DE2608863C2 - - Google Patents
Info
- Publication number
- DE2608863C2 DE2608863C2 DE19762608863 DE2608863A DE2608863C2 DE 2608863 C2 DE2608863 C2 DE 2608863C2 DE 19762608863 DE19762608863 DE 19762608863 DE 2608863 A DE2608863 A DE 2608863A DE 2608863 C2 DE2608863 C2 DE 2608863C2
- Authority
- DE
- Germany
- Prior art keywords
- titanium
- aluminum
- range
- containing compound
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—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
Description
Die vorliegende Erfindung betrifft ein Verfahren zum Herstellen von Polyäthylen durch Polymerisation von Äthylen bei Temperaturen im Bereich von 0 bis 100° C und Drücken des monomeren Äthylens im Bereich von 1 bis 10 bar, mittels eines Ziegler-Katalysatorsystems ausThe present invention relates to a method for producing Polyethylene by polymerizing ethylene at temperatures in the range from 0 to 100 ° C and pressures of the monomeric ethylene in the range from 1 to 10 bar, using a Ziegler catalyst system
- (1) einer Titan enthaltenden Verbindung sowie(1) a titanium containing compound as well
- (2) einer Aluminium enthaltenden Verbindung.(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. Im gegebenen Zusammenhang repräsentative Publikationen sind die DE-AS 10 83 053, die BE-PS 5 51 283, J. Polym. Sci. Bd. 55 (1961), Nr. 161, Seiten 145 bis 152, die DE-OS 17 45 027, die DE-AS 10 22 382, die US-PS 31 28 266, die US-PS 34 40 237, die GB-PS 8 69 492 sowie die DE-AS 10 24 715.Such methods are known in a number of variants, each of which used titanium-containing compound (1) of special chemical and / or chemical-physical type. In the given context representative publications are DE-AS 10 83 053, BE-PS 5 51 283, J. Polym. Sci. 55 (1961), No. 161, pages 145 to 152, the DE-OS 17 45 027, DE-AS 10 22 382, US-PS 31 28 266, US-PS 34 40 237, GB-PS 8 69 492 and DE-AS 10 24 715.
Die Modifikationen in der Art der Titan enthaltenden Verbin dung (1) werden vorgenommen, um bestimmte Ziele zu erreichen, z. B. die folgenden:The modifications in the nature of the titanium containing compound (1) are made to achieve certain goals, e.g. B. the following:
-
(a) Katalysatorsysteme, die eine erhöhte Ausbeute an Poly
merisat zu liefern vermögen, nämlich
- (a₁) Katalysatorsysteme mit einer erhöhten Produktivität, d. h. Systeme, bei denen die Menge an gebildetem Poly merisat pro Gewichtseinheit Titan enthaltender Ver bindungen (1) erhöht ist bzw.
- (a₂) Katalysatorsysteme mit einer erhöhten Aktivität, d. h. Systeme, bei denen die Menge an gebildetem Poly merisat pro Gewichtseinheit Titan enthaltender Ver bindung (1) und pro Zeiteinheit erhöht ist.
- (A 1) catalyst systems with increased productivity, ie systems in which the amount of polymer formed per unit weight of titanium-containing compounds (1) is increased or
- (A₂) catalyst systems with an increased activity, ie systems in which the amount of polymer formed per unit weight of titanium-containing compound (1) and per unit 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 wer den, die möglichst wenig bzw. kein Halogen enthal ten.
- (b₁) the yield according to (a) is increased and / or
- (b₂) Titanium-containing compounds (1) are used who 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 also have their positive effects unfold relatively low temperatures; - what z. B. for Dry phase polymerizations can be important.
- (d) Katalysatorsysteme, durch welche die morphologischen Eigen schaften der Polymerisate in bestimmter Weise beeinflußt werden, etwa im Sinne einer einheitlichen Korngröße und/ oder eines hohen Schüttgewichtes; - was z. B. für die tech nologische Beherrschung der Polymerisationssysteme, die Aufarbeitung der Polymerisate und/oder die Verarbeitbar keit der Polymerisate von Bedeutung sein kann.(d) Catalyst systems through which the morphological properties affect the polymers in a certain way in the sense of a uniform grain size and / or a high bulk density; - what z. B. for the tech technological mastery of the polymerization systems that Processing of the polymers and / or processable speed 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 are easy to use; - e.g. B. those that are in Have (inert) hydrocarbon auxiliary media prepared.
