DE10102647A1 - Catalysts used for the polymerisation of cyclo-olefin compounds, especially norbornene containing a nickel-phosphoraniminato complex and a borane or borate, - Google Patents
Catalysts used for the polymerisation of cyclo-olefin compounds, especially norbornene containing a nickel-phosphoraniminato complex and a borane or borate,Info
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
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- 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
- C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F132/08—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
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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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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Abstract
Description
Die Erfindung betrifft einen Katalysator, enthaltend
The invention relates to a catalyst containing
-
a) einen Nickel-phosphoraniminato Komplex der Formel [NiX(NPR3]4
wobei
X ein kovalent gebundener oder schwach koordinierender Li gand,
R unabhängig voneinander ein C1-C20 Alkyl, C6-C20 Aralkyl oder ein C1-C20 Alkyl-phospha-cyclopentanyl bedeuten unda) a nickel-phosphoraniminato complex of the formula [NiX (NPR 3 ] 4 wherein
X is a covalently bound or weakly coordinating ligand,
R independently of one another are a C 1 -C 20 alkyl, C 6 -C 20 aralkyl or a C 1 -C 20 alkylphosphacyclopentanyl and - b) ein Boran oder Borat,b) a borane or borate,
sowie ein Verfahren zur Polymerisation von Cycloolefinen.and a process for the polymerization of cycloolefins.
Die Polymerisation von Norbornen führt je nach Katalysator und Reaktionsmechanismus zu unterschiedlichen Polymeren. Eine Viel zahl von Übergangsmetallverbindungen katalysiert die ringöffnende Methathesepolymerisation (ROMP). Das so hergestellt Polynorbornen enthält ungesättigte C=C-Doppelbindungen in der Polymerkette und besitzt eine niedere Glasübergangstemperatur. Es wird als typi sches Elastomer verwendet.The polymerization of norbornene leads depending on the catalyst and Reaction mechanism to different polymers. A lot The number of transition metal compounds catalyzes the ring-opening Methathesis polymerization (ROMP). The polynorbornene manufactured in this way contains unsaturated C = C double bonds in the polymer chain and has a low glass transition temperature. It is considered typi cal elastomer used.
Die durch Dichlorethylaluminium initiierte kationische Polymeri sation von Norbornen führt zu 2,7-verknüpften Polynorbornen mit niederem Molekulargewicht.The cationic polymer initiated by dichloroethyl aluminum norbornene leads to 2,7-linked polynorbornene low molecular weight.
Im Gegensatz zur ringöffnenden Methathesepolymerisation (ROMP) werden bei der vinylischen Polymerisation Polymere ohne ungesät tigte C=C-Doppelbindungen und mit besseren thermischen Eigen schaften erhalten. Als Katalysatoren sind Komplexe des Nickels (EP-A 0445755, US 5,468,819), des Kobalts, Chrom, Zirkonium oder Palladium bekannt. Im allgemeinen werden diese Metallkomplexe durch Methylaluminoxan (MAO) aktiviert. Je nach verwendetem Kata lysator können semikristalline und unlöslich Polymere erhalten werden.In contrast to ring-opening methathesis polymerization (ROMP) are polymers without vinyl in the vinyl polymerization C = C double bonds and with better thermal properties preserved. Complexes of nickel are used as catalysts (EP-A 0445755, US 5,468,819), cobalt, chromium, zirconium or Palladium known. Generally, these metal complexes activated by methylaluminoxane (MAO). Depending on the kata used Analyzers can obtain semi-crystalline and insoluble polymers become.
In Chlorbenzol bei Raumtemperatur lösliches vinylisches Polynor bornen wird in Makromol. Rapid Commun. 20, Seiten 232-235 (1999) beschrieben. Als Katalysator wird ein Nickelphosphoranimi natokomplex/MAO verwendet. Aufgrund der hohen Lewisacidität des MAO sind nachfolgende Umsetzungen mit Verbindungen, die polare Gruppen enthalten, nicht möglich.Vinylic polynor soluble in chlorobenzene at room temperature will be born in Makromol. Rapid Commun. 20, pages 232-235 (1999). A nickel phosphoranimi is used as the catalyst natokomplex / MAO used. Due to the high Lewis acidity of the MAO are subsequent reactions with compounds that are polar Groups included, not possible.
