Supported catalyst component, supported catalyst, process of their preparation and use
Abstract
In the present invention, there is disclosed a supported catalyst component comprising a support material and an alumoxane, wherein the alumoxane is fixed onto the support, The component contains 15 to 40 weight percent of aluminum, based on the total weight of the support material and alumoxane, and wherein not more than 10 percent aluminum present in the supported catalyst component is extractable in a one-hour extraction with toluene at a temperature of 90 degC using 10 mL toluene per gram of the supported catalyst component. Further described is a supported catalyst comprising the above-indicated supported catalyst component and a transition metal compound, process for preparing such supported catalyst component and such supported catalyst as well as the use of said supported catalyst for carrying out an addition polymerization process of one or more addition polymerizable monomers, particularly in a suspension or a gaseous phase.

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Expired 2 November 2015, 10.9 years ago.
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30 claims: 10 independent, 20 dependent
- 1PATENTOVÉ NÁROKY 1. Nanesená katalytická komponenta, vyznačující se tím, že obsahuje nosičový materiál a aluminoxan, přičemž tato komponenta obsahuje 15 až 40 hmotnostních procent hliníku, vztaženo na celkovou hmotnost nosičového materiálu a aluminoxanu, přičemž v této katalytické komponentě je extrahovatelný podíl maximálně 10 procent hmotnostních hliníku při jednohodinové extrakci toluenem při teplotě 90 °C za použití 10 mililitrů toluenu na gram nanesené katalytické komponenty, a tato nanesená katalytická komponenta je získatelná (A) zahříváním nosičového materiálu obsahujícího aluminoxan ve formě volně tekoucího prášku pod inertní atmosférou po dobu a při teplotě dostatečné k fixování aluminoxanu na nosičový materiál.
- 2Nanesená katalytická komponenta podle nároku 1, vyznačující se tím, že po zahřívacím stupni (A) následuje:(B) podrobení tohoto nosičového materiálu obsahujícího aluminoxan zpracování v jednom nebo více promývacích stupních za účelem odstranění aluminoxanu, kteiý není fixován na nosičový materiál.
- 3Nanesená katalytická komponenta podle nároku 2, vyznačující se tím, že promývací stupeň se provádí za podmínek refluxování promývacího rozpouštědla, suspendováním nanesené katalytické komponenty v aromatickém uhlovodíku a zahříváním této suspenze při teplotě varu tohoto aromatického uhlovodíku.
- 4Nanesená katalytická komponenta podle některého z nároků laž 3, vyznačující se t í m , že maximálně 9 procent hmotnostních hliníku, přítomného v nanesené katalytické komponentě, je extrahovatelný.
- 5Nanesená katalytická komponenta podle některého z nároků laž 4, vyznačující se t í m , že nosičovým materiálem je oxid křemičitý.
- 6Nanesená katalytická komponenta podle některého z nároků 1 až5, vyznaču j ící se t í m , že uvedeným aluminoxanem je methylaluminoxan.
- 7Nanesená katalytická komponenta podle některého z nároků 1 až6, vyznačující se t í m , že obsahuje 20 až 40 hmotnostních procent hliníku, vztaženo na celkovou hmotnost nosičového materiálu a aluminoxanu. -42CZ 293261 B6
- 8Nanesený katalyzátor, vyznačující se tím, že obsahuje:- nanesenou katalytickou komponentu podle některého z nároků 1 až 7, a - sloučeninu přechodného kovu.
- 9Nanesený katalyzátor podle nároku 8, vyznačující se tím, že sloučeninou přechodného kovu je můstková monocyklopentadienylová sloučenina přechodného kovu ze 4. skupiny nebo můstková biscyklopentadienylová sloučenina přechodného kovu ze 4. skupiny.
- 10Nanesený katalyzátor podle nároku 8 nebo 9, vyznačující se tím, že molámí poměr hliníkových atomů k atomům přechodného kovu je od 1 do 5000.
- 11Nanesený katalyzátor podle některého z nároků 8 až 10, vyzn aču j í cí se tí m , že obsahuje 0,1 až 1000 mikromolů sloučeniny přechodného kovu na gram nosičového materiálu.
- 12Nanesený katalyzátor podle některého z nároků 8 až 11,vyznačující se tím, že je v předpolymerované formě získané tak, že se podrobí olefin v přítomnosti tohoto naneseného katalyzátoru polymeračním podmínkám.
- 13Způsob přípravy nanesené katalytické komponenty, vyznačující se tím. že se (A) zahřívá nosičový materiál obsahující aluminoxan ve formě volně tekoucího prášku pod inertní atmosférou po dobu a při teplotě dostatečné k fixování aluminoxanu k nosičovému materiálu, - přičemž se zvolí podmínky v zahřívacím stupni (A) vedoucí k získání nanesené katalytické komponenty, která obsahuje 15 až 40 hmotnostních procent hliníku, vztaženo na celkovou hmotnost nosičového materiálu a aluminoxanu, přičemž v této nanesené katalytické komponentě je extrahovatelný podíl maximálně 10 procent hmotnostních hliníku při jednohodinové extrakci toluenem při teplotě 90 °C za použití 10 mililitrů toluenu na gram nanesené katalytické komponenty.
- 14Způsob podle nároku 13,vyznačující se tím, že po zahřívacím stupni (A) se:(B) podrobí nosičový materiál obsahující aluminoxan zpracování v jednom nebo více promývacích stupních za účelem odstranění aluminoxanu nefixovaného na nosičový materiál.
- 15Způsob podle nároku 14, vyznačující se tím, že promývací stupeň se provádí za podmínek refluxování promývacího rozpouštědla, suspendováním nanesené katalytické komponenty v aromatickém uhlovodíku a zahříváním této suspenze při teplotě varu tohoto aromatického uhlovodíku.
- 16Způsob podle některého z nároků 13 až 15,vyznačující se tím, že tepelné zpracovávání se provádí při teplotě v rozmezí od 75 °C do 250 °C.
- 17Způsob podle některého z nároků 14 až 16, vyznačující se tím, že promývacím rozpouštědlem je aromatické uhlovodíkové rozpouštědlo.
- 18Způsob podle nároku 17, vyznačující se tím, že uvedeným aromatickým uhlovodíkovým rozpouštědlem je toluen.
- 19Způsob podle některého znároků 13 až 18, vy zn ač uj íc í se t í m , že tepelné zpracovávání se provádí za sníženého tlaku. -43CZ 293261 B6
- 20Způsob podle některého z nároků 13 až 19, vyznačující se tí m , že nosičovým materiálem je oxid křemičitý.
- 21Způsob podle některého z nároků 13 až 20, vyznačující se tím, že aluminoxanem je methylaluminoxan.
- 22Způsob přípravy naneseného katalyzátoru, vyznačující se tím, že se:- připraví nanesená katalytická složka podle některého z nároků 13 až 21, - přidá se sloučenina přechodného kovu, buďto před, nebo po zahřívacím stupni (A) nebo případně promývacím stupni (B), s tou podmínkou, že po přidání této sloučeniny přechodného kovu se takto získaný produkt nepodrobí působení teploty stejné nebo vyšší než je rozkladová teplota sloučeniny přechodného kovu.
- 23Způsob podle nároku 22, vyznačující se tím, že sloučenina přechodného kovu se přidá po provedení zahřívacího stupně.
- 24Způsob podle nároku 23, vy z n a č uj í c í se t í m , že sloučenina přechodného kovu se přidá po případném promývacím stupni.
- 25Způsob podle některého z nároků 22 až 24, vy zn ač u j í c í se t í m , že sloučeninou přechodného kovu je můstková monocyklopentadienylová nebo mono(substituovaná cyklopentadienyl)ová sloučenina přechodného kovu ze 4. skupiny nebo můstková biscyklopentadienylová nebo bis(substituovaná cyklopentadienyl)ová sloučenina přechodného kovu ze 4. skupiny.
- 26Způsob podle některého z nároků 22 až25, vy zn ač u j í c í se t í m , že molámí poměr hliníkových atomů, k atomům přechodného kovu v naneseném katalyzátoru je od 1 do 5000.
- 27Způsob podle některého z nároků 22 až 26, vyznačující se tím, že nanesený katalyzátor obsahuje 0,1 až 1000 mikromolů sloučeniny přechodného kovu na gram nosičového materiálu.
- 28Způsob podle některého z nároků 22 až27, vy zn ač u j í c í se t í m , že se dále podrobí olefin zpracovávání za polymeračních podmínek v přítomnosti naneseného katalyzátoru za vzniku předpolymerizovaného naneseného katalyzátoru.
- 29Použití naneseného katalyzátoru podle některého z nároků 8 až 12 k provádění adiční polymerace jednoho nebo více adičně polymerizovatelných monomerů.
- 30Použití naneseného katalyzátoru podle některého z nároků 8 až 12 k provádění adiční polymerace jednoho nebo více adičně polymerizovatelných monomerů v suspenzi nebo v plynové fázi.
Independent claims30
503 paragraphs in 26 sections, as filed
The present invention relates to a supported catalyst component comprising a support material and an aluminoxane obtainable by heating the support material under specific conditions, a supported catalyst comprising a supported catalyst component and a transition metal compound such as a metallocene compound, a process for preparing said supported catalyst component and a process for preparing said catalyst. a catalyst to effect addition polymerization. preferably in suspension or in the gas phase.
BACKGROUND OF THE INVENTION
Prior art unsupported aluminoxane metallocene catalysts are known to have high catalytic activity in olefin polymerization. Under polymerization conditions where the polymer is produced in the form of solid particles, these homogeneous (soluble) catalysts form deposits of polymer on the reactor walls and stirrers, and these deposits should be removed from the portions at short intervals to prevent efficient heat exchange that is required to cool the reactor contents, and further cause excessive wear of the moving parts. Furthermore, these polymers produced with the aid of these soluble catalysts have a low bulk density, which limits the commercial use not only of the polymers as such, but also limits the use of the process itself.
In order to solve this problem and to overcome the above drawbacks, it has been proposed to use some of the supported aluminoxane-metallocene catalysts in the particle formation polymerization processes.
U.S. Pat. No. 5,057,475 describes deposited metallocene aluminoxane catalysts in which the aluminoxane may be a commercially available aluminoxane or may be an in situ aluminoxane on a solid support material, for example, a substance obtained by adding a trialkylaluminum compound to a a water-containing carrier, such as by adding trimethylaluminum to a water-containing silica. In a preferred embodiment of this U.S. Pat. No. 5,057,475, a metallocene component and an aluminoxane (which was previously combined with a modifier compound) are combined in a first step in a suitable solvent. In a subsequent step, this solution is contacted with the carrier material. The solvent is then removed, usually under vacuum. The solution thus obtained is subsequently heated to remove the solvent. Alternatively, the non-dehydrated gel is added to a solution containing a trialkylaluminum compound to prepare an aluminoxane compound deposited on the surface of the silica gel particles. The solvent is then removed and the residual solids are dried to give a free-flowing powder. According to a typical example, the dried silica is suspended with aluminoxane in toluene, then filtered, washed with pentane and finally dried under vacuum. The metallocene compound is usually combined with aluminoxane in toluene or heptane, and the solution is subsequently combined with pre-treated silica. Finally, toluene or heptane is removed under vacuum to separate the supported catalyst.
