeter ble tilsatt for å utfelle LiCl. Blandingen ble filtrert gjennom Celite.
Petroleumeter ble fjernet via et vakuum til oppnåelse av et gråhvitt, fast stoff som ble omkrystallisert fra pentan. Produktet ble identifisert som MegSiCMe^s )-(NC6H4-p-n-Bu)HfCl2 (1,54 g, 0,0027 mol).

Claims (5)

1. Metllocenforbindelse, karakterisert ved at den har den generelle formel: hvor: M og M' er Zr, Hf eller Tl; (C5H4_XRX) er en cyklopentadienylring som er substituert med fra 0 til 4 grupper R, "x" er 0, 1, 2, 3 eller 4 som betegner substitusjonsgraden, og hver substituentgruppe R er uavhengig et radikal valgt fra Ci-Cgo-hydrokarbylradikaler, substituerte Cj-Cgo-hydrokarbylradikaler hvor ett eller flere hydrogenatomer er erstattet med et halogenatom, Ci-C20~ hydrokarbylsubstituerte metalloidradikaler hvor metalloidet er valgt fra gruppe IVA i det periodiske system, og halogen-radikaler, eller (C5H4_XRX) er en cyklopentadienylring hvori to tilstøtende R-grupper er sammenføyet fra en C4-C2o_ring_ struktur slik at det oppnås en mettet eller umettet polycyklisk cyklopentadienylligand; (JR'Z_2) er en heteroatomllgand hvor J er et element med koordinasjonstall 3 fra gruppe VA eller et element med koordinasjonstall 2 fra gruppe VIA i det periodiske system, og hver R' er uavhengig et radikal valgt fra Cj-Cgn-bydro-karbylradikaler, substituerte Cj-Cgo-hydrokarbylradikaler hvor ett eller flere hydrogenatomer er erstattet med et halogenatom, og "z" er koordinasjonstallet til elementet J; hver Q er uavhengig en hvilken som helst enverdig, anionisk ligand eller to Q'er er et toverdig, anionisk chelaterings-mlddel; B er en kovalent brodannende gruppe inneholdende et element fra gruppe IVA eller VA i det periodiske system, valgt fra dialkyl-, alkyl-, aryl- eller diarylsilisium- eller —germanlumradikal, eller fenylamido, t-butylamido, metylamido, t-butylfosfido, etylfosfido, fenylfosfido, metylen, dimetylmetylen, dietylmetylen, etylen, dimetyletylen, dietyletylen, dipropyletylen; og L er en Lewis-base hvor "w" betegner et tall fra 0 til 3, men unntatt forbindelser av den generelle formel: hvor M har den ovenfor angitte betydning, (C5H4_X»R<2>X») er en cyklopentadienylring som er substituert med fra 0 til 4 R<2->grupper, x' er 1, 2, 3 eller 4, og hvor R<2> og de i gruppene Si(R<2>)2 og YR<2> er uavhengig valgt fra hydrogen, silyl, alkyl, aryl og kombinasjoner derav med opptil 10 karbon-at ome r , Q' er uavhengig valgt fra halogen, alkyl, aryl, fenoksy, alkoksy med opptil 10 karbonatomer eller -NR<2> hvor R<2> har den ovenfor angitte betydning, idet n er 1 eller 2 avhengig av valensen til M, og Y er nitrogen eller fosfor.
2. Forbindelse ifølge krav 1, karakterisert ved at heteroatomet i liganden JR'Z_2 er nitrogen, fosfor, oksygen eller svovel.
3. Forbindelse ifølge krav 1 eller 2, karakterisert ved atM og/eller M' er zirkonium eller hafnium.
4. Forbindelse ifølge hvilket som helst av kravene 1-3, karakterisert ved at Q er et hydrid-, halogen- eller hydrokarbylradikal forskjellig fra en cyklisk cyklopentadienylgruppe.
5. Forbindelse ifølge krav 4, karakterisert ved at Q er substituert eller usubstituert Ci-Cgo-hydrokarbyl, alkoksyd, aryloksyd, amid, arylamid, fosfid eller arylfosfid, forutsatt at når en hvilken som helst av Q er en hydrokarbylgruppe, så er en slik Q-gruppe forskjellig fra (C5E\4_XRX), eller begge er sammen en alkylidengruppe eller en hydrokarbylmetallocykelgruppe.
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WO1993021242A1 (en) * 1992-04-20 1993-10-28 Exxon Chemical Patents Inc. Ethylene/branched olefin copolymers
US5955625A (en) * 1995-01-31 1999-09-21 Exxon Chemical Patents Inc Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts
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AU643237B2 (en) 1993-11-11
HU905878D0 (en) 1991-03-28
DK0420436T3 (da) 1996-12-02
AU6443990A (en) 1991-04-18
KR920702365A (ko) 1992-09-03
EP0662484A2 (en) 1995-07-12
EP0491842A1 (en) 1992-07-01
FI904506A0 (fi) 1990-09-12
HU214667B (hu) 1998-04-28
DE420436T1 (de) 1996-02-15
DE69030442D1 (de) 1997-05-15
EP0643066A3 (en) 2004-01-07
NO178895C (no) 1996-06-26
KR910006335A (ko) 1991-04-29
FI113538B (fi) 2004-05-14
NZ235095A (en) 1992-01-29
NO178895B (no) 1996-03-18
JPH03188092A (ja) 1991-08-16
BR9004537A (pt) 1991-09-10
GR3034632T3 (en) 2001-01-31
KR100190735B1 (ko) 1999-06-01
PT95272A (pt) 1991-05-22
BR9007642A (pt) 1992-07-21
AR244355A1 (es) 1993-10-29
DE69028057T3 (de) 2001-01-25
NO920971D0 (no) 1992-03-12
JP2994746B2 (ja) 1999-12-27
ES2079332T1 (es) 1996-01-16
DE69028057D1 (de) 1996-09-19
GR3021539T3 (en) 1997-02-28
EP0420436A1 (en) 1991-04-03
US20060178491A1 (en) 2006-08-10
AU6248390A (en) 1991-03-21
ATE141275T1 (de) 1996-08-15
DE662484T1 (de) 1996-06-27
DK0491842T3 (da) 1997-10-27
CA2024899A1 (en) 1991-03-14
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IL95549A0 (en) 1991-06-30
NO178891C (no) 1996-06-26
CA2065745A1 (en) 1991-03-14
PT95272B (pt) 2001-06-29
DE69028057T2 (de) 1997-01-16
NO903928L (no) 1991-03-14
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US7205364B1 (en) 2007-04-17
HUT55791A (en) 1991-06-28
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