Die WO 96/37529 beschreibt ein Verfahren zur Herstellung von Co polymeren aus Norbornen und kationisch polymerisierbaren Monome ren wie Ethylvinylether, Butadien, Isobuten oder Vinylanisol. Die Polymerisation erfolgt in Gegenwart eines Multikomponenten Kata lysatorsystems, das ein Übergangsmetallion der Gruppe 8 enthält. Unter anderem wird ein Katalysatorsystem aus Nickelethylhexanoat, Trispentafluorphenylboran und Triethylaluminium verwendet.WO 96/37529 describes a method for producing Co polymers from norbornene and cationically polymerizable monomers ren such as ethyl vinyl ether, butadiene, isobutene or vinyl anisole. The Polymerization takes place in the presence of a multicomponent kata analyzer system containing a Group 8 transition metal ion. Among other things, a catalyst system made of nickel ethyl hexanoate, Trispentafluorophenylborane and Triethylaluminium used.
Die Aufgabe der vorliegenden Erfindung war es, den genannten Nachteilen abzuhelfen und einen Katalysator zur Verfügung zu stellen, der die Polymerisation von Cycloolefinen zu Polycycloo lefinen mit hohem Molekulargewicht und enger Molekulargewichts verteilung ermöglicht. Desweiteren sollte der Katalysator keine Komponenten enthalten, die die anschließende Umsetzung mit Ver bindungen mit polaren Gruppen stören. Eine weitere Aufgabe ist die Herstellung von Blockcopolymeren oder Pfropfcopolymeren, die einen Polycycloolefinblock enthalten.The object of the present invention was the above To remedy disadvantages and a catalyst available make the polymerization of cycloolefins to polycycloo high molecular weight, narrow molecular weight lefins distribution enables. Furthermore, the catalyst should not Contain components that the subsequent implementation with Ver disrupt bonds with polar groups. Another job is the production of block copolymers or graft copolymers which contain a polycycloolefin block.
Hierfür eignet sich ein Katalysator gemäß Anspruch 1.A catalyst according to claim 1 is suitable for this.
Der Katalysator enthält einen Nickelphosphoraniminatokomplex der Formel [NiX(NPR3)]4. X steht für ein kovalent gebundenen oder schwach koordinierenden Liganden. Beispiele hierfür sind die Ha logenide wie Fluorid, Chlorid, Bromid, Jodid, Triodid, Rhodanid, Cyanid, Bortetrafluoridanion, Oxohalogenide wie Perchlorat, Car boxylate, Formiate, Acetate, Trifluoracetate, Benzoate, Triflate, sowie Alkyloxy- bzw. Aryloxy-, Thio-, Selenato- oder Teluratoli ganden mit einem C1- bis C20-Alkyl oder C6- bis C20-Aryl, wie Phe nyl, Diphenyl oder Naphthyl.The catalyst contains a nickel phosphoraniminato complex of the formula [NiX (NPR 3 )] 4 . X stands for a covalently bound or weakly coordinating ligand. Examples of these are the halides, such as fluoride, chloride, bromide, iodide, triodide, rhodanide, cyanide, boron tetrafluoride anion, oxohalides, such as perchlorate, car boxylates, formates, acetates, trifluoroacetates, benzoates, triflates, and also alkyloxy- or aryloxy-, thio- , Selenato- or Teluratoli existed with a C 1 - to C 20 -alkyl or C 6 - to C 20 -aryl, such as phenyl, diphenyl or naphthyl.
Die an Phosphor gebundenen Reste R können unabhängig voneinander C1- bis C20-Alkyl, C6- bis C20-Aralkyl oder C1- bis C20-Alkylphos phacyclopentanyl sein.The radicals R bonded to phosphorus can be, independently of one another, C 1 to C 20 alkyl, C 6 to C 20 aralkyl or C 1 to C 20 alkylphos phacyclopentanyl.
Der Katalysator enthält ferner ein Boran oder Borat. Bevorzugt werden Trisperfluorarylborane wie Tris(pentafluorphenyl)boran verwendet. Geeignet sind auch Alkyl- oder Arylborate wie Triphe nylmethyliumtetra(phenyl)boran.The catalyst also contains a borane or borate. Prefers become trisperfluoroarylboranes such as tris (pentafluorophenyl) borane used. Alkyl or aryl borates such as triphe are also suitable nylmethyliumtetra (phenyl) borane.