U.S. Pat. No. 5,026,797 describes a process for treating a porous particulate carrier material based on a water-insoluble inorganic oxide with an aluminoxane in a solvent suitable for the aluminoxane, such as an aromatic hydrocarbon, followed by rinsing the carrier material with an aromatic hydrocarbon solvent. until no aluminoxane is detected in the supernatant. This patent teaches that it is possible to adjust the amount of aluminum aluminoxane atoms bound to the treated oxide-based support material in the range of 2 to 10 weight percent.
Subsequently, the carrier material so treated is combined with a zirconium compound. The thus obtained carrier material containing the aluminoxane and the zirconium compound is used together with another aluminoxane in solution to carry out the polymerization reaction.
U.S. Pat. No. 5,147,949 describes deposited metallocene aluminoxane catalysts prepared by adding a water-impregnated catalyst support material to a stirred solution containing a trialkylaluminum, and then adding a metallocene component to the product thus obtained.
U.S. Pat. No. 5,240,894 describes a process for preparing a supported catalyst by preparing a reaction solution comprising a metallocene and an aluminoxane, then adding a porous support material, evaporating the suspension thus obtained to remove residual solvent from the support material. whereupon the catalyst is optionally pre-polymerized with an olefinic monomer. A good bulk density of the polymer is only achieved when a prepolymerized supported catalyst is used.
U.S. Patent No. 5,252,529 discloses solid olefin polymerization catalysts comprising a particulate carrier material containing at least one percent by weight water, an aluminoxane compound, and a metallocene compound. To prepare this catalyst, the reaction product of the particulate support and aluminoxane is separated from the diluent (toluene) by decanting or drying under reduced pressure.
European patent application EP 368 644 describes a process for preparing a deposited metallocene aluminoxane catalyst in which non-dehydrated silica gel is added to a stirred triethylaluminum solution, to which a metallocene solution to which triethylaluminum has been added is added. After the addition of trimethylaluminum treated metallocene to the triethylaluminum treated silica gel solid material, the catalyst thus obtained is dried to a free-flowing powder. The catalyst may be dried by filtration or by evaporation of the solvent at a temperature of up to 85 ° C.
European Patent Application EP 323 716 describes a process for preparing a deposited metallocene aluminoxane catalyst by adding non-dehydrated silica gel to a stirred solution of trialkylaluminum, followed by adding metallocene to the reacted mixture, removing the solvent and drying the solid to a free-flowing powder. After addition of the metallocene, the solvent is removed and the residual solids are dried at a temperature of up to 85 ° C.
European Patent Application EP 523 416 describes a supported catalyst component for olefin polymerization prepared from an inorganic carrier material and a metallocene. The metallocene and support material are intimately mixed in a solvent. Preferably, the catalyst component so obtained is extracted with a suitable solvent, such as toluene, to remove a metallocene that is not fixed. Aluminoxane may be added as a catalyst in a subsequent phase.
European Patent Application EP 567 952 discloses a supported polymerization catalyst comprising a reaction product of a supported organoaluminum compound and a metallocene catalyst compound. The supported catalyst is prepared by combining trimethylaluminum with a previously dried support material in an aliphatic inert suspension medium to which water has been added. The suspension may be used as such or filtered and the solids thus obtained may be resuspended in an aliphatic inert suspending medium and then combined with the metallocene compound. Upon completion of this reaction, the supernatant solution is separated and the solid remaining is washed one to five times with an inert suspending medium such as toluene, n-decane, diesel or dichloromethane.
-2GB 293261 B6
It is apparent from a review of prior art publications that it would be desirable to develop a supported catalyst component, a supported catalyst, and a polymerization process that prevent or substantially reduce problems related to reactor failure conditions, including the formation of polymer deposits on the reactor walls and agitator. reactor, especially when performing gas phase polymerization or slurry polymerization. It is further preferred that the polymer produced in gas phase or slurry polymerization is in the form of a free-flowing product, and preferably has a high bulk density.
SUMMARY OF THE INVENTION
According to one aspect of the present invention there is provided a supported catalyst component comprising a support material and an aluminoxane, said component comprising 15 to 40 weight percent aluminum based on the total weight of the support material and the aluminoxane, wherein the deposited catalyst component is an extractable portion of not more than 10 weight percent aluminum by 1 hour toluene extraction at 90 ° C using 10 milliliters of toluene per gram of catalyst component, and the supported catalyst component is obtainable by (A) heating the aluminoxane-containing support material in in the form of a free-flowing powder under an inert atmosphere for a time and at a temperature sufficient to fix the aluminoxane to the support material.
In a preferred embodiment, the supported catalyst component as defined above is obtainable by heating step (A) followed by:
(B) subjecting the aluminoxane-containing support material to treatment in one or more washing steps to remove aluminoxane that is not fixed to the support material.
This washing step is preferably carried out under reflux conditions of the washing solvent, by suspending the supported catalyst component in the aromatic hydrocarbon and heating the suspension at the boiling point of the aromatic hydrocarbon.
In this deposited catalyst component of the invention, preferably up to 9 percent by weight of the aluminum present in the deposited catalyst component is extractable.
The support material for the supported catalyst component according to the invention is preferably silica and said aluminoxane is preferably methylaluminoxane.
The supported catalyst component of the invention preferably contains 20 to 40 weight percent aluminum based on the total weight of the support material and the aluminoxane.
A further aspect of the present invention is a supported catalyst comprising:
a supported catalyst component as defined above, and
a transition metal compound.
The transition metal compound in the supported catalyst of the invention is preferably a Group 4 bridged monocyclopentadienyl compound or a Group 4 bridged biscyclopentadienyl compound.
-3GB 293261 B6
The transition metal compound may be a compound containing at least one cyclic or non-cyclic π-linked anionic ligand group.
In the supported catalyst of the invention, the molar ratio of aluminum atoms to transition metal atoms is preferably in the range of 1 to 5000.
The supported catalyst of the invention preferably contains 0.1 to 1000 micromoles of transition metal compound per gram of support material.
Preferably, the supported catalyst of the invention is in a prepolymerized form, which is obtained by subjecting an olefin in the presence of the supported catalyst to polymerization conditions.
In a further aspect, the present invention relates to a process for the preparation of a supported catalyst component comprising:
(A) heating the aluminoxane-containing support material in the form of a free-flowing powder under an inert atmosphere for a time and at a temperature sufficient to fix the aluminoxane to the support material,
- selecting the conditions in the heating step (A) to obtain a deposited catalyst component comprising 15 to 40 weight percent aluminum based on the total weight of the support material and aluminoxane, wherein the extractable portion of the deposited catalyst component has a maximum of 10 weight percent aluminum with 1 hour toluene extraction at 90 ° C using 10 ml toluene per gram of catalyst component applied.
In a preferred embodiment of the process after the heating step (A):
(B) subjecting the aluminoxane-containing support material to treatment in one or more wash steps to remove aluminoxane not fixed to the support material.
Preferably, the washing step is carried out under reflux conditions of the washing solvent by suspending the supported catalyst component in the aromatic hydrocarbon and heating the suspension at the boiling point of the aromatic hydrocarbon. Preferably, the wash solvent is an aromatic hydrocarbon solvent, most preferably the aromatic hydrocarbon solvent is toluene.
The heat treatment is preferably carried out at a temperature ranging from 75 ° C to 250 ° C. It is also preferred that the heat treatment is carried out under reduced pressure.
In a further aspect, the present invention relates to a process for preparing a supported catalyst comprising:
(A) heating the aluminoxane-containing support material under an inert atmosphere and for a time and at a temperature sufficient to fix the aluminoxane to the support material, optionally thereafter optionally:
(B) subjecting the aluminoxane-containing support material to treatment in one or more washing steps to remove aluminoxane not fixed on the support material, selecting conditions in this heating step (A) and optionally washing step (B) to form a deposited catalytic catalyst; a component comprising 15 to 40 weight percent aluminum based on the total weight of the deposited material and aluminoxane, wherein the deposited catalyst component has an extractable fraction of at most 10 percent
Aluminum for one hour of toluene extraction at 90 ° C using 10 milliliters of toluene per gram of catalyst component applied, and before step (A) or (B) or after step (A) or (B) is added a transition metal compound, provided that upon addition of the transition metal compound, the product so obtained is not subjected to temperatures equal to or higher than the decomposition temperature of the transition metal compound.
Preferably, the transition metal compound is added after the heating step. According to another preferred solution, the transition metal compound is added after an optional washing step.
In the process, the transition metal compound is a bridged 4-group monocyclopentadienyl or mono (substituted cyclopentadienyl) transition metal compound or a biscyclopentadienyl or bissus-substituted cyclopentadienyl 4-group transition metal compound.
In the process according to the invention, it is further preferred that the olefin is subjected to further processing under polymerization conditions in the presence of a supported catalyst to form a prepolymerized supported catalyst.
In another aspect, the present invention relates to the use of a supported catalyst as defined above for effecting addition polymerization of one or more addition polymerizable monomers.
In a further aspect, the present invention relates to the use of a supported catalyst as defined above for effecting addition polymerization of one or more addition polymerizable monomers in suspension or gas phase.
All references to elements or metals of a particular group in the description of the present invention refer to groups in the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1989. It should also be noted that all references to group group indication refer to groups or groups corresponding to this periodic table of elements, using the IUPAC group numbering system. As used herein, a hydrocarbyl group refers to an aliphatic group, a cycloaliphatic group, an aromatic group, or any combination thereof. The term hydrocarbyloxy group refers to a hydrocarbyl group having in its structure an oxygen bond between the group and the element to which it is attached. Throughout the specification and the appended claims, where the term "substituted cyclopentadienyl" is used, this term includes ring-substituted or polynucleic derivatives of the cyclopentadienyl moiety, wherein said substituent is hydrocarbyl, hydrocarbyloxy, hydrocarbylamino, cyano, halogen, silyl, germyl, a siloxy group or mixtures of these groups or two of these substituents represents a hydrocarbylene group, wherein said substituent (or two of these together) contains up to 30 non-hydrogen atoms. Specifically, the term "substituted cyclopentadienyl" includes indenyl, tetrahydroindenyl, fluorenyl, and octahydrofluorenyl.
Unexpectedly, it has been found that polymers having a good bulk density can be prepared in a polymerization process leading to particle formation without deposits or substantially reduced deposits in the reactor when using a supported catalyst in which aluminoxane is fixed to a support material . According to the present invention, good bulk density values for ethylene-based polymers and interpolymers are at least 0.20 grams / cm<sup>3</sup>, preferably at least 0.25 grams / cm<sup>3</sup>and, in an even more preferred embodiment, a value of at least 0.30 grams / cm<sup>3</sup>. It is believed that the rate of deposit formation in the reactor with the amount of aluminoxane to be
-53293261 B6 leaches from the support material during polymerization under given polymerization conditions, which may result in the active catalyst being present in the homogeneous phase, which is dissolved in the diluent, and thus, small polymer particles may form under particulate conditions or formation of polymer particles of poor morphology that may adhere to metal parts or static parts of the reactor. In addition, it is further believed that the bulk density of the polymer is related to the manner in which the aluminoxane is fixed to the support and depends on the amount of unfixed aluminoxane on the support, i.e. the amount of aluminum that can be extracted from the support with toluene at 90 ° C. . Thus, the fixation of the aluminoxane on the support material achieved by the specific processing of the present invention results in substantially no aluminoxane leaching from the support material under polymerization conditions and thus substantially no soluble active catalyst particles are present in the polymerization mixture. It has been found that the supported catalyst can be used not only to prepare ethylene polymers and copolymers having high polyethylene bulk density values in the traditional high density range (i.e., from 0.970 to 0.940 grams / cm)<sup>3</sup>) in carrying out a slurry or gas phase polymerization process, but also copolymers having densities of less than 0,940 grams / cm<sup>3</sup> up to 0.880 grams / cm<sup>3</sup> or even lower density values, while maintaining good bulk density values while avoiding or substantially reducing the formation of deposits in the reactor.