- (f) Katalysatorsysteme, die es ermöglichen, bei Polymeri sationen unter Einwirkung von Molekulargewichtsreglern, wie Wasserstoff, mit relativ geringen Mengen an Regler auszukommen; - was z. B. für die Thermodynamik der Ver fahrensführung von Bedeutung sein kann.(f) Catalyst systems that allow polymeri sations under the influence of molecular weight regulators, like hydrogen, with relatively small amounts of regulator get along; - what z. B. for the thermodynamics of Ver driving can be important.
- (g) Katalysatorsysteme, die auf spezielle Polymerisationsver fahren zugeschnitten sind; etwa solche, die z. B. entweder auf die spezifischen Besonderheiten der Suspensionspoly merisation oder auf die spezifischen Besonderheiten der Trockenphasenpolymerisation abgestimmt sind.(g) catalyst systems based on special polymerization processes driving are tailored; such as those z. B. either on the specific features of the suspension poly merisation or on the specific characteristics of the Dry phase polymerization are coordinated.
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 many A number of goals that can be modified by modifying the Only then achieve the type of compound (1) containing titanium can if you reset other goals.
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, the general aim is to find such modifications with which one can not only the goals set, but also other desired Must reset goals as little as possible.
In diesem Rahmen liegt auch die Aufgabenstellung der vorlie genden Erfindung: Eine neue Art von Titan enthaltenden Ver bindungen (1) aufzuzeigen, mit denen man gegenüber bekannten Titan enthaltenden Verbindungen (1) - unter vergleichbarer Zielsetzung - bessere Ergebnisse erreichen kann.The task at hand lies within this framework Invention: A new type of titanium containing Ver to show bindings (1) with which one is known Titanium-containing compounds (1) - under comparable Objective - 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 Polymeri sat einbringt und andererseits erlaubt, durch einfache Maß nahmen das Molekulargewicht des Polymerisats über sehr weite Bereiche zu steuern.In particular, it was a task for the present Invention, a new type of titanium containing compounds (1) show that on the one hand no halogen in the polymer brings sat and allowed on the other hand, by simple measure took the molecular weight of the polymer over a very wide Control areas.
Es wurde gefunden, daß die gestellte Aufgabe gelöst werden kann, wenn bei dem eingangs definierten Verfahren eingesetzt wird ein Katalysatorsystem ausIt has been found that the task can be solved if a catalyst system is used in the process defined at the outset out
- (1) einem Bis(cyclopentadienyl)titan-dimethyl,(1) a bis (cyclopentadienyl) titanium dimethyl,
- (2) einem Aluminiumtrialkyl mit bis zu 4 Kohlenstoffatomen pro Alkylgruppe sowie(2) an aluminum trialkyl with up to 4 carbon atoms per Alkyl group as well
- (3) Wasser(3) water
mit den Maßgaben, with the stipulations
- (i) daß das Molverhältnis (1) : (2) im Bereich von 1 : 2 bis 1 : 50 und das Molverhältnis (2) : (3) im Bereich von 3 : 1 bis 1 : 1 liegt, sowie(i) that the molar ratio (1): (2) ranges from 1: 2 to 1:50 and the molar ratio (2): (3) in the range of 3: 1 up to 1: 1, and
- (ii) daß man zunächst die Aluminium enthaltende Verbindung (2) mit dem Wasser (3) in einem inerten Kohlenwasserstoff als Lö sungsmittel vereinigt, 10 Sekunden bis 60 Minuten bei Raum temperatur beläßt und dann gemeinsam mit der Titan enthalten den Verbindung (1) zur Polymerisation einsetzt.(ii) that first the aluminum-containing compound (2) with the water (3) in an inert hydrocarbon as Lö solvent combined, 10 seconds to 60 minutes at room temperature and then together with the titanium uses the compound (1) for the polymerization.
