DE2608863A1 - Ethylene polymerisation using Ziegler catalyst system - contg. bis-cyclopentadienyl-titanium di-alkyl cpd., aluminium tri-alkyl cpd. and water - Google Patents
Ethylene polymerisation using Ziegler catalyst system - contg. bis-cyclopentadienyl-titanium di-alkyl cpd., aluminium tri-alkyl cpd. and waterInfo
- Publication number
- DE2608863A1 DE2608863A1 DE19762608863 DE2608863A DE2608863A1 DE 2608863 A1 DE2608863 A1 DE 2608863A1 DE 19762608863 DE19762608863 DE 19762608863 DE 2608863 A DE2608863 A DE 2608863A DE 2608863 A1 DE2608863 A1 DE 2608863A1
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- titanium
- bis
- cyclopentadienyl
- water
- catalyst system
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
Abstract
Description
Verfahren zum Herstellen von PolyäthylenProcess for the manufacture of polyethylene
Die vorliegende Erfindung betrifft ein Verfahren zum Herstellen von Polyäthylen durch Polymerisation von Äthylen bei Temperaturen im Bereich von -80 bis 1200C mittels eines Ziegler-Katalysatorsystems aus (1) einer Titan enthaltenden Verbindung sowie (2) einer Aluminium enthaltenden Verbindung.The present invention relates to a method of making Polyethylene by polymerization of ethylene at temperatures in the range of -80 up to 1200C by means of a Ziegler catalyst system composed of (1) one containing titanium Compound and (2) an aluminum-containing compound.
Solche Verfahren sind in etlichen Varianten bekannt, wobei jeweils die eingesetzte Titan enthaltende Verbindung (1) von besonderer chemischer und/oder chemisch-physikalischer Art ist.Such methods are known in a number of variants, in each case the used titanium-containing compound (1) of particular chemical and / or is of a chemical-physical nature.
Die Modifikationen in der Art der Titan enthaltenden Verbindung (1) werden vorgenommen, um bestimmte Ziele zu erreichen, z.B. die folgenden: (a) Katalysatorsysteme, die eine erhöhte Ausbeute an Polymerisat zu liefern vermögen, nämlich (a1) Katalysatorsysteme mit einer erhöhten Produktivität, d.h, Systeme, bei denen die Menge an gebildetem Polymerisat pro Gewichtseinheit Titan enthaltender Verbindungen (1) erhöht ist bzw.The modifications in kind of the titanium-containing compound (1) are made to achieve specific goals, such as the following: (a) catalyst systems, capable of delivering an increased yield of polymer, namely (a1) catalyst systems with increased productivity, i.e. systems in which the amount of Polymer per unit weight of titanium-containing compounds (1) is increased or
(a2) Katalysatorsysteme mit einer erhöhten Aktivität, d.h. Systeme, bei denen die Menge an gebildetem Polymerisat pro Gewichtseinheit Titan enthaltender Verbindung (1) und pro Zeiteinheit erhöht ist. (a2) catalyst systems with an increased activity, i.e. systems, in which the amount of polymer formed per unit weight of titanium containing Connection (1) and per unit of time is increased.
(b) Katalysatorsysteme, durch die weniger bzw. kein Halogen in das Polymerisat eingebracht wird; - was zu erreichen ist, indem (b1) die Ausbeute gemäß (a) gesteigert wird und/oder (b2) Titan enthaltende Verbindungen (1) eingesetzt werden, die möglichst wenig bzw. kein Halogen enthalten.(b) Catalyst systems, through which less or no halogen in the Polymer is introduced; - What can be achieved by (b1) the yield according to (a) is increased and / or (b2) titanium-containing compounds (1) are used that contain as little or no halogen as possible.
(c) Katalysatorsysteme, die ihre positiven Wirkungen auch bei relativ niederen Temperaturen entfalten; - was z.B. für Trockenphasenpolymerisationen von Bedeutung sein kann.(c) Catalyst systems that have their positive effects even at relative unfold lower temperatures; - what e.g. for dry phase polymerizations of Meaning can be.