The supported catalyst component of the present invention comprises a support material and an aluminoxane, and generally no more than 10 percent of the aluminum present in the supported catalyst component is extractable at 1 hour toluene extraction at 90 ° C using 10 milliliters of toluene per gram of supported catalyst component. In a preferred embodiment of the invention, at most 9 percent of the aluminum present in the supported catalyst component is extractable and most preferably at most 8 percent of the aluminum present in the supported catalyst component. It has been found that if the amount of extractable fraction is below these levels, using supported catalysts based on the supported catalyst components provides a polymer of good bulk density.
The toluene extraction test is carried out as follows. One gram of supported catalyst component or supported catalyst of known aluminum content is added to 10 ml of toluene, and the mixture is then heated to 90 ° C under an inert atmosphere. The suspension thus obtained is stirred well at the above temperature for one hour. Then, the suspension is filtered using reduced pressure to assist filtration. The solids are then washed twice with 3-5 ml of 90 ° C toluene per gram of solids. The solids were dried at 120 ° C for one hour, at which point the aluminum content of the solids was determined. The difference between the initial aluminum content and the aluminum content after extraction divided by the initial aluminum content and multiplication by 100 percent yields a value representing the amount of extractable aluminum.
The aluminum content is determined by suspending 0.5 g of supported catalyst component or supported catalyst in 10 ml of hexane. The suspension is then treated with 10-15 ml of 6N sulfuric acid, followed by addition of a known excess of EDTA. This excess EDTA is then back titrated with zinc chloride.
At a level of 10 percent of the extractable fraction, the bulk density of the polymer obtained by polymerization using the supported catalyst (or catalyst component) described in the present description is quite sensitive to small variations in the percentage of extractable aluminum. Because of this sensitivity of the bulk density of the polymer and the boundary region errors in determining the percentage of extractable aluminum (estimated at 1 percent absolute value), an alternative test should be used to characterize the supported catalyst component and supported catalyst of the present invention. supported catalyst in the polymerization of ethylene in a hydrocarbon diluent at temperature
And at a pressure of 1.5 MPa and determining the scale of scale formation in the reactor and / or the bulk density of the ethylene polymer thus obtained. Substantially no fouling of the reactor, i.e. substantially no polymer deposits on the reactor walls or on the stirrer, or a bulk density of at least 0.20 grams / cm<sup>3</sup> and preferably at least 0.25 gram / cm<sup>3</sup>are a feature of the supported catalyst components and catalysts of the present invention.
Suitable carrier materials for the present invention preferably have a surface area determined by nitrogen porosimetry using a BET method in the range of 10 m<sup>2</sup>/ gram up to 1000 m<sup>2</sup>/ gram, and preferably from 100 m<sup>2</sup>/ gram up to 600 m<sup>2</sup>/gramme. The porosity of the support is preferably in the range of 0.1 cm<sup>3</sup>/ gram up to 5 cm<sup>3</sup>per gram, preferably from 0.1 cm<sup>3</sup>/ gram up to 3 cm<sup>3</sup>/ gram, and most preferably from 0.2 cm<sup>3</sup>/ gram up to 2 cm<sup>3</sup>/gramme. The average particle size is not critical, but usually ranges from 1 µm to 200 µm.
Examples of suitable support materials for the supported catalyst components include porous polymeric materials such as styrene divinylbenzene copolymers, and solid inorganic oxides such as silica, alumina, magnesium oxide, titanium oxide, thorium oxide and mixed oxides. silicon and one or more Group 2 or Group 13 metal oxides, such as mixed silicon and magnesium oxides and mixed silicon and aluminum oxides. Preferably, silica, alumina and mixed silicon oxides and one or more Group 2 or Group 13 oxides are used as carrier materials. A preferred example of such mixed oxides is silicon-aluminum oxides. Most preferred are silica. The silica may be in granular form, agglomerated form in pyrolytic form, or in another form. Suitable silica based carrier materials useful in the present invention are available from GRACE Davison (division of WR GRACE & amp; Co) and are designated CD 3216.30, Davison Syloid 245, Davison 948 and Davison 952, and from Degussa AG, which has the commercial name Aerosil 812.
Optionally, prior to use, the carrier material may be subjected to a heat treatment and / or chemical treatment to reduce the water or hydroxyl group content of the carrier material. Typical pre-heat treatment is carried out at a temperature ranging from 30 ° C to 1000 ° C for 10 minutes to 50 hours under an inert atmosphere or under reduced pressure.
The supported catalyst component further comprises an aluminoxane component. The aluminoxane (sometimes also referred to as alumoxane) is an oligomeric or polymeric aluminumoxy compound containing chains of alternating aluminum and oxygen atoms, with substituents attached to the aluminum atoms, preferably an alkyl group. The exact structure of these aluminoxanes is unknown, but is generally assumed to be represented by the following general formula:
[-AKRj-OL for cyclic aluminoxanes, and with the general formula:
R<sub>2</sub>A1-O [-A1- (R) -O]<sub>m</sub>-A1R2 in the case of linear compounds in which:
R is independently at each occurrence a hydrocarbyl group having 1 to carbon atoms, preferably an alkyl group or a halide, and m is an integer ranging from 1 to 50, preferably at least 4.
Aluminoxanes are usually the reaction products of water and alkylaluminum, which may contain halide or alkoxide groups in addition to the alkyl group. Reaction of several different alkylaluminum compounds, such as trimethylaluminum and triisobutylaluminum, with water yields so-called modified or mixed aluminoxanes. Preferred aluminoxanes are methylaluminoxane and methylaluminoxane modified with a small amount of other lower alkyl groups, such as an isobutyl group. The aluminoxanes generally contain a small to substantial amount of the starting alkylaluminum compound.
The process chosen for the preparation of the aluminoxane is not important for the purposes of the present invention. In the preparation of this aluminoxane. in which the reaction between water and alkylaluminum is used, the water may be combined with the alkylaluminum in various forms, such as a liquid, steam or solid, for example in the form of crystalline water. A particular method of preparing aluminoxane type compounds by contacting an alkylaluminum compound with an inorganic salt containing crystalline water is disclosed in U.S. Patent 4,542,199. In a particularly preferred embodiment, an alkylaluminum compound is contacted with a recoverable water containing material such as hydrated alumina (e.g. aluminum), silica, or other substances. This process is disclosed in European Patent Application EP 338 044.
The supported catalyst component typically contains 15 to 40 weight percent aluminum, preferably 20 to 40 weight percent, and more preferably 25 to 40 weight percent aluminum based on the total weight of the deposited material and aluminoxane. An amount of aluminum corresponding to at least 15% by weight, preferably at least 20% by weight, and most preferably at least 25% by weight, is advantageous since this allows the storage of relatively high proportions of the transition metal compound on the support material and thereby achieves a relatively high activity. In this way, an improvement in the overall catalytic efficiency can be achieved, especially when it is related to the support material.
The supported catalyst component as such or suspended in a diluent may be stored or transported under inert conditions or may be used to prepare the supported catalyst of the present invention.
In another aspect, the present invention relates to a supported catalyst comprising a supported catalyst component of the present invention and a transition metal compound, preferably a transition metal compound comprising at least one cyclic or non-cyclic π-linked anionic ligand group, preferably according to the invention a cyclopentadienyl or substituted cyclopentadienyl moiety. Suitable complexes include derivatives of any transition metal, including lanthanides, but are preferably Group 3, 4, 5 or lanthanide metals which are in the +2, +3 or +4 formal oxidation state. Preferred compounds include metal complexes containing 1 to 3 π-linked anionic ligand groups, which may be cyclic or non-cyclic delocalized π-linked anionic ligand groups. Examples of π-linked anionic ligand groups include conjugated or unconjugated, cyclic or non-cyclic dienyl groups, allyl groups, and arene groups. By the term "π-linked" is meant that the ligand group is bound to the transition metal via π-bonding. Each atom in this delocalized π-bonded group may be independently substituted with a radical selected from the group consisting of halogens, hydrocarbyl groups, halohydrocarbyl groups and hydrocarbyl-substituted metalloid groups, wherein said metalloid is selected from group 14 of the Periodic Table of the Elements.
-8EN 293261 B6
The term "hydrocarbyl" includes straight chained, branched chain or cyclic alkyl radicals, furthermore aromatic radicals having from 6 to 20 carbon atoms, aromatic radicals substituted with alkyl groups of 7 to 20 carbon atoms, and alkyl radicals substituted with aryl groups containing 7 to 20 carbon atoms. In addition, two or more of these residues may together form a fused ring system or a hydrogenated fused ring system. Suitable hydrocarbyl-substituted organometaloid radicals include mono-, di- and trisubstituted organometaloid radicals of elements of Group 14, wherein each hydrocarbyl group contains 1 to 20 carbon atoms. Examples of suitable hydrocarbyl-substituted organometaloid residues include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, and trimethylgeimyl.
Examples of suitable anionic, delocalized π-linked groups include cyclopentadienyl, indenyl fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, deca and it is also possible to include hydrocarbyl-substituted derivatives of 1 to 10 carbon atoms. Preferred anionic delocalized π-linked groups include cyclopentadienyl, pentamethylcyclopentadienyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl and 2-methyl-4-phenylindenyl.
The term "metallocene compound" as used herein refers to a transition metal compound containing a cyclopentadienyl derivative. Suitable metallocene compounds useful in the present invention include bridged or non-bridged mono-, bis- and tricyclopentadienyl or substituted cyclopentadienyl transition metal compounds.
Suitable non-bridged monocyclopentadienyl or mono (substituted cyclopentadienyl) transition metal derivatives may be represented by the general formula:
CpMX<sub>n</sub> in which:
Cp is cyclopentadienyl or a derivative thereof,
M is a transition metal from Group 3,4 or 5 in a formal oxidation state of 2,3 or 4,
X, independently of its location, is an anionic ligand group (other than a cyclic, aromatic, π-linked anionic ligand group), wherein X contains up to 50 non-hydrogen atoms, and n represents one less than the formal oxidation state M 1, 2 or 3, preferably number 3.
Examples of such ligand groups X include hydrocarbyl, hydrocarbyloxy, hydride, halogen, silyl, germyl, amide, and silyloxy, or two X groups together may form a hydrocarbylene group (including a hydrocarbylene group).
Suitable bridged monocyclopentadienyl or mono (substituted cyclopentadienyl) transition metal compounds include the well-known complexes with limited geometric structure. Examples of such complexes and methods for their preparation can be found in the patent
-9E 293261 B6 / \
Cp * Application EP-A-416 815, U.S. Pat. No. 5,374,696 (corresponding to
WO-93/19104), as well as U.S. Patents 5,055,438,
US 5,057,475, US 5,096,867, US 5,064,802 and US 5,132,380.