Gegenstand der vorliegenden Erfindung ist dementsprechend das im Patentanspruch definierte Verfahren. Accordingly, the present invention relates to the Process defined claim.
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. Diesem Vorteil noch dominierend übergelagert ist, daß bei dem erfindungsgemäßen Verfahren das Molekulargewicht der ent stehenden Polymerisate nicht nur über sehr weite Bereiche, sondern auch in einfachster Weise durch die Wahl der Polymeri sationstemperatur eingestellt werden kann: Steigende Poly merisationstemperaturen führen zu sinkenden Molekulargewich ten, sinkende Polymerisationstemperaturen zu steigenden Mole kulargewichten. Dieser Effekt geht so weit, daß nach dem neuen Verfahren - bei relativ hohen Temperaturen - flüssige Oligome bis - bei relativ niederen Temperaturen - hochmolekulare Kunststoffe entstehen.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 The new procedure is that it allows to go beyond the relative Amount of water used with the molecular weight of Regulate polymers, increasing relative amounts of Water to falling molecular weights and at the same time too strong increasing reaction speeds lead vice versa. This advantage is still dominantly superimposed on that the molecular weight of the ent standing polymers not only over very wide areas, but also in the simplest way through the choice of polymer sation temperature can be set: Rising poly merization temperatures lead to falling molecular weights lower polymerisation temperatures to increasing moles ocular weights. This effect goes so far that according to the new Process - at relatively high temperatures - liquid oligomes to - at relatively low temperatures - high molecular weight Plastics are created.
Dieser Sachverhalt ist aus dem Stand der Technik nicht herleitbar: So ist der DE-AS 10 83 053 ein Arbeiten mit Wasser oder einem Umsetzungsprodukt aus einem Aluminiumtrialkyl und Wasser fremd: auch ist hier Wasserstoff für die Regelung der Molekulargewichte maßgeblich. Gemäß der BE 5 51 283 sowie J. Polym Sci. Bd. 55 (1961), Nr. 161, Seiten 145 bis 152 muß man, um Erfolg zu haben, mit einem Katalysatorsystem auf der Basis von Salzen oder Oxyalkylverbindungen des Bis(cyclopentadienyl)-titan arbeiten. Die DE-OS 17 45 027 verlangt das Arbeiten mit anderen Titanverbindungen sowie die Anwendung von Höchstdruck bei der Polymerisation. Die Verfahren aus der DE-AS 10 22 382, der US-PS 31 28 266 sowie der US-PS 34 40 237 arbeiten mit klassischen Zieglersystemen als Polymerisationsinitiatoren; d. h. die Regelungsbreite der Molekulargewichte ist relativ eng. Das nämliche gilt für die Arbeitsweisen gemäß der GB-PS 8 69 492 und der DE-AS 10 24 715. This state of affairs cannot be deduced from the state of the art DE-AS 10 83 053 working with water or a reaction product made from an aluminum trialkyl and water: hydrogen is also here decisive for the regulation of the molecular weights. According to BE 5 51 283 and J. Polym Sci. Vol. 55 (1961), No. 161, pages 145 to 152 you have to to be successful with a catalyst system based on salts or oxyalkyl compounds of bis (cyclopentadienyl) titanium work. The DE-OS 17 45 027 requires working with other titanium compounds as well the application of maximum pressure in the polymerization. The procedure out DE-AS 10 22 382, US-PS 31 28 266 and US-PS 34 40 237 work with classic Ziegler systems as polymerization initiators; d. H. the regulation range of the molecular weights is relatively narrow. The The same applies to the working methods according to GB-PS 8 69 492 and DE-AS 10 24 715.
Zu dem erfindungsgemäßen Verfahren ist zu bemerken, daß seine Besonderheit in dem eingesetzten neuen Katalysatorsystem liegt.Regarding the method according to the invention it should be noted that its peculiarity lies in the new catalyst system used.