(d) Katalysatorsysteme, durch welche die morphologischen Eigenschaften der Polymerisate in bestimmter Weise beeinflußt werden, etwa im Sinne einer einheitlichen Korngröße und/ oder eines hohen Schüttgewichtes; - was z.B. für die technologische Beherrschung der Polymerisationssysteme, die Aufarbeitung der Polymerisate und/oder die Verarbeitbarkeit der Polymerisate von Bedeutung sein kann.(d) catalyst systems through which the morphological properties the polymers are influenced in a certain way, for example in the sense of a uniform Grain size and / or a high bulk density; - what e.g. for the technological Mastery of the polymerization systems, the work-up of the polymers and / or the processability of the polymers can be important.
(e) Katalysatorsysteme, die einfach und sicher herzustellen und gut handzuhaben sind; - z.B. solche, die sich in (inerten) Kohlenwasserstoff-Hilfsmedien zubereiten lassen.(e) Catalyst systems that are easy and safe to manufacture and good are to be handled; - e.g. those that are in (inert) hydrocarbon auxiliary media have it prepared.
(f) Katalysatorsysteme, die es ermöglichen, bei Polymerisationen unter Einwirkung von Molekulargewichtsreglern, wie Wasserstoff, mit relativ geringen Mengen an Regler auszukommen; - was z.B. für die Thermodynamik der Verfahrensführung von Bedeutung sein kann.(f) Catalyst systems that allow under polymerizations Exposure to molecular weight regulators, such as hydrogen, in relatively small amounts to get along with regulators; - what e.g. for the thermodynamics of the process management of Meaning can be.
(g) Katalysatorsysteme, die auf spezielle Polymerisationsverfahren zugeschnitten sind; etwa solche, die z.B. entweder auf die spezifischen Besonderheiten der Suspensionspolymerisation oder auf die spezifischen Besonderheiten der Trockenphasenpolymerisation abgestimmt sind.(g) catalyst systems based on special polymerization processes are tailored; such as those that, for example, either focus on the specific characteristics suspension polymerization or the specific features of dry phase polymerization are matched.
Nach den bisherigen Erfahrungen gibt es unter den mannigfachen Zielen etliche Ziele, die man durch Modifikationen in der Art der Titan enthaltenden Verbindung (1) nur dann erreichen kann, wenn man andere Ziele zurücksetzt.According to previous experience, there are multiple goals several goals that can be achieved by modifications in the nature of the titanium-containing compound (1) can only be achieved by setting other goals aside.
Unter diesen Gegebenheiten ist man im allgemeinen bestrebt, solche Modifikationen zu finden, mit denen man nicht nur die gesteckten Ziele erreicht, sondern auch andere erwünschte Ziele möglichst wenig zurücksetzen muß.Under these circumstances one generally strives to achieve such To find modifications with which one not only achieves the set goals, but also has to reset other desired goals as little as possible.
In diesem Rahmen liegt auch die Aufgabenstellung der vorliegenden Erfindung: Eine neue Art von Titan enthaltenden Verbindungen (1) aufzuzeigen, mit denen man gegenUber bekannten Titan enthaltenden Verbindungen (1) - unter vergleichbarer Zielsetzung - bessere Ergebnisse erreichen kann.The task at hand also lies within this framework Invention: To show a new type of titanium-containing compounds (1) with compared to known titanium-containing compounds (1) - under comparable Goal setting - can achieve better results.
Insbesondere war es eine Aufgabenstellung zur vorliegenden Erfindung, eine neue Art von Titan enthaltenden Verbindungen (1) aufzuzeigen, die einerseits kein Halogen in das Polymerisat einbringt und andererseits erlaubt, durch einfache Maßnahmen das Molekulargewicht des Polymerisats Uber sehr weite Bereiche zu steuern.In particular, it was an object of the present invention to to show a new type of titanium-containing compounds (1) on the one hand does not introduce any halogen into the polymer and, on the other hand, allows, by simple Measures to control the molecular weight of the polymer over a very wide range.