In particular, preferred bridged monocyclopentadienyl or mono (substituted cyclopentadienyl) transition metal compounds correspond to the general formula I:
OF'
M <sup>(AND)</sup> \ (X) "in which:
M represents a metal of group 3 to 5, in particular a metal of group 4, in particular titanium,
Cp 'represents a substituted cyclopentadienyl group bound to Z', which group is bound by the π method<sup>5</sup> to M, or is further substituted with one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halogen, hydrocarbyloxy, amino, and mixtures thereof, wherein said substituent contains up to 20 non-hydrogen atoms, or optionally, two together these other substituents (except for halogen and amino) cause Cp * to have a fused ring structure,
Z 'is a divalent moiety other than a cyclic or non-cyclic π-bonding anionic ligand, wherein the moiety Z' contains boron or a member of group 14 of the Periodic Table of the Elements, and optionally nitrogen, phosphorus, sulfur or oxygen, containing up to 20 non-hydrogen atoms, and optionally optionally together CP and Z 'may form a fused ring system,
X, independently of its location, represents an anionic ligand group (other than a cyclic π-bonding group) containing up to 50 non-hydrogen atoms, and n is 1 or 2, depending on the valency of M.
In accordance with the above, M is preferably a Group 4 metal, especially titanium, n is 1 or 2, X is a monovalent ligand group containing up to 30 non-hydrogen atoms, most preferably a hydrocarbyl group containing 1 to 20 carbon atoms .
When n is 1 and the Group 3-5 metal (preferably Group 4 metal) is in the formal oxidation state of +3, then X is preferably a stabilizing ligand.
By the term "stabilizing ligand" is meant that the ligand stabilizes the metal complex by:
(1) either nitrogen, phosphorus, oxygen, or sulfur chelation bonds, or (2) via π<sup>3</sup> bonds with resonant, delocalized π-electron structure.
Examples of Group 1 stabilizing ligands are silyl, hydrocarbyl, amide or phosphide ligands substituted with one or more aliphatic or aromatic ether, thioether, amine or phosphine functional groups, especially those amine or phosphine groups which are tertiary substituted,
The stabilizing ligand contains 3 to 30 non-hydrogen atoms. The most preferred stabilizing ligands from group 1 above are 2-dialkylaminobenzyl or 2- (dialkylaminomethyl) phenyl groups having 1 to 4 carbon atoms in the alkyl groups.
Examples of stabilizing ligands from group 2 above include C 3 -C 10 hydrocarbyl groups containing ethylenic unsaturated bonds such as allyl, 1-methylallyl, 2-methylallyl, 1,1-dimethylallyl or 1-methylallyl. A 2,3-trimethylallyl group.
More preferably, the metal coordination complexes correspond to the general formula II:
<img file="CZ293261B6_D0001.tif" />
(Π) in which:
R 'at each occurrence is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogens, and combinations thereof, containing up to 20 non-hydrogen atoms, or two of these R's (except cyano) or halogen) together may form a bivalent derivative,
X at each occurrence is independently selected from the group consisting of hydride, halogen, alkyl, aryl, silyl, germyl, aryloxy, alkoxy, amide, siloxy, and combinations thereof containing up to 20 non-hydrogen atoms,
Y is a divalent anionic ligand group containing nitrogen, phosphorus, oxygen or sulfur, which group contains up to 20 non-hydrogen atoms, and Y is attached to Z or M via said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together to form a condensed ring system,
M is a Group 4 metal, in particular titanium,
Z is SiR * 2, CR *<sub>2</sub>, SiR *<sub>2</sub>SiR *<sub>2</sub>, CR *<sub>2</sub>CR *<sub>2</sub>CR = CR ', CR *<sub>2</sub>SíR *<sub>2</sub>, GeR *<sub>2</sub>"BR * or BR"<sub>2</sub>, whereas:
each R * independently of its location is selected from the group consisting of hydrogen, hydrocarbyl, silyl, halogenated alkyl, halogenated aryl containing up to 20 non-hydrogen atoms and mixtures thereof, or two or more R groups of Z, or R is Z together with Y to form a fused ring system when n is 1 or 2.
More preferably, Y is -O-, -S-, -NR * -, -PR * -. According to a very preferred embodiment, Y represents a nitrogen or phosphorus-containing group corresponding to the general formula or -N (R ') - or -P (R') - in which R 'has the same meaning as defined above, i.e. an amide group or a phosphide group.
The most preferred metal coordination complexes correspond to formula III:
<img file="CZ293261B6_D0002.tif" />
(ΠΙ) in which:
M means titanium,
R 'at each occurrence is independently selected from the group consisting of hydrogen, silyl, hydrocarbyl or combinations thereof containing up to 20 carbon or silicon atoms, preferably up to 10 carbon or silicon atoms, or two R' groups of the substituted cyclopentadienyl group the parts are connected together.
E is silicon or carbon,
X independently at each occurrence is selected from the group consisting of hydride, halogen, alkyl, aryl, aryloxy or alkoxy containing up to 10 carbon atoms, m is 1 or 2, and n is 1 or 2.
Examples of the most preferred metal coordination compounds mentioned above are those wherein R 'on the amide group is methyl, ethyl, propyl, butyl, pentyl, hexyl (including isomers), norbomyl, benzyl, phenyl a group or cyclododecyl group, hereinafter (ER'2)<sub>m</sub> is dimethylsilane or 1,2-ethylene; R 'on the cyclic π-bonding group, independently of its location in each case, represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, norbomyl, benzyl or phenyl, or two R & apos; groups are joined to form indenyl, tetrahydroindenyl, and X is chloro, bromo, iodo, methyl, ethyl, propyl, butyl, pentyl, hexyl, norbomyl, benzyl or phenyl.
Specific examples of highly preferred compounds include: dimethyl- (t-butylamido) (tetramethyl-h)<sup>5</sup>-cyclopentadienyl) -1,2-ethanediyltitanium, dibenzyl- (tert-butylamido) (tetramethyl-h)<sup>5</sup>-cyclopentadienyl) -1,2-ethanediyltitanium dimethyl- (tert-butylamido) (tetramethyl-h)<sup>5</sup>(cyclopentadienyl) dimethylsilanetitanium
-12EN 293261 B6 Dibenzyl- (t-butylamido) (tetramethyl-h)<sup>5</sup>-cyclopentadienyl) dimethylsilanetitanium, dimethyl- (methylamido) (tetramethyl-h<sup>5</sup>-cyclopentadienyl) dimethylsilanetitanium, dibenzyl- (methylamido) (tetramethyl-h)<sup>5</sup>-cyclopentadienyl) dimethylsilanetitanium, dimethyl- (phenylamido) (tetramethyl-h)<sup>5</sup>-cyclopentadienyl) dimethylsilanetitanium, dibenzyl- (phenylamido) (tetramethyl-h)<sup>5</sup>-cyclopentadienyl) dimethylsilanetitanium, dimethyl- (benzylamido) (tetramethyl-h)<sup>5</sup>-cyclopentadienyl) dimethylsilanetitanium, dibenzyl- (benzylamido) (tetramethyl-h)<sup>5</sup>-cyclopentadienyl) dimethylsilanetitanium, dimethyl- (t-butylamido) (h<sup>5</sup>-cyclopentadienyl) -1,2-ethanediyltitanium, dibenzyl- (tert-butylamido) (h)<sup>5</sup>-cyclopentadienyl) -1,2-ethanediyltitanium, dimethyl- (tert-butylamido) (h)<sup>5</sup>-cyclopentadienyl) dimethylsilanetitanium, dibenzyl- (tert-butylamido) (h<sup>5</sup>(cyclopentadienyl) dimethylsilanetitanium, dimethyl- (methylamido) (h<sup>5</sup>-cyclopentadienyl) dimethylsilanetitanium, dibenzyl- (tert-butylamido) (h<sup>5</sup>-cyclopentadienyl) dimethylsilanetitanium, dimethyl- (tert-butylamido) indenyldimethylsilanetitanium, dibenzyl- (tert-butylamido) indenyldimethylsilanetitanium, dibenzyl- (benzylamido) indenyldimethylsilanetitanium, and the corresponding zirconium and hafnium coordination complexes.
Transition metal compounds in which the transition metal is in the formal oxidation state of +2 and processes for their preparation are described in detail in International Patent Application WO 9 500 526 (which corresponds to U.S. Patent Application 241,523, filed May 12, 1994). Suitable complexes include those containing one, and only one, cyclic, delocalized, anionic, π-bonding group, which complexes correspond to formula IV:
ZX
L - M — X * (IV) in which:
M means titanium or zirconium in the formal oxidation state +2,
L is a group containing a cyclic, delocalized, anionic π-system through which this group is bound to M, which group is also bound to Z,
-13GB 293261 B6
Z is bonded to M via a σ-bond, which group contains boron or a member of group 14 of the Periodic Table of the Elements, and also contains nitrogen, phosphorus, sulfur or oxygen, which group contains up to 60 non-hydrogen atoms, and
X * represents a neutral, conjugated or non-conjugated diene, optionally substituted with one or more hydrocarbyl groups, wherein X * contains up to 40 carbon atoms and forms a π-complex with M.
Preferred transition metal compounds of formula IV include those in which Z, M and X * have the same meaning as previously defined and L is C<sub>5</sub>H<sub>4</sub> a group bound to Z and further bound Π<sup>5</sup> in a bonding manner to M, or represents this n<sup>5</sup> a linking group substituted by one to four substituents independently selected from the group consisting of hydrocarbyl, silyl, germyl, halogen, cyano and combinations thereof, said substituent containing up to 20 non-hydrogen atoms, and optionally two (except cyano) substituents and halogen) together cause L to have a fused ring structure.
Even more preferred transition metal compounds having a formal oxidation state of +2 include those of formula V:
R '
<img file="CZ293261B6_D0003.tif" />
R '(V) in which:
R at each occurrence is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano and combinations thereof, said R 'containing up to 20 non-hydrogen atoms, and optionally two of these R' groups (wherein R ', however, is not hydrogen, halogen or cyano) together may form a divalent derivative attached at adjacent positions of the cyclopentadienyl ring to form a fused ring structure,
X * means neutral Ji<sup>4</sup> - a diene-bonding group containing up to 30 non-hydrogen atoms which form a π-complex with M,
Y is -O-, -S-, -NR * -, -PR-,
M represents titanium or zirconium in the formal oxidation state of +2, and
Z * means SiR *<sub>2</sub>, CR *<sub>2</sub>, SiR *<sub>2</sub>SiR *<sub>2</sub>, CR *<sub>2</sub>CR *<sub>2</sub>, CR * = CR *<sub>2</sub>SiR *<sub>2</sub>, or GeR *<sub>2</sub>where
R * is independently hydrogen or selected from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl and combinations thereof, wherein R contains up to 10 non-hydrogen atoms, and optionally two or two; more R * groups from the meaning of Z (where R * is not an atom
Or R * group of Z * and R * group of Y together form a fused ring system.