Unter Beachtung dieser Besonderheit kann das Verfahren ansonsten in praktisch allen einschlägig üblichen technologischen Ausgestaltungen durchgeführt werden, etwa als diskontinuier liches, taktweises oder kontinuierliches Verfahren, sei es z. B. als Suspensions-Polymerisationsverfahren, Lösungs-Poly merisationsverfahren oder Trockenphasen-Polymerisationsver fahren; - wobei es allerdings im letztgenannten Fall die größ ten Vorteile bringt. Die erwähnten technologischen Ausgestal tungen - mit anderen Worten: die technologischen Varianten der Polymerisation von Olefinen nach Ziegler - sind aus der Literatur und Praxis wohlbekannt, so daß sich nähere Ausfüh rungen zu ihnen erübrigen.Taking this special feature into account, the process can otherwise in practically all relevant standard technological Refinements are carried out, for example as a discontinuous tactical, cyclical or continuous process, be it e.g. B. as a suspension polymerization process, solution poly merization process or dry phase polymerization process drive; - However, in the latter case it is the largest benefits. The technological shape mentioned in other words: the technological variants the polymerization of olefins according to Ziegler - are from the Literature and practice are well known, so that more detailed information is available to spare them.
Was die stoffliche Seite des neuen Katalysatorsystems betrifft, so ist noch das Folgende zu bemerken: As far as the material side of the new catalyst system is concerned, the following should also be noted:
Als Titan enthaltende Verbindung dient das Bis(cyclopentadienyl) titan-dimethyl.Bis (cyclopentadienyl) serves as the compound containing titanium titanium dimethyl.
Als Aluminiumtrialkyle mit bis zu 4 Kohlenstoffatomen pro Alkylgruppe eignen sich die bei Ziegler-Katalysatorsystemen üblichen, z. B. Aluminiumtrimethyl, Aluminiumtriäthyl, Aluminiumtriisobutyl.As aluminum trialkyls with up to 4 carbon atoms per alkyl group are the usual in Ziegler catalyst systems, for. B. Aluminum trimethyl, aluminum triethyl, aluminum triisobutyl.
In einen stopfbuchslosen 1 l-Rührautoklaven wurden nach sorg
fältigem Evakuieren und Ausheizen zu 350 ml vorgereinigtem
Toluol bei 21° C 0,0026 Mol Wasser und 0,0052 Mol Trimethyl
aluminium gegeben. Nach 40 Minuten wurden 0,000125 Mol Bis
(cyclopentadienyl)titan-dimethyl hinzugefügt und 7 bar Äthylen
(polymerisations-rein) aufgepreßt. Nach 90 Minuten wurde die
Reaktion abgebrochen, das Polyäthylen abfiltriert und getrock
net.
Ausbeute: 15,3 g
Molekulargewicht: 208 000 g/Mol.After careful evacuation and heating to a volume of 350 ml of pre-cleaned toluene at 21 ° C., 0.0026 mol of water and 0.0052 mol of trimethyl aluminum were placed in a 1 l stirred autoclave. After 40 minutes, 0.000125 mol of bis (cyclopentadienyl) titanium dimethyl were added and 7 bar of ethylene (pure for polymerization) were injected. After 90 minutes, the reaction was stopped, the polyethylene was filtered off and dried.
Yield: 15.3 g
Molecular weight: 208,000 g / mol.
In einen stopfbuchslosen 1 l-Rührautoklaven wurden nach sorg
fältigem Evakuieren und Ausheizen zu 350 ml vorgereinigtem
Toluol 0,0052 Mol Trimethylaluminium und 0,0026 Mol Wasser
gegeben. Nach 40 Minuten wurden dann 0,000125 Mol Bis(cyclo
pentadienyl)titan-dimethyl hinzugefügt, auf 50° C thermostati
siert und 7 bar Äthylen (polymerisations-rein) aufgepreßt.
Nach 90 Minuten wurde die Reaktion abgebrochen, das Polyäthylen
abfiltriert und getrocknet.
Ausbeute: 19,25 g
Molekulargewicht: 90 000 g/Mol.
After careful evacuation and baking, 0.0052 mol of trimethylaluminum and 0.0026 mol of water were added to 350 ml of pre-cleaned toluene in a glandless 1 l stirred autoclave. After 40 minutes, 0.000125 mol of bis (cyclopentadienyl) titanium dimethyl were then added, thermostated to 50 ° C. and 7 bar of ethylene (polymerization-pure) pressed on. After 90 minutes the reaction was stopped, the polyethylene was filtered off and dried.