Es wurde gefunden, daß die gestellte Aufgabe gelöst werden kann, wenn bei dem eingangs definierten Verfahren eingesetzt werden als Titan enthaltende Verbindung (1) ein Bis(cyclopentadienyl)-titan-dialkyl, als Aluminium enthaltende Verbindung (2) ein Aluminiumtrialkyl sowie als eine weitere Komponente Wasser.It has been found that the problem can be solved if in the process defined at the outset are used as titanium-containing compounds (1) a bis (cyclopentadienyl) titanium dialkyl compound containing aluminum (2) an aluminum trialkyl and, as a further component, water.
Gegenstand der vorliegenden Erfindung ist dementsprechend ein Verfahren zum Herstellen von Polyäthylen durch Polymerisation von Athylen bei Temperaturen im Bereich von -80 bis 120, insbesondere 0 bis 1000C mittels eines Ziegler-Katalysatorsystems aus (1) einer Titan enthaltenden Verbindung sowie (2) einer Aluminium enthaltenden Verbindung.The present invention accordingly relates to a method for the production of polyethylene by polymerizing ethylene at temperatures in the range from -80 to 120, in particular 0 to 1000C by means of a Ziegler catalyst system the end (1) a titanium-containing compound; and (2) an aluminum containing compound.
Das erfindungsgemäße Verfahren ist dadurch gekennzeichnet, daß eingesetzt wird ein Katalysatorsystem aus (1) einem Bis(cyclopentadienyl)titan-dialkyl mit bis zu 4 Kohlenstoffatomen pro Alkylgruppe, (2) einem Aluminiumtrialkyl mit bis zu 4 Kohlenstoffatomen pro Alkylgruppe sowie (3) Wasser mit den Maßgaben, daß das Molverhältnis (1) : (2) im Bereich von 1 : 1 bis 1 : 105, insbesondere 1 : 2 bis 1 : 50 und das Molverhältnis (2) : (3) im Bereich von 6 : 1 bis 6 : 49, insbesondere 3 : 1 bis 1 : 1 liegt.The method according to the invention is characterized in that it is used a catalyst system from (1) a bis (cyclopentadienyl) titanium dialkyl with up to 4 carbon atoms per alkyl group, (2) an aluminum trialkyl with up to to 4 carbon atoms per alkyl group and (3) water with the proviso that the Molar ratio (1): (2) in the range from 1: 1 to 1:105, in particular 1: 2 to 1:50 and the molar ratio (2): (3) in the range from 6: 1 to 6:49, in particular 3: 1 to 1: 1.
Ein Vorteil des erfindungsgemäßen Verfahrens ist, daß mit der eingesetzten Titan enthaltenden Verbindung (1) kein Halogen in die Polymerisate eingebracht wird. Ein weiterer Vorteil des neuen Verfahrens ist, daß es erlaubt, über die relative Menge des mit eingesetzten Wassers das Molekulargewicht der Polymerisate zu regeln, wobei steigende relative Mengen an Wasser zu sinkenden Molekulargewichten und zugleich zu stark steigenden Reaktionsgeschwindigkeiten führen et vice versa.An advantage of the method according to the invention is that with the used Titanium-containing compound (1) no halogen is introduced into the polymers. Another advantage of the new method is that it allows information about the relative The amount of water used to regulate the molecular weight of the polymers, with increasing relative amounts of water leading to decreasing molecular weights and at the same time lead to sharply increasing reaction rates and vice versa.
Diesem Vorteil noch dominierend übergelagert ist, daß bei dem erfindungsgemäßen Verfahren das Molekulargewicht der entstehenden Polymerisate nicht nur über sehr weite Bereiche, sondern auch in einfachster Weise durch die Wahl der Polymerisationstemperatur eingestellt werden kann: Steigende Polymerisationstemperaturen führen zu sinkenden Molekulargewichten, sinkende Polymerisationstemperaturen zu steigenden Molekulargewichten. Dieser Effekt geht so weit, daß nach dem neuen Verfahren - bei relativ hohen Temperaturen - flüssige Oligome bis - bei relativ niederen Temperaturen - hochmolekulare Kunststoffe entstehen.This advantage is still dominantly superimposed that in the case of the invention Process the molecular weight of the resulting polymers not just about a lot wide ranges, but also in the simplest possible way through the choice of the polymerization temperature can be set: Rising polymerisation temperatures lead to lower polymerisation temperatures Molecular weights, decreasing polymerization temperatures to increasing molecular weights. This effect goes so far that according to the new process - at relatively high temperatures - liquid oligomes up to - at relatively low temperatures - high molecular weight plastics develop.