Preferably, R ', independently at each occurrence, is hydrogen, hydrocarbyl, silyl, halogen, and combinations thereof, wherein R' contains up to 10 non-hydrogen atoms, or two R 'groups, ( wherein R 'is not a hydrogen atom or a halogen atom) together form a divalent derivative of this structure, and most preferably R' represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group (including all isomers where it is present), a cyclopentyl group, a cyclohexyl group, a norbomyl group, a benzyl group or a phenyl group, or two R 'groups (except for a hydrogen or halogen atom) are linked to each other,<sub>5</sub>The R '4 group thus represents, for example, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group or an octahydrofluorenyl group.
In addition, it is further preferred that at least one R 'group or the R * group represents an electron donating group. By the term "electron donor" is meant that this group provides the electron more readily than a hydrogen atom. In view of the above, a nitrogen or phosphorus group Y is highly preferred, and corresponds to the formula -N (R) - or -P (R ') - wherein R represents a hydrocarbyl group containing 1 to 10 carbon atoms.
Examples of suitable X * groups include:
s-trans-Jl<sup>4</sup>-1,4-diphenyl-1,3-butadiene, s-trans-n<sup>4</sup>-3-methyl-1,3-pentadiene, s-trans-n<sup>4</sup>-1,4-dibenzyl-1,3-butadiene, s-trans-n<sup>4</sup>-2,4-hexadiene, s-trans-x<sup>4</sup>-1,3-pentadiene, s-trans-n<sup>4</sup>-1,4-ditholyl-1,3-butadiene, s-trans-n<sup>4</sup>-1,4-bis (trimethylsilyl) -1,3-butadiene, s-cis-n<sup>4</sup>-1,4-diphenyl-1,3-butadiene, s-cis-J1<sup>4</sup>-3-methyl-1,3-pentadiene, s-cis-J1<sup>4</sup>-1,4-dibenzyl-1,3-butadiene, s-cis-Jt<sup>4</sup>-2,4-hexadiene, s-trans-n<sup>4</sup>-1,3-pentadiene, s-cis-n<sup>4</sup>-1,4-ditolyl-1,3-butadiene, and s-cis-Jt<sup>4</sup>-1,4-bis (trimethylsilyl) -1,3-butadiene, said s-cis diene group forming a π-complex with a metal as defined above.
The most preferred transition metal compounds having a formal oxidation state of +2 include the amidosilane or amidoalkadiyl compounds of formula V, wherein:
-Z * —Y— means - (ER <sub>2</sub>)<sub>m</sub><sup>N</sup>(R) -,
And each R is independently selected from the group consisting of hydrogen, silyl, hydrocarbyl, and combinations thereof, wherein said R 'group contains up to 10 carbon or silicon atoms, or two R groups per substituted the cyclopentadienyl group (when R'is not hydrogen) together form a divalent derivative attached to adjacent positions of the cyclopentadienyl ring,
R represents a hydrocarbyl group containing 1 to 10 carbon atoms,
R is, independently at each occurrence, a hydrogen atom or a hydrocarbyl group containing 1 to 10 carbon atoms.
E at each location is silicon or carbon, and m is 1 or 2.
Examples of metal complexes of the present invention include compounds wherein R is methyl, ethyl, propyl, butyl, pentyl, hexyl (including any isomers of the preceding groups, if any), cyclododecyl, norbomyl, benzyl or phenyl, (ER <sub>2</sub>)<sub>m</sub> represents a dimethylsilane or ethanediyl group, and said cyclic delocalized π-bonding group is cyclopentadienyl, tetramethylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl or octahydrofluorenyl.
Suitable transition metal containing bis-cyclopentadienyl or substituted cyclopentadienyl compounds include those having a bridging group attached to the cyclopentadienyl groups and those which do not contain such bridging groups.
The bridged bis-cyclopentadienyl or bis (substituted cyclopentadienyl) transition metal derivatives include compounds represented by the general formula:
Cp<sub>2</sub>MX<sub>n</sub>, in which:
Cp represents a π-bonded cyclopentadienyl group or a π-bonded substituted cyclopentadienyl group, and
M and X are as defined above for the compound of formula (II), and n 'is 1 or 2, being two less than the oxidation state of M.
Preferred n is 2. Examples of such bridged transition metal biscyclopentadienyl derivatives include biscyclopentadienylzirconium dimethyl, biscyclopentadienylzirconium dibenzyl, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butyl cyclopentadienyl) zirconium dimethyl;
B6 bis (tert-butylcyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dibenzyl, bis (fluorenyl) zirconium dimethyl.
bis (pentamethylcyclopentadienyl) zirconium bis [2- (N, N-dimethylamino) benzyl], and the corresponding titanium and hafnium derivatives.
Preferred bridging groups include those corresponding to the general formula (ER <sub>2</sub>)<sub>x</sub>wherein E is silicon or carbon, R independently of its location is hydrogen or a group selected from silyl, hydrocarbyl, and combinations thereof, wherein the R group contains up to 30 carbon or silicon atoms, and x is 1 to 8 Preferably R is independently methyl, benzyl, tert-butyl or phenyl at all locations.
Examples of bridging ligands containing two π-bonding groups are:
(dimethylsilyl-bis-cyclopentadienyl), (dimethylsilyl-bis-methylcyclopentadienyl), (dimethylsilyl-bis-ethylcyclopentadienyl), (dimethylsilyl-bis-tert-butylcyclopentadienyl), (dimethylsilyl-bis-tetramethylcyclopentadienyl), (dimethylsilyl-bis-indole) , (dimethylsilyl-bis-tetrahydroindenyl), (dimethylsilyl-bis-fluorenyl), (dimethylsilyl-bis-terahydrofluorenyl), (dimethylsilyl-bis-2-methyl-4-phenylindenyl), (dimethylsilyl-bis-2-methylindenyl), ( dimethylsilyl-cyclopentadienyl-fluorenyl), (1,1,2,2-tetramethyl-1,2-disilyl-bis-cyclopentadienyl), (1,2-bis- (cyclopentadienyl) ethane), and (isopropylidene-cyclopentadienyl-fluorenyl).
Examples of the above-mentioned bridged biscyclopentadienyl or bis (substituted cyclopentadienyl) complexes include compounds corresponding to the following general formula (VI):
-17GB 293261 B6
<img file="CZ293261B6_D0004.tif" />
(VI) in which:
X, X. E, R, m and n have the same meaning as defined for the complexes of formula III.
The two substituents X taken together can form a neutral π-bonded conjugated diene containing 4 to 30 non-hydrogen atoms forming a π-complex with M, wherein M, which is preferably zirconium or hafnium, is in a formal oxidation state of +2.
The aforementioned metal complexes are particularly suitable for preparing polymers having a stereoregular molecular structure. In connection with this ability, it is preferred that the complex has Cs symmetry or has a chiral, stereorigid structure. Examples of compounds of the first type include compounds having various delocalized π-bonding systems, such as one cyclopentadienyl group and one fluorenyl group. Similar systems based on Ti (in valency IV) or Zr (in valency IV) have been reported to be useful in the preparation of syndiotactic olefin polymers in Ewen et al., J. Am. Chem. Soc., Vol. 110, pp. 6,255-6,256 (1980). Examples of chiral structures include bis-indenyl complexes. Similar systems based on Ti (in valence IV) or Zr (in valence IV) have been reported to be suitable for the preparation of isotactic olefin polymers in Wild et al., J. Organomet. Chem. Vol. 232, pp. 233-47 (1982).
Examples of complexes of formula (IV) include:
(dimethylsilyl-bis-cyclopentadienyl) zirconium dimethyl, (dimethylsilyl-bis-tetramethylcyclopentadienyl) zirconium dimethyl, (dimethylsilyl-bis-tert-butylcyclopentadienyl) zirconium diphenyl, (dimethylsilyl-bis-tert-tetramethylcyclopentadienyl), (dimethylsilyl-bis-indenyl) zirconium bis (2-dimethylaminobenzyl),
-18EN 293261 B6 Isopropylidene-cyclopentadienyl-fluorenyl) zirconium dimethyl, [2,2-biphenyldiylbis (3,4-dimethyl-1-cyclopentadienyl)] - titaniumdibenzyl, [6,6-dimethyl-2,2-biphenyl-bis (3,4-dimethyl- 1-cyclopentadienyl] zirconium dimethyl, and the corresponding titanium-hafnium complexes.
Suitable transition metal-based tricyclopentadienyl or substituted cyclopentadienyl compounds include those having a bridging group linked by two cyclopentadienyl groups, and compounds containing these bridging groups.
Suitable non-bridged transition metal tricyclopentadienyl derivatives are represented by the general formula:
Cp<sub>3</sub>MX<sub>n</sub> ·, in which:
Cp, M and X are as defined above, and n is a number three less than the formal oxidation state of M, being 0 or 1, preferably 1.
In a preferred embodiment, the ligand group X is a hydrocarbyl group, a hydrocarbyloxy group, a hydride group, a halogen, a silyl group, a germyl group, an amide group, and a siloxy group.
Preferably, the transition metal compound is a bridged Group 4 monocyclopentadienyl transition metal compound or a Group 4 bridged biscyclopentadienyl transition metal compound, more preferably the bridged monocyclopentadienyl transition metal compound, in particular the compound wherein: the metal is titanium.
Other compounds suitable for use in the preparation of the catalyst compositions of the present invention, in particular compounds containing other Group 4 metals, will be apparent to those skilled in the art.
In general, the molar ratio of aluminum atoms (derived from the aluminoxane component) to transition metal atoms in the supported catalyst is in the range of from 1 to 5000, preferably from 25 to 1000, and most preferably from 50 to 500. At too low a range, the supported catalyst is not very active, and at too high a ratio, the use of the catalyst is not economical due to the relatively high cost of using large amounts of aluminoxane.
The amount of transition metal compound in the supported catalyst of the present invention is not important, but is usually in the range of 0.1 to 1000 micromoles of transition metal compound per gram of support material. Preferably, the supported catalyst comprises 1 to 250 micromoles of transition metal compound per gram of support material. According to the present invention, it has been found that an increased proportion of aluminum in the support material results in the catalysts thus obtained having a higher efficiency in terms of transition metal compared to catalysts having a lower proportion of aluminum but of approximately the same aluminum to transition metal. These support components with a higher proportion of aluminum also lead to supported catalysts having higher potencies, expressed in terms of aluminum or support material.
-19GB 293261 B6
The supported catalysts of the present invention can be used as such or prepolymerized form obtained by subjecting the supported catalyst to polymerization conditions to polymerize olefins.
The deposited catalyst component of the present invention is obtainable by heating the support material containing aluminoxane under an internal atmosphere, wherein the processing time and the applied temperature are sufficient to fix the aluminoxane to the support material.
The aluminoxane-containing support material can be obtained by combining it with a support material containing 0 and at most 20 weight percent water, preferably 0 to at most 6 weight percent water, based on the total weight of the support and water, using a diluent. As regards the catalytic properties of the supported catalyst, good results can be obtained when using substantially water-free support materials. In addition, it has been found that carrier materials containing a relatively small amount of water can be used without causing any problems. The water-containing support materials, when combined under the same conditions with the same amount of aluminoxane, provide the catalyst components deposited therein with a slightly higher aluminum content than the substantially water-free support materials. It is believed that water reacts with the residual amount of the alkylaluminum compound present in the aluminoxane, while converting the alkylaluminum compound to another aluminoxane. A further advantage is that in this way less alkylaluminum is lost to waste or via recycle streams. The aluminoxane is preferably used in dissolved form.