Yield: 19.25 g
Molecular weight: 90,000 g / mol.
Claims (3)
- (1) einer Titan enthaltenden Verbindung sowie
- (2) einer Aluminium enthaltenden Verbindung.
- (1) a titanium containing compound as well
- (2) an aluminum-containing compound.
- (1) einem Bis(cyclopentadienyl)titan-dimethyl,
- (2) einem Aluminiumtrialkyl mit bis zu 4 Kohlenstoffatomen pro Alkylgruppe sowie
- (3) Wasser
- (1) a bis (cyclopentadienyl) titanium dimethyl,
- (2) an aluminum trialkyl with up to 4 carbon atoms per alkyl group and
- (3) water
- (i) daß das Molverhältnis (1) : (2) im Bereich von 1 : 2 bis 1 : 50 und das Molverhältnis (2) : (3) im Bereich von 3 : 1 bis 1 : 1 liegt, sowie
- (ii) daß man zunächst die Aluminium enthaltende Verbindung (2) mit dem Wasser (3) in einem inerten Kohlenwasserstoff als Lö sungsmittel vereinigt, 10 Sekunden bis 60 Minuten bei Raum temperatur beläßt und dann gemeinsam mit der Titan enthalten den Verbindung (1) zur Polymerisation einsetzt.
- (i) the molar ratio (1): (2) is in the range from 1: 2 to 1:50 and the molar ratio (2): (3) is in the range from 3: 1 to 1: 1, and
- (ii) that the aluminum-containing compound (2) is first combined with the water (3) in an inert hydrocarbon as solvent, left for 10 seconds to 60 minutes at room temperature and then together with the titanium contain the compound (1) Polymerization begins.
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 |
Publications (2)
Publication Number | Publication Date |
---|---|
DE2608863A1 DE2608863A1 (en) | 1977-09-08 |
DE2608863C2 true DE2608863C2 (en) | 1989-06-01 |
Family
ID=5971467
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
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 |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE2608863A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5525678A (en) | 1994-09-22 | 1996-06-11 | Mobil Oil Corporation | Process for controlling the MWD of a broad/bimodal resin produced in a single reactor |
US6153551A (en) | 1997-07-14 | 2000-11-28 | Mobil Oil Corporation | Preparation of supported catalyst using trialkylaluminum-metallocene contact products |
US7148173B2 (en) | 1998-04-27 | 2006-12-12 | Repsol Quimica, S.A. | Catalytic systems for the polymerization and copolymerization of alpha-olefins |
Families Citing this family (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3007433C2 (en) * | 1980-02-28 | 1982-06-16 | Maizena Gmbh, 2000 Hamburg | Process for the production of polymer compositions from polyolefins and starch and / or lignin and optionally cellulose fibers |
DE3007725A1 (en) * | 1980-02-29 | 1981-09-17 | Hansjörg Prof. Dr. 2000 Hamburg Sinn | METHOD FOR PRODUCING POLYETHYLENE, POLYPROPYLENE AND COPOLYMERS |
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 |
ZA844157B (en) * | 1983-06-06 | 1986-01-29 | Exxon Research Engineering Co | 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 |
US5191052A (en) * | 1985-06-21 | 1993-03-02 | Exxon Chemical Patents Inc. | Copolymers of ethylene and 1,3-butadiene |
US4897455A (en) * | 1985-06-21 | 1990-01-30 | Exxon Chemical Patents Inc. | Polymerization process |
IL80888A (en) * | 1985-12-12 | 1991-12-12 | Exxon Chemical Patents Inc | Olefin polymerization catalysts,their preparation and use thereof |
US5077255A (en) * | 1986-09-09 | 1991-12-31 | Exxon Chemical Patents Inc. | New supported polymerization catalyst |
CA1338046C (en) * | 1986-09-19 | 1996-02-06 | Howard Curtis Welborn Jr. | High pressure high temperature polymerization of ethylene |
EP0260999A1 (en) * | 1986-09-19 | 1988-03-23 | Exxon Chemical Patents Inc. | High pressure, high temperature polymerization of ethylene |