Desweiteren kann der Katalysator in zumeist untergeordneten Men gen ein Aluminiumalkyl, beispielsweise Trimethylaluminium oder Triethylaluminium enthalten. Furthermore, the catalyst can be found in mostly subordinate menus an aluminum alkyl, for example trimethylaluminum or Triethyl aluminum included.
Bevorzugt liegt das molare Verhältnis Bor/Nickel im Bereich von 1 bis 10, besonders bevorzugt im Bereich von 2 bis 5. Das molare Verhältnis von Aluminium zu Nickel liegt im allgemeinen im Be reich von 0 bis 1, bevorzugt im Bereich von 0,02 bis 0,2.The molar boron / nickel ratio is preferably in the range of 1 to 10, particularly preferably in the range from 2 to 5. The molar The ratio of aluminum to nickel is generally in the range ranges from 0 to 1, preferably in the range from 0.02 to 0.2.
Das erfindungsgemäße Verfahren zur Polymerisation von Cycloolefi nen wird in Gegenwart des oben beschriebenen Katalysators durch geführt. Das Verfahren kann prinzipiell lösungsmittelfrei durch geführt werden. Bevorzugt wird die Polymerisation in einem aroma tischen Kohlenwasserstoff, beispielsweise Toluol oder Chlorben zol, als Lösungsmittel durchgeführt.The inventive method for the polymerization of cycloolefi NEN is in the presence of the catalyst described above guided. The process can in principle be solvent-free be performed. Polymerization in an aroma is preferred table hydrocarbon, for example toluene or chlorobene zol, carried out as a solvent.
Besonders eignet sich das Verfahren zur Polymerisation von Nor bornen oder Norbornenderivaten, zum Beispiel 5-Methyl-2-Norbor nen, 5-Hexyl-2-norbornen, 5-Ethylidenyl-2-norbornen, Vinylnorbor nen, Dicyclopentadien, Dihydrodicyclopentadien, Tetracyclodode cen, Tetracyclododecadien, Dimethyltetracyclododecen, Ethyltetra cyclododecen, Ethyltetracyclododecen, Ethylidenyltetracyclodode cen, Phenyltetracyclodecen und halogenierte Norbornadiene sowie Norbornadiene mit vollständig halogenierten Alkylgruppen.The process is particularly suitable for the polymerization of Nor boron or norbornene derivatives, for example 5-methyl-2-norbor nen, 5-hexyl-2-norbornene, 5-ethylidenyl-2-norbornene, vinyl norbor nen, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclodode cen, tetracyclododecadiene, dimethyltetracyclododecene, ethyltetra cyclododecene, ethyl tetracyclododecene, ethylidenyl tetracyclodode cen, phenyltetracyclodecene and halogenated norbornadienes and Norbornadienes with fully halogenated alkyl groups.
Der Katalysator wird in der Regel in Mengen eingesetzt, so daß das molare Verhältnis von Cycloolefin zu Nickel im Bereich von 100 bis 100000 liegt.The catalyst is generally used in amounts so that the molar ratio of cycloolefin to nickel in the range of 100 to 100,000.
Die Polymerisation wird in der Regel bei Temperaturen im Bereich von 0 bis 100°C und Drücken im Bereich von 1 bar bis 10 bar durch geführt.The polymerization is usually at temperatures in the range from 0 to 100 ° C and pressures in the range from 1 bar to 10 bar guided.
Die Polymerisation kann mit
The polymerization can be carried out with
- a) einem polaren Kettenabbruchmittel odera) a polar chain terminator or
- b) einem vinylischen Monomer oderb) a vinyl monomer or
- c) einem C=C-Doppelbindungen enthaltenen Polymeren beendet wer den.c) a polymer containing C = C double bonds is terminated the.