Zu dem erfindungsgemäßen Verfahren ist im übrigen zu bemerken, daß seine Besonderheit im eigentlichen in der eingesetzten neuen Titan enthaltenden Katalysatorkomponente (1) sowie der Mitverwendung des Wassers (3) liegt.In relation to the method according to the invention, it should also be noted that its peculiarity in the actual contained in the new titanium used Catalyst component (1) and the use of the water (3) is located.
Unter Beachtung dieser Besonderheit kann das Verfahren ansonsten in praktisch allen einschlägig üblichen technologischen Ausgestaltungen durchgeführt werden, etwa als diskontinuierliches, taktweises oder kontinuierliches Verfahren, sei es z.B. als Suspensions-Polymerisationsverfahren, Lösungs-Polymerisationsverfahren oder Trockenphasen-Polymerisationsverfahren; - wobei es allerdings im letztgenannten Fall die größten Vorteile bringt. Die erwähnten technologischen Ausgestaltungen - mit anderen Worten: die technologischen Varianten der Polymerisation von Olefinen nach Ziegler - sind aus der Literatur und Praxis wohlbekannt, so daß sich nähere Ausführungen zu ihnen erübrigen. Zu bemerken ist allenfalls noch, daß bei dem neuen Verfahren der bei der Polymerisation herrschende Druck des monomeren Äthylens an sich nicht kritisch ist, aber aus ökonomischen Gründen im allgemeinen zweckmäßigerweise im Bereich von 1 bis 10 bar liegen sollte.If this peculiarity is observed, the procedure can otherwise be carried out in practically all relevant customary technological configurations carried out as a discontinuous, intermittent or continuous process, be it e.g. as a suspension polymerization process, solution polymerization process or dry phase polymerization processes; - although it is in the latter Case brings the greatest benefits. The technological developments mentioned - in other words: the technological variants of the polymerization of olefins according to Ziegler - are well known from literature and practice, so that closer Explanations about them are superfluous. At most it should be noted that with the new one Process the pressure of the monomeric ethylene prevailing during the polymerization is not critical, but generally expedient for economic reasons should be in the range from 1 to 10 bar.
Das Zusammenstellen des erfindungsgemäß einzusetzenden Katalysatorsystems kann in einschlägig üblicher Weise erfolgen, z.B. durch einfaches Zusammenbringen seiner Komponenten innerhalb oder außerhalb des Polymerisationsraumes. Wie sich gezeigt hat, ist es jedoch im allgemeinen von Vorteil, zunächst die Aluminium enthaltende Verbindung (2) mit dem Wasser zu vereinigen - vorteilhafterweise in einem inerten Kohlenwasserstoff als Lösungsmittel - , einige Zeit "reifen" zu lassen (etwa 10 Sekunden bis 60 Minuten bei Raumtemperatur) und dann gemeinsam mit der Titan enthaltenden Verbindung (1) zur Polymerisation einzusetzen.The assembly of the catalyst system to be used according to the invention can be done in the relevant customary manner, e.g. by simply bringing them together its components inside or outside the polymerization room. How yourself has shown, however, it is generally advantageous to start with the aluminum-containing To combine compound (2) with the water - advantageously in an inert Hydrocarbon as solvent - to "mature" for some time (around 10 Seconds to 60 minutes at room temperature) and then together with the titanium containing Use compound (1) for the polymerization.
Was die stoffliche Seite des neuen Katalysatorsystems betrifft, so ist noch das Folgende zu bemerken: Als Bis(cyclopentadienyl)titan-dialkyl eignet sich vornehmlich das Bis(cyclopentadienyl)titan-dimethyl.As for the material side of the new catalyst system, so the following should also be noted: As bis (cyclopentadienyl) titanium dialkyl bis (cyclopentadienyl) titanium-dimethyl is particularly suitable.