US5084534A (en) * | 1987-06-04 | 1992-01-28 | Exxon Chemical Patents, Inc. | High pressure, high temperature polymerization of ethylene |
ES2082745T3 (en) | 1987-04-03 | 1996-04-01 | Fina Technology | METALLOCAN CATALYTIC SYSTEMS FOR THE POLYMERIZATION OF OLEFINS PRESENTING A SILICON HYDROCARBON BRIDGE. |
US5064797A (en) * | 1987-04-03 | 1991-11-12 | Phillips Petroleum Company | Process for producing polyolefins and polyolefin catalysts |
US4939217A (en) * | 1987-04-03 | 1990-07-03 | Phillips Petroleum Company | Process for producing polyolefins and polyolefin catalysts |
IL87717A0 (en) * | 1987-09-14 | 1989-02-28 | Exxon Chemical Patents Inc | Preparation of 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 |
US5830087A (en) * | 1995-06-26 | 1998-11-03 | Lisco, Inc. | Multi-layer golf ball |
US5710222A (en) | 1992-06-22 | 1998-01-20 | Fina Technology, Inc. | Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems |
FI96866C (en) | 1993-11-05 | 1996-09-10 | Borealis As | Support olefin polymerization catalyst, its preparation and use |
IT1273661B (en) * | 1994-07-20 | 1997-07-09 | Spherilene Srl | CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
US5741195A (en) * | 1994-09-30 | 1998-04-21 | Lisco, Inc. | High visibility inflated game ball |
ES2116188B1 (en) | 1994-12-30 | 1999-04-01 | Repsol Quimica Sa | PROCESS OF OBTAINING POLYOLEFINES WITH WIDE, BIMODAL OR MULTIMODAL MOLECULAR WEIGHT DISTRIBUTIONS. |
ES2120868B1 (en) * | 1995-08-03 | 2000-09-16 | Repsol Quimica Sa | METALOGEN TYPE HETEREOGENEOUS CATALYST SYSTEM, FOR PROCESSES OF OBTAINING POLYOLEFINS. |
US6114477A (en) * | 1996-02-09 | 2000-09-05 | Exxon Chemical Patents Inc. | Polymerization process |
ATE198210T1 (en) | 1996-10-31 | 2001-01-15 | Repsol Quimica Sa | CATALYST SYSTEMS FOR THE POLYMERIZATION AND COPOLYMERIZATION OF ALPHA-OLEFINS |
EP0856524A1 (en) | 1997-02-01 | 1998-08-05 | Repsol Quimica S.A. | Heterogeneous catalyst components for olefins polymerization, preparation process and use thereof |
US6552126B2 (en) | 1997-03-03 | 2003-04-22 | Spalding Sports Worldwide, Inc. | Golf ball cover containing a blend of ionomer and plastomer, and method of making same |
US6160145A (en) * | 1998-10-23 | 2000-12-12 | Albemarle Corporation | Transition metal compounds having conjugate aluminoxate anions and their use as catalyst components |
US6462212B1 (en) | 1998-10-23 | 2002-10-08 | Albemarle Corporation | Transition metal compounds having conjugate aluminoxate anions and their use 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 |
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 |
US6812182B2 (en) | 1998-10-23 | 2004-11-02 | Albemarle Corporation | Compositions formed from hydroxyaluminoxane and their use as catalyst components |
DE19930594B4 (en) * | 1999-07-02 | 2006-02-09 | Basell Polyolefine Gmbh | Process for the preparation of polyolefin (co) polymers with broadened molecular weight distribution and / or polydispersity of the comonomer content and use of the method |
DE19962744A1 (en) * | 1999-12-23 | 2001-06-28 | Basf Ag | Transition metal-catalyzed polymerization of olefinic monomers in a water-containing polymerization medium |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1024715B (en) * | 1954-11-23 | 1958-02-20 | Du Pont | Continuous process for the polymerization of ethylene alone or in a mixture with other olefins |
BE551283A (en) * | 1955-09-27 | |||
DE1022382B (en) * | 1956-04-12 | 1958-01-09 | Hoechst Ag | Process for the polymerization of lower olefins |