Durch die Beendigung der Polymerisation mit einem Alkohol, wie Methanol oder Ethanol, Wasser oder organischen oder anorganischen Säuren können Polycycloolefine mit einer Glasübergangstemperatur von 100°C oder höher, insbesondere von 200°C oder höher bei einem gewichtsmittleren Molekulargewicht MW im Bereich von 50.000 bis 2.000.000, insbesondere im Bereich von 500.000 bis 1.000.000 und einer Uneinheitlichkeit MW/Mn von 1,3, insbesondere 1,2 oder da runter erhalten werden. By terminating the polymerization with an alcohol such as methanol or ethanol, water or organic or inorganic acids, polycycloolefins with a glass transition temperature of 100 ° C or higher, in particular of 200 ° C or higher with a weight average molecular weight M W in the range from 50,000 to 2,000,000, in particular in the range from 500,000 to 1,000,000 and a non-uniformity M W / M n of 1.3, in particular 1.2 or below, can be obtained.
Durch Zugabe eines vinylischen Monomeren, beispielsweise Styrol kann ein funktionalisiertes Polynorbornen erhalten werden. Das Molekulargewicht kann durch die Zeit, nach der Styrol zugegeben wird, kontrolliert werden. Durch die Zugabe von Polymeren, die C=C-Doppelbindungen enthalten, können neue Polynorbornenblock- bzw. Pfropfcopolymere erhalten werden. So ergeben beispielsweise an einem der beiden Enden mit Vinyl- oder Allylgruppen funktiona lisierte Oligomere oder Polymere beispielsweise des Polystyrols, Polysiloxan oder Polyalkylenoxid Blockcopolymere des Typs AB bzw. ABA.By adding a vinyl monomer, for example styrene a functionalized polynorbornene can be obtained. The Molecular weight can be increased by the time after which styrene is added will be controlled. By adding polymers that C = C double bonds, new polynorbornene block or graft copolymers can be obtained. For example functional at one of the two ends with vinyl or allyl groups lized oligomers or polymers of, for example, polystyrene, Polysiloxane or polyalkylene oxide block copolymers of type AB or ABA.
Durch Umsetzung mit Polymeren, die mehrere C=C-Doppelbindungen enthalten, z. B. Polybutadien, Polyisopren oder durch ringöffnende Methatese-Polymerisation erhaltenes Polynorbornen, erhält man Pfropfcopolymere.By reaction with polymers that have multiple C = C double bonds included, e.g. B. polybutadiene, polyisoprene or ring-opening Polynorbornene obtained from methate polymerization is obtained Graft copolymers.
Bevorzugt enthalten die Block- bzw. Pfropfcopolymere einen Anteil des Polycyclolefinblockes von 25 bis 75 mol-%, bezogen auf das gesamte Block- bzw. Pfropfcopolymer.The block or graft copolymers preferably contain a proportion of the polycyclolefin block from 25 to 75 mol%, based on the entire block or graft copolymer.
[NiBr(NPMe3)]4 wurde wie in Krieger et al., Z. anorg. allg. Chem. 1998, 624 Seite 781 beschrieben, hergestellt.[NiBr (NPMe 3 )] 4 was as described in Krieger et al., Z. anorg. allg. Chem. 1998, 624 page 781.
Poly(ethylenglycol)monomethacrylat (M = 300 g/mol, Dichte 1,050 g/cm3)Poly (ethylene glycol) monomethacrylate (M = 300 g / mol, density 1.050 g / cm 3 )
Allyl-terminiertes Polystyrol wurde durch Terminierung von anio nisch initiiertem Polystyrol mit Allylbromid erhalten (M = 10.000 g/mol).Allyl-terminated polystyrene was terminated by anio nisch initiated polystyrene with allyl bromide (M = 10,000 g / mol).