Alternatively, the aluminoxane-containing support material may be obtained by combining a support material containing 5 and 30 weight percent water, preferably 6 to 20 weight percent water, based on the total weight of the support material and water, in a diluent with a compound of formula:
R η'ΑΙΧ 3-<sub>n</sub>*, in which:
R is independently hydrocarbyl at all sites of its occurrence,
X is halogen or hydrocarbyloxy, and n * is an integer from 1 to 3.
In a preferred embodiment, n * is 3. In the case where the aluminoxane is prepared in situ by reaction of a compound of formula:
R * A1X 3_<sub>n</sub>* with water, then the molar ratio of R n * AlX <sub>3</sub>_<sub>n</sub>The water is usually in the range from 10: 1 to 1: 1, preferably in the range from 5: 1 to 1: 1.
The carrier material is added to the aluminoxane compound or to the compound of the formula R η.ΑΙΧ 3_<sub>n</sub>· Preferably dissolved in a solvent, most preferably dissolved in a hydrocarbon solvent, or a solution of aluminoxane or a compound of formula R η.ΑΙΧ <sub>3</sub>_<sub>n</sub>. added to the support material. The carrier material can be used as such in dry form or suspended in a hydrocarbon diluent. Both aliphatic and aromatic hydrocarbons can be used in this regard. Suitable aliphatic hydrocarbons include, for example, pentane, isopentane, hexane, heptane, octane, isooctane, nonane, isononane, decane, cyclo
Hexane, methylcyclohexane and combinations of two or more of these diluents. Suitable examples of aromatic diluents include benzene, toluene, xylene and other alkyl or halogen substituted aromatic compounds. In a most preferred embodiment, the diluent used is an aromatic hydrocarbon, in particular toluene. A suitable concentration of the solid support in the hydrocarbon medium is in the range of 0.1 to 15 weight percent, preferably in the range of 0.5 to 10 weight percent, and most preferably 1 to 7 weight percent. Contact time and temperature are not critical parameters in this case. Preferably, the temperature is from 0 ° C to 60 ° C, more preferably from 10 ° C to 40 ° C. The contact time ranges from 15 minutes to 40 hours, preferably from 1 hour to 20 hours.
Before the aluminoxane-containing support material is subjected to a heating step, the diluent or solvent is removed to obtain a free-flowing powder. This treatment is preferably carried out by applying a method whereby only the liquid is removed and the aluminum compound remains the aluminum compound on the solid, such as by applying heat, reduced pressure, evaporation, or a combination of these methods.
This heating step (A), followed by optionally washing step (B), is carried out in such a way that a very large proportion (more than 90 weight percent) of aluminoxane that remains on the supported catalyst component is fixed. In the heating step, the aluminoxane is fixed to the support material, and in the optional washing step the aluminoxane, which is not fixed, is largely removed and the supported catalyst component of the present invention is obtained. The upper temperature limit of this heat treatment is preferably lower than the temperature at which the carrier material agglomerates to form lumps, which are very difficult to re-disperse, and below the decomposition temperature of the aluminoxane.
If the metallocene compound is added prior to this heat treatment, as explained below, then the heating temperature should be lower than the decomposition temperature of the metallocene compound. The aluminoxane-containing carrier material, which is a free-flowing substance or powder, is preferably heat heated at a temperature ranging from at least 75 ° C, preferably from at least 85 ° C, and most preferably from at least 100 ° C, to a temperature of up to 250 ° C, preferably up to 200 ° C, with a heat treatment time ranging from 15 minutes to 72 hours, preferably up to 24 hours. According to an even more preferred embodiment, the heating is carried out at a temperature ranging from 160 ° C to 200 ° C for a time ranging from 30 minutes to 4 hours. Good results are obtained by heating for 8 hours at 100 ° C as well as heating for 2 hours at 175 ° C. Any person skilled in the art can, based on preliminary experiments, define the conditions for this heat treatment to achieve the desired result. In this context, it should be noted that the longer the heat treatment, the greater the amount of aluminoxane fixed to the support material. The heat treatment is carried out under reduced pressure or under an inert atmosphere, such as nitrogen gas, but it is preferred to carry out the process under reduced pressure. Depending on the conditions of this heating step, the aluminoxane can be fixed to the support material to such an extent that the washing step can be omitted.
In the optionally performed washing step (B), the number of washes and the solvent used are such that a sufficient removal of the unfixed aluminoxane is obtained to obtain the supported catalyst component of the invention. The washing conditions should be such that the unfixed aluminoxane is soluble in the washing solvent. The deposited aluminoxane-containing material that has already been subjected to heat treatment is preferably subjected to one to five washing steps using an aromatic hydrocarbon solvent and washing at a temperature ranging from 0 ° C to 110 ° C. More preferably, the treatment is carried out at a temperature ranging from 20 ° C to 100 ° C. Preferred examples of aromatic solvents include toluene, benzene and xylenes. More preferably, the aromatic hydrocarbon solvent is toluene. At the end of the wash
The solvent used is removed by a method which also removes the aluminoxane dissolved in the solvent, such as filtration or decanting. In a preferred embodiment of the invention, the wash solvent is removed such that the wash solvent is removed. a free-flowing powdered catalyst component was obtained.
The washing step may preferably be carried out under reflux conditions of the washing solvent. The washing step carried out under reflux conditions allows control of the particle size distribution, preferably in such a way as to achieve a similar particle size distribution to the starting support material, and it has also been found that under these conditions a support catalyst having increased polymerization is obtained. activity. Typically, the supported catalyst component is suspended in the aromatic hydrocarbon after the heating step, and the suspension thus obtained is heated to reflux or heated to the reflux temperature of the aromatic hydrocarbon. The suspension is maintained under these reflux conditions for 5 minutes to 72 hours. Any agglomerated particles that may have formed during the heating step are deagglomerated or dispersed during the washing step under reflux conditions. The longer the reflux conditions are maintained, the better the dispersion is obtained. The concentration of the supported catalyst component in the aromatic hydrocarbon is not critical, but is usually in the range of 1 to 500 grams per liter of hydrocarbon, preferably in the range of 10 to 250 grams per liter. Preferred aromatic hydrocarbons include toluene, benzene and xylenes. More preferably, the aromatic hydrocarbon solvent is toluene. Stirring is applied during the reflux stage.
The supported catalyst component of the present invention is preferably subjected to a dispersion treatment prior to combining the supported catalyst component with a transition metal compound after the washing or refluxing step described above. It has been found that this increases the catalytic activity of the final supported catalyst. In general, hydrocarbons such as aliphatic, cycloaliphatic or aromatic hydrocarbons are used as the dispersing medium. Suitable examples are C 6 -C 20 aliphatic hydrocarbons, preferably C 6 -C 10 hydrocarbons or mixtures of these aliphatic hydrocarbons. The temperature in this case is not important, but a suitable temperature is from 0 ° C to 50 ° C. The duration of this treatment is usually at least 5 minutes and can be up to 72 hours. The upper limit is not critical, but is determined by practical reasons.
The transition metal compound is preferably added after the heating step, and even more preferably both after the heating step and the optional washing step and dispersing step. If the transition metal compound is added prior to any of the above steps, care should be taken not to expose the transition metal compound to excessive temperatures that could lead to decomposition or inactivation of the compound. In a preferred embodiment, the transition metal compound is added after the washing step to avoid washing the transition metal from the support together with the aluminoxane.
The transition metal is contacted with an aluminoxane-containing support material, and preferably a supported catalyst component of the invention, in a diluent, preferably under conditions where the transition metal compound is soluble. Suitable solvents include aliphatic and aromatic hydrocarbons, preferably aliphatic hydrocarbons such as hexane. The metallocene compound is preferably added to a suspension of the carrier material, preferably dissolved in the same diluent in which the carrier is suspended. Generally, the aluminoxane-containing carrier is suspended in the diluent to achieve a concentration of 1 to 20 weight percent, preferably 2 to 10 weight percent. Contact time and temperatures are not critical parameters. Preferably, the temperature is in the range of 10 ° C to 60 ° C, even more preferably, the temperature is in the range of 20 ° C to 45 ° C. The contacting time ranges from 5 minutes to 100 hours, preferably from 0.5 hours to 3 hours. Typically, the diluent used is removed after addition of the metallocene compound. This removal may be by any suitable method, such as by applying heat and / or reduced pressure, evaporation, filtration or decantation, or a combination of these methods. When heating is applied, the temperature should not exceed the decomposition temperature of the metallocene compound.
In some cases, it may be advantageous to subject the olefin in the presence of the supported catalyst to polymerization conditions to obtain a prepolymerized supported catalyst.
In a very preferred embodiment, the process for preparing the supported catalyst of the present invention comprises the following steps:
heating the methylaluminoxane-containing silica support material at a temperature ranging from 75 ° C to 250 ° C under an inert atmosphere, preferably under reduced pressure;
optionally followed by subjecting the product thus obtained in the heating step to one or more washing steps using toluene;
- which is selected when performing the heating step and washing step such conditions as to obtain a coated component in which up to 9 percent aluminum present in the supported catalyst component is extractable in a one hour extraction with toluene of 90 ° C using 1 g of supported catalyst component per 10 ml of toluene, and
- after carrying out the heating step and optionally the washing step, adding a transition metal compound selected from the group consisting of bridged monocyclopentadienyl or mono (substituted cyclopentadienyl) transition metal compounds of 4 and bridged biscyclopentadienyl and bis (substituted cyclopentadienyl) transition metal compounds of 4, with that condition, according to claim 1, characterized in that after addition of the transition metal compound, the product thus obtained is not subjected to temperatures equal to or higher than its decomposition temperature.
Preferably, the supported catalyst comprises 20 to 40 weight percent aluminum based on the total weight of the support and aluminoxane. According to another preferred embodiment, the molar ratio of aluminum atoms to transition metal atoms in the catalyst thus obtained ranges from 25 to 1000. Preferably, the supported catalyst of the invention also contains 0.1 to 1000 micromoles of transition metal compound per gram of support material.
The supported catalyst thus obtained can be used as such, without separation or purification, but preferably the catalyst is first regenerated in the form of free-flowing particles. The catalyst thus separated can be stored under an inert atmosphere for long periods of time, for example for one to several months. Prior to use, the supported catalyst may be readily suspended in a diluent, preferably a hydrocarbon diluent. The catalyst thus obtained does not require the use of additional activators or cocatalysts.
In another aspect, the present invention relates to an addition polymerization process, wherein one or more addition polymerizable monomers are contacted with the supported catalyst of the present invention under addition polymerization conditions.
Suitable polymerizable monomers include ethylenically unsaturated monomers, acetylenic compounds, conjugated or unconjugated dienes, polyenes, and carbon monoxide. Preferred olefins include, for example, alpha-olefins containing 2 to 200 carbon atoms, preferably 2 to 12 carbon atoms, even more preferably 1 to 8 atoms
And a combination of two or more of these alpha-olefins. Particularly preferred alpha-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentane, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-dicene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, or a combination thereof. Preferred alpha-olefins include ethylene, propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and a combination of ethylene and / or propene with one or more of these other alpha-olefins. Preferred monomers include styrene, halogen-substituted or alkyl-substituted styrenes, vinyl chloride, acrylonitrile, methyl acrylate, methyl methacrylate, tetrafluoroethylene, methacrylonitrile, vinyl dichloride, vinylcyclobutene, 1,4-hexadiene and 1,7-octadiene. Suitable addition polymerizable monomers also include any mixtures of these monomers.