DE1083053B (en) * | 1956-06-15 | 1960-06-09 | Hoechst Ag | Process for the production of unbranched polyethylenes |
US3440237A (en) * | 1958-05-22 | 1969-04-22 | Monsanto Co | Production of polyethylene with water-modified ziegler catalyst |
GB869492A (en) * | 1960-03-21 | 1961-05-31 | Shell Res Ltd | Improvements in or relating to the low-pressure polymerisation of olefinic compoundsand catalysts therefor |
US3128266A (en) * | 1960-12-23 | 1964-04-07 | Sun Oil Co | Polymerization of ethylene |
AT282188B (en) * | 1967-03-06 | 1970-06-25 | Ici Ltd | PROCESS FOR THE POLYMERIZATION OF AETHYLENE |
-
1976
- 1976-03-04 DE DE19762608863 patent/DE2608863A1/en active Granted
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5525678A (en) | 1994-09-22 | 1996-06-11 | Mobil Oil Corporation | Process for controlling the MWD of a broad/bimodal resin produced in a single reactor |
US6153551A (en) | 1997-07-14 | 2000-11-28 | Mobil Oil Corporation | Preparation of supported catalyst using trialkylaluminum-metallocene contact products |
US7148173B2 (en) | 1998-04-27 | 2006-12-12 | Repsol Quimica, S.A. | Catalytic systems for the polymerization and copolymerization of alpha-olefins |
Also Published As
Publication number | Publication date |
---|---|
DE2608863A1 (en) | 1977-09-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE2608863C2 (en) | ||
DE2608933C2 (en) | ||
DE2324766C2 (en) | Process for the low pressure polymerization of alpha-olefins having 2 to 6 carbon atoms | |
EP0069951B1 (en) | Process for the production of polyolefins | |
DE2615390C3 (en) | Process for the polymerization of ethylene, alone or together with α-olefins with 3 - 20 carbon atoms or with diolefins | |
EP0571826B1 (en) | Continuous process for the production of ethylene homopolymers and copolymers in gas fluidized bed | |
DE4120009A1 (en) | SOLUBLE CATALYST SYSTEMS FOR THE PRODUCTION OF POLYALK-1-ENEN WITH HIGH MOLES | |
DE19720267A1 (en) | (Co)polymerisation of ethylene | |
DE2000834B2 (en) | Process for the low pressure polymerization of ethylene and a catalyst for carrying out this process | |
DE3426193C2 (en) | ||
DE2814692C2 (en) | ||
DE3038640C2 (en) | ||
EP0401776B1 (en) | Process for preparing a poly-alpha-olefin | |
DE1064239B (en) | Process for the production of polyvinyl chloride | |
EP0264733B1 (en) | Process for preparing ethylene homo- or copolymers by means of a ziegler catalytic system | |
DE3030055A1 (en) | METHOD FOR PRODUCING ETHYLENE HOMOPOLYMERISATS AND ETHYLEN-COPOLYMERISATEN WITH (ALPHA) -MONOOLEFINEN | |
EP0230019B1 (en) | Process for preparing ethyl polymers by means of a ziegler catalyst system | |
DE1024715B (en) | Continuous process for the polymerization of ethylene alone or in a mixture with other olefins | |
DE1645282B2 (en) | PROCESS FOR SEPARATING A POLYMERIZATE OF A 1-OLEFIN WITH 4-10 CARBON ATOMS FROM A SOLUTION | |
DE3324136C2 (en) | ||
DE2350795C2 (en) | Process for the continuous polymerization and copolymerization of ethylene | |
EP0260647A2 (en) | Process for preparing ethylene polymers by means of a Ziegler catalyst system | |
EP0064637B1 (en) | Process for producing homo and copolymers of monoolefins by polymerization of the respective monomers with the aid of a ziegler-type catalyst comprising a vanadium-containing compound | |
EP0643729B1 (en) | Catalyst systems for polymerising c2- to c10-alk-1-enes | |
DE1302641B (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
8110 | Request for examination paragraph 44 | ||
D2 | Grant after examination | ||
8364 | No opposition during term of opposition |