In einem im Vakuum ausgeheizten und mit Argon befüllten 100 ml- Stickstoffrundkolben wurde ein Gemisch aus 0,5 mg [NiBr(NPMe3)]4 (2 µmol Ni, M = 914.71 g/mol) und 1,8 g Norbornen (M = 94,16 g/mol, 19 mmol, 3 ml einer 80 Gew.-% Lösung in Toluol) vor gelegt. Zum Starten der Polymerisation wurden 5,0 mg Perfluortri phenylboran (10 µmol, M = 511,99 g/mol, gelöst in 10 ml Toluol) schnell zugegeben. Nachdem 15 min mit einem Magnetstab gerührt worden war, wurde das Reaktionsgemisch in 200 ml angesäuertes Me thanol (Methanol: HClconc. = 200 : 1) eingegossen. Das ausgefallene Polymer wurde abfiltriert, mit wenig Methanol gewaschen und bei 90°C zwei Tage im Membranpumpenvakuum getrocknet.A mixture of 0.5 mg of [NiBr (NPMe 3 )] 4 (2 μmol of Ni, M = 914.71 g / mol) and 1.8 g of norbornene (M = 94.16 g / mol, 19 mmol, 3 ml of an 80 wt .-% solution in toluene) before. To start the polymerization, 5.0 mg of perfluorotriphenylborane (10 μmol, M = 511.99 g / mol, dissolved in 10 ml of toluene) were added quickly. After stirring with a magnetic rod for 15 min, the reaction mixture was poured into 200 ml of acidified methanol (methanol: HCl conc. = 200: 1). The precipitated polymer was filtered off, washed with a little methanol and dried at 90 ° C. in a membrane pump vacuum for two days.
In einem im Vakuum ausgeheizten und mit Argon befüllten 100 ml- Stickstoffrundkolben wurde ein Gemisch aus 0,5 mg (NiBr(NPMe3)]4 (2 µmol Ni, M = 914,71 g/mol) und 1,8 g Norbornen (19 mmol, M = 94,16 g/mol) vorgelegt. Zum Starten der Polymerisation wurden 0,5 mg Perfluortriphenylboran (10 µmol, M = 511,99 g/mol, gelöst in 7 ml Toluol) schnell zugegeben. Nachdem 7 min mit einem Magnetstab gerührt worden war, wurden 2,9 g (10 mmol, M = 300 g/mol, 3,0 ml) Polyethylenglykolmonomethylmethacrylat zu dem viskosen Reaktionsgemisch zugegeben, wobei augenblicklich ein farbloser Feststoff ausfiel. Zur Vervollständigung der Reaktion wurde weitere 8 min gerührt und das Reaktionsgemisch anschließend in 200 ml angesäuertem Methanol (Methanol : HCl = 200 : 1) ausge fällt. Der Feststoff wurde abfiltriert, mit wenig Methanol gewa schen und 2 Tage bei 60°C im Membranpumpenvakuum getrocknet.A mixture of 0.5 mg (NiBr (NPMe 3 )] 4 (2 µmol Ni, M = 914.71 g / mol) and 1.8 g norbornene (in a 100 ml nitrogen round-bottom flask heated in vacuo and filled with argon) 19 mmol, M = 94.16 g / mol) and 0.5 mg perfluorotriphenylborane (10 µmol, M = 511.99 g / mol, dissolved in 7 ml toluene) were added quickly to start the polymerization 2.9 g (10 mmol, M = 300 g / mol, 3.0 ml) of polyethylene glycol monomethyl methacrylate was added to the viscous reaction mixture, a colorless solid instantaneously precipitating out, and stirring was continued for a further 8 min to complete the reaction and the reaction mixture was then precipitated in 200 ml of acidified methanol (methanol: HCl = 200: 1) The solid was filtered off, washed with a little methanol and dried for 2 days at 60 ° C. in a membrane pump vacuum.
In einem im Vakuum ausgeheizten und mit Argon befüllten 100 ml- Stickstoffrundkolben wurde ein Gemisch aus 0,5 mg [NiBr(NPMe3)]4 (2 µmol Ni, M = 914,71 g/mol) und 1,8 g Norbornen (19 mmol, M = 94,16 g/mol) vorgelegt. Zum Starten der Polymerisation wurden 5,0 mg Perfluortriphenylboran (10 µmol, M = 511,99 g/mol, gelöst in 7 ml Toluol) schnell zugegeben. Nachdem 7 min mit einem Ma gnetstab gerührt worden war, wurden 3 g eines allylterminierten PS (M = 10000, gelöst in Chloroform) zugegeben und weitere 8 min gerührt. Das Reaktionsgemisch wurde anschließend in angesäuertes Methanol (Methanol : HCl = 200 : 1) eingegossen, der Feststoff abfiltriert und zwei Tage im Membranpumpenvakuum getrocknet. Zur Abtrennung des überschüssigen PS wurde das Produkt dreimal mit je 15 ml Chloroform extrahiert (über Nacht) und nach Umfällen aus Chlorbenzol 2 Tage bei 60°C im Membranpumpenvakuum getrocknet.A mixture of 0.5 mg [NiBr (NPMe 3 )] 4 (2 µmol Ni, M = 914.71 g / mol) and 1.8 g norbornene (in a 100 ml nitrogen round-bottom flask heated in vacuo and filled with argon) 19 mmol, M = 94.16 g / mol) submitted. To start the polymerization, 5.0 mg of perfluorotriphenylborane (10 μmol, M = 511.99 g / mol, dissolved in 7 ml of toluene) were added quickly. After stirring for 7 min with a magnetic rod, 3 g of an allyl-terminated PS (M = 10,000, dissolved in chloroform) were added and stirring was continued for 8 min. The reaction mixture was then poured into acidified methanol (methanol: HCl = 200: 1), the solid was filtered off and dried in a membrane pump vacuum for two days. To remove the excess PS, the product was extracted three times with 15 ml of chloroform (overnight) and, after reprecipitation from chlorobenzene, dried for 2 days at 60 ° C. in a membrane pump vacuum.