The supported catalyst may be prepared in situ in the polymerization mixture by introducing into the mixture both the supported catalyst component of the present invention and a suitable metallocene compound. The supported catalyst component and the supported catalyst of the present invention can be advantageously used for a high pressure, solution, slurry, or gas phase polymerization process. The high pressure process is usually carried out at temperatures ranging from 100 ° C to 400 ° C and at pressures above 50 MPa. The slurry process typically employs an inert hydrocarbon diluent at temperatures ranging from 0 ° C to just below the temperature at which the resulting polymer is substantially soluble in the inert polymerization medium. Preferably, these temperatures range from 20 ° C to 115 ° C, more preferably from 60 ° C to 105 ° C. In the solution process, temperatures ranging from the temperature at which the resulting polymer is soluble in an inert solvent up to 275 ° C are used. In general, the solubility of a polymer depends on its density. In the case of ethylene copolymers having a density of 0.86 grams / cm<sup>3</sup>The solution polymerization can be carried out at temperatures below about 60 ° C. Preferably, the temperatures of the solution polymerization are in the range of 75 ° C to 260 ° C, more preferably in the range of 80 ° C to 170 ° C. Aliphatic hydrocarbons are usually used as inert solvents and preferably. The solution and slurry polymerization processes are generally carried out at pressures ranging from 0.1 MPa to 10 MPa. In the gas phase polymerization process, temperatures are in the range of from 20 ° C to 100 ° C, more preferably from 40 ° C to 80 ° C. In gas phase polymerization processes, the pressure is usually in the range of vacuums to 10 MPa. A typical embodiment of the gas phase polymerization process can be found in U.S. Pat. Nos. 4,588,790, 4,543,399, 5,352,749, 5,405,922, and US Patent Specification 122,582, filed Sep. 17, 1993- corresponding to the international published patent application WO 9 507 942.
When using a carrier for the gas phase polymerization process, the carrier preferably has a mean particle diameter in the range of 20 to 200 µm, more preferably in the range of 30 to 150 µm, and most preferably in the range of 35 µm to 100 pm. When using a carrier material for a slurry polymerization process, the carrier material preferably has a mean particle diameter in the range of 1 to 200 µm, more preferably in the range of 5 to 100 µm, and most preferably in the range of 20 to 80 µm. pm. Preferably, when used in a high pressure polymerization process, the support material has a mean particle diameter in the range of 1 to 40 µm, more preferably in the range of 2 to 30 µm, and most preferably in the range of 3 µm to 20 pm.
When using the supported catalyst of the present invention, when used in a slurry or gas phase polymerization process, it is not only possible to prepare ethylene copolymers having a density typical of high density polyethylene, i.e. in the range of 0.970 g / cm.<sup>3</sup> to 0.940 g / cm @ 2, but surprisingly, it has been found that copolymers having substantially lower densities can also be prepared by the catalyst. Thus, copolymers with densities lower than 0.940 g / cm @ 2 can be prepared<sup>3</sup>, and in particular geese less than 0.930 g / cm @ 2<sup>3</sup> up to densities of 0.880 g / cm<sup>3</sup> or even lower values, while maintaining good bulk density while avoiding or substantially eliminating fouling of the reactor. Thus, ethylene polymers and copolymers having a weight average molecular weight of up to 1,000,000 and even higher can be prepared.
In the polymerization process of the present invention, soil removal or binding agents can be used to protect the supported catalyst from the action of catalytic poisons such as water, oxygen, and polar compounds. These contaminants can generally be used in amounts depending on the amount of contaminants, and are usually added to the monomer and diluent feed or reactor. Typical impurity scavengers include trialkylaluminum compounds or boron compounds and aluminoxanes.
Molecular weight control agents such as hydrogen or other chain transfer agents can also be used in the polymerization process of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The supported catalyst component, supported catalyst, process for their preparation and use, and the results obtained will be illustrated in the following with the aid of specific examples, which are illustrative only and do not limit the scope of the invention. Unless otherwise indicated, all parts and percentages are by weight.
Examples
The following carrier materials were used in these examples: granulated silica, commercially available from Grace GmbH under the designation SD 3216.30, spherical silica, commercially available under the designation Sylopol 2212 from Grace Davison (division of WRGrace & Co.) with surface coating area 250 m<sup>2</sup>/ gram and a pore volume of 1.4 cm<sup>3</sup>/gramme. Unless otherwise indicated, the types of silica used were heated at 250 ° C for 3 hours under vacuum to give a final water content of substantially 0 as determined by differential scanning calorimetry. When water-containing silica was used, the material was used as supplied without heat treatment.
The aluminoxane used in these examples was a 10 weight percent solution of methylaluminoxane (MaO) in toluene, which is commercially available from Witco & GmbH. The metallocene used was a 0.0714 M dimethyl - {(t-butylamino) (tetramethyl-J) solution.<sup>5</sup>cyclopentadienyl) (dimethyl) silane} titanium (referred to herein as MCpTi) in Isopar ™ E (registered trademark of Exxon Chemical Company).
The bulk density of the polymers produced was determined by the ASTM 1895 method. The aluminum content of the support was determined by treatment with sulfuric acid, followed by addition of EDTA and back titration with zinc chloride.
All experiments were performed under a nitrogen atmosphere unless otherwise noted.
Example 1
In this embodiment, 11.1 grams of SD 3216.30 silica was charged into a 1000 mL vessel. Then 300 grams of MAO solution was added and the reaction thus obtained
The mixture was stirred for 16 hours. The solvent was then removed under reduced pressure at 20 ° C to give 38 grams of free-flowing powder having an aluminum content of 31.6 percent. The sample was divided into four equal portions of 9 grams each heated at a different temperature for 2 hours under reduced pressure. After this treatment, the aluminum content of each sample was measured and each sample was suspended in toluene (100 mL), stirred for 1 hour, filtered, and the support was washed with two 50 mL portions of fresh toluene and dried. under vacuum at 120 ° C for one hour. The results of the analyzes for aluminum are given in Table I below.
Table I
Heat treatment / washing with toluene at room temperature
<td>Temperature (° C)</td><td>[Al] after heating (wt%)</td><td>[Al] after washing (wt%)</td>
<td> 125</td><td> 30,7</td><td> 20,3</td>
<td> 150</td><td> 30,0</td><td> 25,7</td>
<td> 175</td><td> 30,8</td><td> 30,3</td>
<td> 200</td><td> 31,1</td><td> 31,4</td>
The above procedure was repeated using 12.1 grams of silica and 327 grams of MAO solution to give 42 grams of free-flowing powder having an aluminum content of 31.3 percent. This sample was divided into four equal portions and each portion was heated in the same manner as above, followed by the same washing procedure except that toluene at 90 ° C was used. The results obtained are summarized in Table II below.
Table II
Heat treatment / washing with toluene at 90 ° C
<td>Temperature (° C)</td><td>[Al] after heating (wt%)</td><td>[Al] after washing (wt%)</td>
<td> 125</td><td> 31,0</td><td> 16,4</td>
<td> 150</td><td> 30,7</td><td> 25,8</td>
<td> 175</td><td> 30,7</td><td> 29,3</td>
<td> 200</td><td> 31,0</td><td> 29,1</td>
These results show that in the case of a heat treatment carried out for the same time, an increase in the temperature of the heat treatment results in a larger proportion of aluminoxane being fixed on the silica. At 90 ° C, a larger percentage of unfixed aluminum was removed in the toluene wash compared to the toluene wash at room temperature, which applies to the washings carried out for the same time.
Example 2
According to this embodiment, 6.2 grams of SD 3216.30 silica was charged into a 250 ml vessel. 168 grams of MAO solution were then added and the mixture was stirred for 16 hours. After this time, toluene was removed under reduced pressure at 20 ° C and then the solid was dried under vacuum at 20 ° C for 16 hours to give a free-flowing powder. The solid weight was 22.1 grams and the aluminum content was 26.8 percent.
-26GB 293261 B6
Example 3
Example 2 was repeated using 3 grams of silica and 56.6 grams of MAO solution to give 7.6 grams of free-flowing powder having an aluminum content of 26.1 percent. 5.2 grams of this support was suspended in toluene (50 mL) at 20 ° C and stirred for 1 hour. The resulting mixture was filtered and the support was washed with two portions of 20 ml of fresh toluene and dried under vacuum at 20 ° C for 1 hour. The weight of this product was 3.0 grams and the aluminum content was 18.2 percent.
Example 4
Example 2 was repeated using 3 grams of silica and 75.6 grams of MAO solution to give a free-flowing powder. The powder was then heated at 100 ° C for two hours under vacuum. The weight of this product was 8.4 grams and the aluminum content was 29.0 percent. 4.4 g of this support was suspended in toluene (50 ml) at 20 ° C and the mixture was stirred for 1 hour. The mixture was filtered and the support was washed with two portions of 20 ml of fresh toluene, and then dried under vacuum at 20 ° C for 1 hour. The weight of the product was 2.2 grams and the aluminum content was 17.3 percent.
Example 5
Example 2 was repeated using 3 grams of silica and 56.6 grams of MAO solution to give a free-flowing powder. The powder was heated at 150 ° C for two hours under vacuum. The weight of this product was 7.2 grams and the aluminum content was 26.6 percent.
Example 6
Example 2 was repeated using a 1000 ml flask, 12.1 grams of silica and 327 grams of MAO solution to give a free-flowing powder. 9.5 grams of this powder were heated at 175 ° C for two hours under vacuum. The aluminum content was 30.7 percent. 2.7 g of this support was suspended in hexane (40 ml) at 20 ° C and the mixture was stirred for 4 hours. The mixture was filtered and the support was washed with two 30 ml portions of fresh hexane and dried under vacuum at 20 ° C for 1 hour. The weight of the product thus obtained was 2.4 grams and the aluminum content was 30.4 percent.
Example 7
The procedure of Example 2 was repeated. A powdered product was obtained, which was heated at 150 ° C for two hours under vacuum. The weight of the product was 7.25 grams and the aluminum content was 26.6 percent. Then, 3 grams of the carrier material was suspended in toluene (40 ml) at 20 ° C and the mixture was stirred for 1 hour. The mixture was filtered and the support was washed with two 10 ml portions of fresh toluene, and then dried under vacuum at 20 ° C for one hour. The weight of the product was 2.4 grams with an aluminum content of 24.1 percent.
-27GB 293261 B6
Example 8
Example 2 was repeated using 3 grams of silica and 75.5 grams of MAO solution to give a free-flowing powder. The powder was then heated at 150 ° C for two hours under vacuum. The weight of this product was 8.4 grams and the aluminum content was 29.8 percent. 5.0 grams of this support was suspended in toluene (40 mL) at 20 ° C and the mixture was stirred for 1 hour. The mixture was filtered and the support was washed with two portions of 20 ml of fresh toluene and dried under vacuum at 20 ° C for 1 hour. The weight of this product was 4.5 grams and the aluminum content was 28.9 percent.