Als Aluminiumtrialkyle eignen sich die bei Ziegler-Katalysatorsystemen üblichen, z.B. Aluminiumtrimethyl, Aluminiumtriäthyl, Aluminiumtriisobutyl.Suitable aluminum trialkyls are those in Ziegler catalyst systems common ones, e.g. aluminum trimethyl, aluminum triethyl, aluminum triisobutyl.
Beispiel 1 In einem stopfbuchslosen 1 l-Rührautoklaven wurden nach sorgfältigem Evakuieren und Ausheizen zu 350 ml vorgereinigtem Toluol bei 210C 0,00025 Mol Bis(cyclopentadienyl)titan-dimethyl, 0,0052 Mol Trimethylaluminium und 0,0026 Mol Wasser gegeben.Example 1 In a 1 l stirred autoclave without a stuffing box, after careful evacuation and heating to 350 ml of pre-cleaned toluene at 210C 0.00025 Moles of bis (cyclopentadienyl) titanium-dimethyl, 0.0052 moles of trimethylaluminum and 0.0026 Given moles of water.
Anschließend wurden 7 bar Äthylen aufgepresst. Nach 90 Minuten wurde die Reaktion abgebrochen, das Polyäthylen abfiltriert und getrocknet.Then 7 bar of ethylene were injected. After 90 minutes it was the reaction stopped, the polyethylene was filtered off and dried.
Ausbeute: 14,4 g Molekulargewicht: 200 000 g/Mol.Yield: 14.4 g molecular weight: 200,000 g / mol.
Vergleichsversuch In einem stopfbuchslosen 1 l-Rührautoklaven wurden nach sorgfältigem Evakuieren und Ausheizen zu 350 ml vorgereinigtem Toluol bei 210C 0,00025 Mol Bis(cyclopentadienyl)titan-dimethyl und 0,0052 Mol Trimethylaluminium gegeben. AnschlieRend wurden 7 bar Äthylen aufgepreßt und ständig nachgeregelt. Nach 112 Stunden wurde die Reaktion abgebrochen, das Polyäthylen abfiltriert und getrocknet.Comparative experiment In a 1 l stirred autoclave without a stuffing box after careful evacuation and heating to 350 ml of pre-purified toluene at 210C 0.00025 moles of bis (cyclopentadienyl) titanium-dimethyl and 0.0052 moles of trimethylaluminum given. Then 7 bar of ethylene were injected and continuously readjusted. After 112 hours the reaction was terminated, the polyethylene was filtered off and dried.
Ausbeute: 11,2 g Molekulargewicht: 3 800 000 g/Mol.Yield: 11.2 g Molecular weight: 3,800,000 g / mol.
Beispiel 2 In einen stopfbuchslosen 1 l-Rührautoklaven wurden nach sorgfältigem Evakuieren und Ausheizen zu 350 ml vorgereinigtem Toluol bei 210C 0,0026 Mol Wasser und 0,0052 Mol Trimethylaluminium gegeben. Nach 40 Minuten.wurden 0,000125 Mol Bis-(cyclopentadienyl)titan-dimethyl hinzugefügt und 7 bar Athylen (polymerisation grade) aufgepreßt. Nach 90 Minuten wurde die Reaktion abgebrochen, das Polyäthylen abfiltriert und getrocknet.Example 2 In a 1 l stirred autoclave without a stuffing box, after careful evacuation and heating to 350 ml of pre-cleaned toluene at 210C 0.0026 Moles of water and 0.0052 moles of trimethylaluminum given. After 40 minutes. Were 0.000125 mol of bis (cyclopentadienyl) titanium-dimethyl added and 7 bar of ethylene (polymerization grade) pressed on. The reaction was terminated after 90 minutes, the polyethylene filtered off and dried.
Ausbeute: 15,3 g Molekulargewicht: 208 000 g/Mol.Yield: 15.3 g Molecular weight: 208,000 g / mol.