Analog Beispiel 1 wurde mit unterschiedlichen Ni : Norbornen Ver hältnissen polymerisiert. Die Konzentration von Ni und B, bezogen auf den Reaktionsansatz wurden konstant gehalten. Analogously to Example 1, different Ni: Norbornen Ver conditions polymerized. The concentration of Ni and B related on the reaction batch were kept constant.
Es wurde analog Beispiel 1 polymerisiert und anstelle von Metha nol mit Styrol abgebrochen.It was polymerized analogously to Example 1 and instead of metha nol broken off with styrene.
Beispiel 2 wurde mit Polyethylenglycolmonomethylacrylat mit un terschiedlichem Molekulargewicht wiederholt.Example 2 was with polyethylene glycol monomethyl acrylate with un repeated molecular weight repeated.
Claims (15)
- a) einen Nickel-phosphoraniminato Komplex der Formel
[NiX(NPR3)]4 wobei
X ein kovalent gebundener oder schwach koordinierender Ligand,
R unabhängig voneinander ein C1-C20 Alkyl, C6-C20 Aral kyl oder ein C1-C20 Alkyl-phospha-cyclopentanyl bedeuten und - b) ein Boran oder Borat.
- a) a nickel-phosphoraniminato complex of the formula [NiX (NPR 3 )] 4 being
X is a covalently bound or weakly coordinating ligand,
R independently of one another are a C 1 -C 20 alkyl, C 6 -C 20 aralkyl or a C 1 -C 20 alkylphosphacyclopentanyl and - b) a borane or borate.
- a) [NiBr(NP(CH3)3]4
- b) Tris(perfluoraryl)boran
- c) Aluminiumtrialkyl
- a) [NiBr (NP (CH 3 ) 3 ] 4
- b) Tris (perfluoroaryl) borane
- c) aluminum trialkyl
- a) einem polaren Kettenabbruchmittel oder
- b) einem vinylischen Monomer oder
- c) einem C=C-Doppelbindungen enthaltenden Polymeren beendet.
- a) a polar chain terminator or
- b) a vinyl monomer or
- c) a polymer containing C = C double bonds terminated.
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DE10102647A DE10102647A1 (en) | 2001-01-20 | 2001-01-20 | Catalysts used for the polymerisation of cyclo-olefin compounds, especially norbornene containing a nickel-phosphoraniminato complex and a borane or borate, |
PCT/EP2002/000498 WO2002057330A1 (en) | 2001-01-20 | 2002-01-19 | Nickel catalyst for the polymerisation of norbornene |
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DE10102647A DE10102647A1 (en) | 2001-01-20 | 2001-01-20 | Catalysts used for the polymerisation of cyclo-olefin compounds, especially norbornene containing a nickel-phosphoraniminato complex and a borane or borate, |
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US5468819A (en) * | 1993-11-16 | 1995-11-21 | The B.F. Goodrich Company | Process for making polymers containing a norbornene repeating unit by addition polymerization using an organo (nickel or palladium) complex |
US5677405A (en) * | 1995-05-24 | 1997-10-14 | The B.F. Goodrich Company | Homopolymers and copolymers of cationically polymerizable monomers and method of their preparation |
-
2001
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