Beispiel 3 In einen stopfbuchslosen 1 l-RUhrautoklaven wurden nach sorgfältigem Evakuieren und Aus heizen zu 350 ml vorgereinigtem Toluol 0,0052 Mol Trimethylaluminium und 0,0026 Mol Wasser gegeben. -Nach 40 Minuten wurden dann 0,000125 Mol Bis(cyclopentadienyl)titan-dimethyl hinzugefügt, auf 500C thermostatisiert und 7 bar Äthylen (polymerisation grade) aufgepresst.Example 3 In a 1 l stirred autoclave without a stuffing box, after careful evacuation and heating to 350 ml of prepurified toluene 0.0052 mol Trimethylaluminum and 0.0026 moles of water are added. -After 40 minutes it was 0.000125 Mol of bis (cyclopentadienyl) titanium-dimethyl added, thermostatted to 500C and 7 bar ethylene (polymerisation grade) pressed on.
Nach 90 Minuten wurde die Reaktion abgebrochen, das Polyäthylen abfiltriert und getrocknet.After 90 minutes the reaction was terminated and the polyethylene was filtered off and dried.
Ausbeute: 19,25 g Molekulargewicht: 90 000 g/Mol.Yield: 19.25 g, molecular weight: 90,000 g / mol.
Beispiel 4 In einem stopfbuchslosen 1 l-Rührautoklaven wurden nach sorgfältigem Evakuieren und Ausheizen 350 ml Toluol, 0,00126 Mol Trimethylaluminium und 0,0004 Mol Wasser vereinigt, Die Lösung wurde auf +50C gekühlt und mit Äthylen (polymerisation grade) bei 8 bar gesättigt. Nach 30 Minuten wurden 3,7.10 7 Mol Bis(cyclonentadienyl)titan-dimethyl hinzugefügt. Nach 490 Minuten wurden 4,4 g Polyäthylen erhalten, entspr. einer Aktivität von 420 000 Mol PA/Mol Ti.Example 4 In a 1 l stirred autoclave without a stuffing box, careful evacuation and heating 350 ml of toluene, 0.00126 mol of trimethylaluminum and 0.0004 mol of water combined, the solution was cooled to + 50C and with ethylene (polymerization grade) saturated at 8 bar. After 30 minutes, 3.7.10 7 mol Bis (cyclonentadienyl) titanium dimethyl added. After 490 minutes, 4.4 g of polyethylene were obtained obtained, corresponding to an activity of 420,000 mol PA / mol Ti.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762608863 DE2608863A1 (en) | 1976-03-04 | 1976-03-04 | Ethylene polymerisation using Ziegler catalyst system - contg. bis-cyclopentadienyl-titanium di-alkyl cpd., aluminium tri-alkyl cpd. and water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762608863 DE2608863A1 (en) | 1976-03-04 | 1976-03-04 | Ethylene polymerisation using Ziegler catalyst system - contg. bis-cyclopentadienyl-titanium di-alkyl cpd., aluminium tri-alkyl cpd. and water |
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| Publication Number | Publication Date |
|---|---|
| DE2608863A1 true DE2608863A1 (en) | 1977-09-08 |
| DE2608863C2 DE2608863C2 (en) | 1989-06-01 |
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| DE19762608863 Granted DE2608863A1 (en) | 1976-03-04 | 1976-03-04 | Ethylene polymerisation using Ziegler catalyst system - contg. bis-cyclopentadienyl-titanium di-alkyl cpd., aluminium tri-alkyl cpd. and water |
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Cited By (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0035242A1 (en) * | 1980-02-29 | 1981-09-09 | BASF Aktiengesellschaft | Process for producing polymers and copolymers of ethylene |
| EP0037894A2 (en) * | 1980-02-28 | 1981-10-21 | Cpc International Inc. | Process for preparing polymer compositions based on starch and polyolefins |
| DE3150270A1 (en) * | 1981-12-18 | 1983-06-30 | EC Erdölchemie GmbH, 5000 Köln | High-pressure polymerisation of ethylene |
| DE3240382A1 (en) * | 1982-11-02 | 1984-05-03 | Hoechst Ag, 6230 Frankfurt | Process for the preparation of filled polyolefins |
| EP0129368A1 (en) * | 1983-06-06 | 1984-12-27 | Exxon Research And Engineering Company | Process and catalyst for polyolefin density and molecular weight control |
| US4530914A (en) * | 1983-06-06 | 1985-07-23 | Exxon Research & Engineering Co. | Process and catalyst for producing polyethylene having a broad molecular weight distribution |
| WO1987003604A1 (en) * | 1985-12-12 | 1987-06-18 | Exxon Chemical Patents, Inc. | New polymerization catalyst |
| EP0260999A1 (en) * | 1986-09-19 | 1988-03-23 | Exxon Chemical Patents Inc. | High pressure, high temperature polymerization of ethylene |
| WO1988002009A1 (en) * | 1986-09-19 | 1988-03-24 | Exxon Chemical Patents, Inc. | High pressure, high temperature polymerization of ethylene |
| EP0284708A1 (en) | 1987-04-03 | 1988-10-05 | Fina Technology, Inc. | Metallocene catalyst systems for olefin polymerization having a silicon hydrocarbyl bridge. |
| EP0308177A1 (en) * | 1987-09-14 | 1989-03-22 | Exxon Chemical Patents Inc. | Method for preparing an active metallocene-alumoxane catalyst in situ during polymerization |
| US4897455A (en) * | 1985-06-21 | 1990-01-30 | Exxon Chemical Patents Inc. | Polymerization process |
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| EP0037894A2 (en) * | 1980-02-28 | 1981-10-21 | Cpc International Inc. | Process for preparing polymer compositions based on starch and polyolefins |
| EP0037894A3 (en) * | 1980-02-28 | 1982-03-17 | Cpc International Inc. | Process for preparing polymer compositions based on starch and polyolefins |
| EP0035242A1 (en) * | 1980-02-29 | 1981-09-09 | BASF Aktiengesellschaft | Process for producing polymers and copolymers of ethylene |
| DE3150270A1 (en) * | 1981-12-18 | 1983-06-30 | EC Erdölchemie GmbH, 5000 Köln | High-pressure polymerisation of ethylene |
| DE3240382A1 (en) * | 1982-11-02 | 1984-05-03 | Hoechst Ag, 6230 Frankfurt | Process for the preparation of filled polyolefins |
| EP0129368A1 (en) * | 1983-06-06 | 1984-12-27 | Exxon Research And Engineering Company | Process and catalyst for polyolefin density and molecular weight control |
| US4530914A (en) * | 1983-06-06 | 1985-07-23 | Exxon Research & Engineering Co. | Process and catalyst for producing polyethylene having a broad molecular weight distribution |
| EP0374619A1 (en) * | 1983-11-14 | 1990-06-27 | Idemitsu Kosan Company Limited | Process for the production of polyethylene compositions |
| US4897455A (en) * | 1985-06-21 | 1990-01-30 | Exxon Chemical Patents Inc. | Polymerization process |
| US5191052A (en) * | 1985-06-21 | 1993-03-02 | Exxon Chemical Patents Inc. | Copolymers of ethylene and 1,3-butadiene |
| WO1987003604A1 (en) * | 1985-12-12 | 1987-06-18 | Exxon Chemical Patents, Inc. | New polymerization catalyst |
| US5077255A (en) * | 1986-09-09 | 1991-12-31 | Exxon Chemical Patents Inc. | New supported polymerization catalyst |
| US5183867A (en) * | 1986-09-09 | 1993-02-02 | Exxon Chemical Patents Inc. | Polymerization process using a new supported polymerization catalyst |
| EP0260999A1 (en) * | 1986-09-19 | 1988-03-23 | Exxon Chemical Patents Inc. | High pressure, high temperature polymerization of ethylene |
| WO1988002009A1 (en) * | 1986-09-19 | 1988-03-24 | Exxon Chemical Patents, Inc. | High pressure, high temperature polymerization of ethylene |
| US4939217A (en) * | 1987-04-03 | 1990-07-03 | Phillips Petroleum Company | Process for producing polyolefins and polyolefin catalysts |
| US5064797A (en) * | 1987-04-03 | 1991-11-12 | Phillips Petroleum Company | Process for producing polyolefins and polyolefin catalysts |
| EP0284708A1 (en) | 1987-04-03 | 1988-10-05 | Fina Technology, Inc. | Metallocene catalyst systems for olefin polymerization having a silicon hydrocarbyl bridge. |
| US5084534A (en) * | 1987-06-04 | 1992-01-28 | Exxon Chemical Patents, Inc. | High pressure, high temperature polymerization of ethylene |
| WO1989002448A1 (en) * | 1987-09-14 | 1989-03-23 | Exxon Chemical Patents, Inc. | Method for preparing an active metallocene-alumoxane catalyst in situ during polymerization |
| EP0308177A1 (en) * | 1987-09-14 | 1989-03-22 | Exxon Chemical Patents Inc. | Method for preparing an active metallocene-alumoxane catalyst in situ during polymerization |
| US5340786A (en) * | 1988-02-12 | 1994-08-23 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization catalyst and process for the polymerization of olefins |
| US5006500A (en) * | 1988-10-27 | 1991-04-09 | Exxon Chemical Patents Inc. | Olefin polymerization catalyst from trialkylaluminum mixture, silica gel and a metallocene |
| US5321107A (en) * | 1989-01-31 | 1994-06-14 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization catalyst and process for the polymerization of olefins |
| EP0773239A2 (en) | 1992-06-22 | 1997-05-14 | Fina Technology, Inc. | Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems |
| EP0773238A2 (en) | 1992-06-22 | 1997-05-14 | Fina Technology, Inc. | Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems |
| US6291611B1 (en) | 1993-11-05 | 2001-09-18 | Borealis Holding A/S | Supported olefin polymerization catalyst, its preparation and use |
| WO1996002580A1 (en) * | 1994-07-20 | 1996-02-01 | Montell Technology Company B.V. | Catalysts and processes for the polymerization of olefins |
| US6136932A (en) * | 1994-07-20 | 2000-10-24 | Montell Technology Company B.V. | Catalysts and processes for the polymerization of olefins |
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| US5741195A (en) * | 1994-09-30 | 1998-04-21 | Lisco, Inc. | High visibility inflated game ball |
| US6605676B1 (en) | 1994-12-30 | 2003-08-12 | Repsol Quimica, S.A. | Process for obtaining polyolefins with broad bimodal or multimodal molecular weight distributions |
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| US6133187A (en) * | 1995-08-03 | 2000-10-17 | Repsol Quimica S.A. | Hetergeneous metallocene catalysts and use thereof in olefin polymerization process |
| US5824620A (en) * | 1995-08-03 | 1998-10-20 | Repsol Quimica S.A. | Heterogeneous metallocene catalysts and use thereof in olefin polymerization process |
| US6114477A (en) * | 1996-02-09 | 2000-09-05 | Exxon Chemical Patents Inc. | Polymerization process |
| US7211538B2 (en) | 1996-10-31 | 2007-05-01 | Repsol Quimica S.A. | Catalytic systems for the polimerization and copolimerization of alpha-olefins |
| US6278009B1 (en) | 1997-02-01 | 2001-08-21 | Repsol Quimica S.A. | Heterogeneous catalyst components for olefins polymerization, preparation process and use thereof |
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| US6562991B1 (en) | 1998-10-23 | 2003-05-13 | Albemarle Corporation | Gelatinous compositions formed from hydroxyaluminoxane, solid compositions formed therefrom, and the use of such compositions as catalyst components |
| US6492292B2 (en) | 1998-10-23 | 2002-12-10 | Albemarle Corporation | Gelatinous compositions formed from hydroxyaluminoxane, solid compositions formed therefrom, and the use of such compositions as catalyst components |
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| US6555494B2 (en) | 1998-10-23 | 2003-04-29 | Albemarle Corporation | Transition metal compounds having conjugate aluminoxate anions, their preparation and their use as catalyst components |
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| EP1110977A1 (en) * | 1999-12-23 | 2001-06-27 | Basf Aktiengesellschaft | Transition metal-catalyzed polymerisation of olefinic monomers in aqueous polymeric medium |
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| DE2608863C2 (en) | 1989-06-01 |
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