Example 9
Example 2 was repeated using a 1000 mL vessel, 9.1 grams of silica and 246 grams of MAO solution to give a free-flowing powder. The powder was then heated at 150 ° C for two hours under vacuum. The weight of the product was 29.0 grams and the aluminum content was 29.6 percent. The support was suspended in toluene (300 mL) at 20 ° C and the mixture was stirred for 1 hour. The mixture was filtered and the support washed with two 100 ml portions of fresh toluene and dried under vacuum at 20 ° C for 1 hour. The weight of the product thus obtained was 24.3 grams and the aluminum content was 28.5 percent.
Example 10
Example 2 was repeated using 5 grams of silica and 101 grams of MAO solution to give a free-flowing powder. The powder was heated at 175 ° C for two hours under vacuum. The aluminum content of this product was 28.8 percent. The powder (12.8 g) was resuspended in toluene (130 mL) and the mixture was heated to 90 ° C and stirred and the solid obtained was washed with two 50 mL portions of fresh toluene at 90 ° C. The resulting support was then dried under vacuum at 120 ° C for one hour. The weight of the product was 10.4 grams and the aluminum content was 26.3 percent.
Example 11
Example 2 was repeated using 10 grams of silica and 76 grams of MAO solution to give a free-flowing powder. The powder was heated at 175 ° C for two hours under vacuum. The aluminum content of this product was 17.2 percent. The powder (15.6 g) was resuspended in toluene (150 mL) and the mixture was heated to 90 ° C and stirred for one hour. The mixture was filtered and the resulting solid was washed with two 50 mL portions of fresh toluene at 90 ° C. The resulting support was then dried under vacuum at 120 ° C for one hour. The weight of the support was 13.0 grams and the aluminum content was 16.3 percent.
-28GB 293261 B6
Example 12
Example 2 was repeated using 5 grams of SD 3216.30 silica at 2.8 percent water and 101 grams of MAO solution to give a free-flowing powder. The powder was heated at 175 ° C for two hours under vacuum. The aluminum content of this product was 29.4 percent. The powder (13 g) was resuspended in toluene (130 ml) and the mixture was heated to 90 ° C and stirred for one hour. The mixture was filtered and the resulting solid was washed with two 50 mL portions of fresh toluene at 90 ° C. The resulting support was then dried under vacuum at 120 ° C for one hour. The weight of the product was 11.5 grams and the aluminum content was 29.0 percent.
Example 13
Example 2 was repeated using a 1000 mL vessel, 9 grams of Sylopol 2212 silica and 243 grams of MAO solution to give a free-flowing powder. The powder was then heated at 150 ° C for two hours under vacuum. The weight of this product was 29.3 grams and the aluminum content was
29.8 percent. The support was suspended in toluene (300 mL) at 20 ° C and stirred for 1 hour. The mixture was filtered and the support was washed with two 100 ml portions of fresh toluene and dried under vacuum at 120 ° C for 1 hour. The weight of the product was 25.9 grams and the aluminum content was 29.3 percent.
Example 14
Example 2 was repeated using a 1000 mL vessel, 9.1 grams of silica and 246 grams of MAO solution to give a free-flowing powder. The powder was heated at 175 ° C for two hours under vacuum. The weight of this product was 30.8 grams and the aluminum content was 30.0 percent. The support was suspended in toluene (300 mL) at 20 ° C and stirred for 1 hour. The mixture was filtered and the support was washed with two 100 ml portions of fresh toluene and dried under vacuum at 120 ° C for 1 hour. The weight of the product was 27.1 grams and the aluminum content was 29.0 percent.
Example 15
Example 2 was repeated using 5.1 grams of silica and 101 grams of MAO solution to give a free-flowing powder. Then it was
6.8 grams of this powder was heated at 100 ° C for two hours under vacuum. The support was suspended in toluene (100 mL) at 90 ° C and the mixture was stirred for 1 hour. The mixture was filtered and the support was washed with two 50 mL portions of fresh toluene (90 ° C), and then dried under vacuum at 100 ° C for 1 hour. The weight of this product was 3.4 grams and the aluminum content was 16.6 percent.
-29GB 293261 B6
Example 16
Example 2 was repeated using 5.1 grams of silica and 101 grams of MAO solution to give a free-flowing powder. Then it was
6.8 grams of this powder were suspended in toluene (100 mL) at 90 ° C and the mixture was stirred for one hour. The mixture was filtered and the support was washed with two 50 mL portions of fresh toluene (90 ° C), and then dried under vacuum at 100 ° C for 1 hour. The weight of this product was 3.0 grams and the aluminum content was 13.4 percent.
Example 17
Example 2 was repeated using 5 grams of SD 3216.30 silica containing 2.8 percent water and 101 grams of MAO solution to give a free-flowing powder. 6 grams of this powder were suspended in toluene (100 ml) at 90 ° C and the mixture was stirred for one hour. The mixture was filtered and the support was washed with two 50 mL portions of fresh toluene (90 ° C), and then dried under vacuum at 20 ° C for 1 hour. The weight of this product was 2.9 grams and the aluminum content was 16.4 percent.
Example 18
Example 2 was repeated using 5 grams of SD 3216.30 silica containing 2.8 percent water and 101 grams of MAO solution to give a free-flowing powder. The powder was then heated at 100 ° C for 2 hours. 6 grams of this powder were suspended in toluene (100 mL) at 90 ° C and the mixture was stirred for one hour. The mixture was filtered and the support was washed with two 50 ml portions of fresh toluene (90 ° C), and then dried under vacuum at 20 ° C for 1 hour. The weight of this product was 3.8 grams and the aluminum content was 22.2 percent.
Example 19
Preparation of supported catalysts
The supported catalysts were prepared using the supported catalyst components obtained in Examples 2 to 18 using the following procedure.
Typically, 1 gram of the carrier component was suspended in 20 ml of hexane and the mixture was stirred for 30 minutes. An aliquot of the MCpTi solution (0.0714 M) was then added in sufficient quantity to achieve the transition metal fraction shown in Table III below. The mixture was stirred for 30 minutes and transferred to the polymerization reactor.
Polymerization
A 10 liter autoclave was charged with 6 liters of anhydrous hexane, comonomer if necessary, hydrogen gas if necessary, and the contents were then heated to 80 ° C unless otherwise noted. Ethylene was then added in an amount such that the pressure was raised to the desired level. A portion of the supported catalyst, which is shown in Table III below, was added via a pressurized metering roller. This ethylene was supplied to
The reactor is continuously operated as desired. After the desired polymerization time had passed, the ethylene feed line was closed and the reactor contents were transferred to the sample tank.
Hexane was removed from the polymer by decantation and dried overnight, weighed and the yield was determined.
In Experiment 22, a temperature of 70 ° C was used and 100 ml of 1-octene comonomer was added to the reactor to obtain an ethylene / 1-octene copolymer with a density of 0.9266 g'cm<sup>3</sup>. In experiment 23, a temperature of 50 ° C was used, adding 200 milliliters of 1-octene comonomer to the reactor to obtain an ethylene / octene copolymer with a density of 0.9230 g / cm 2<sup>3</sup>.
The specific polymerization conditions and results obtained are shown in Table III below. From the above results it can be seen that by using the supported catalyst components prepared by various combinations of heat treatment and / or washing treatment, polymers with high bulk density can be prepared. The highest efficiency was achieved by using supported catalyst components and catalysts containing more than 20 weight percent aluminum. Excellent efficiency was obtained when the supported catalyst components were dispersed in toluene at 90 ° C. Poor bulk density results (experiments 1 to 3) were obtained with the supported catalyst components that were neither subjected to heat treatment at a sufficiently high temperature and for a sufficiently long period of time nor subjected to sufficient washing.
Table III
Polymerization experiments
<td>Experiment no.</td><td>The component of example no.</td><td>Al<sup>1</sup> (wt%)</td><td>Ti<sup>2</sup> (pmol / g)</td><td>Al / Ti<sup>3</sup></td>
<td> 1</td><td> 2</td><td> 26,8</td><td> 40</td><td> 248</td>
<td> 2</td><td> 3</td><td> 18,2</td><td> 40</td><td> 169</td>
<td> 3</td><td> 4</td><td> 17,3</td><td> 40</td><td> 160</td>
<td> 4</td><td> 5</td><td> 26,6</td><td> 40</td><td> 246</td>
<td> 5</td><td> 6</td><td> 30,4</td><td> 40</td><td> 281</td>
<td> 6</td><td> 15</td><td> 16,6</td><td> 40</td><td> 154</td>
<td> 7</td><td> 16</td><td> 13,4</td><td> 40</td><td> 124</td>
<td> 8</td><td> 17</td><td> 16,4</td><td> 40</td><td> 152</td>
<td> 9</td><td> 18</td><td> 22,2</td><td> 40</td><td> 206</td>
<td> 10</td><td> 7</td><td> 24,1</td><td> 40</td><td> 223</td>
<td> 11</td><td> 8</td><td> 28,9</td><td> 40</td><td> 268</td>
<td> 13</td><td> 9</td><td> 28,5</td><td> 40</td><td> 264</td>
<td> 14</td><td> 9</td><td> 28,5</td><td> 20</td><td> 528</td>
<td> 15</td><td> 14</td><td> 29,0</td><td> 20</td><td> 537</td>
<td> 16</td><td> 13</td><td> 29,3</td><td> 20</td><td> 543</td>
<td> 17</td><td> 10</td><td> 26,3</td><td> 40</td><td> 244</td>
<td> 18</td><td> 10</td><td> 26,3</td><td> 40</td><td> 244</td>
<td> 19</td><td> 10</td><td> 26,3</td><td> 70</td><td> 139</td>
<td> 20</td><td> 11</td><td> 16,3</td><td> 40</td><td> 151</td>
<td> 21</td><td> 12</td><td> 29,0</td><td> 40</td><td> 269</td>
<td> 22</td><td> 12</td><td> 29,0</td><td> 40</td><td> 269</td>
<td> 23</td><td> 12</td><td> 29,0</td><td> 40</td><td> 269</td>
-31 GB 293261 B6
Table III (continued)
Polymerization experiments
<td>Experiment no.</td><td>[Ti] (pmol)</td><td>Pressure<sup>5</sup> (MPa)</td><td>Time<sup>6</sup> (minutes)</td><td>Yield<sup>7</sup> (grams)</td>
<td> 1</td><td> 40</td><td> 1,0</td><td> 30</td><td> 100</td>
<td> 2</td><td> 56</td><td> 1,0</td><td> 50</td><td> 97</td>
<td> 3</td><td> 40</td><td> 1,0</td><td> 38</td><td> 137</td>
<td> 4</td><td> 40</td><td> 1,0</td><td> 35</td><td> 171</td>
<td> 5</td><td> 40</td><td> 1,0</td><td> 3,0</td><td> 255</td>
<td> 6</td><td> 20</td><td> 1,5</td><td> 60</td><td> 179</td>
<td> 7</td><td> 20</td><td> 1,5</td><td> 60</td><td> 120</td>
<td> 8</td><td> 20</td><td> 1,5</td><td> 60</td><td> 185</td>
<td> 9</td><td> 20</td><td> 1,5</td><td> 60</td><td> 315</td>
<td> 10</td><td> 40</td><td> 1,0</td><td> 72</td><td> 180</td>
<td> 11</td><td> 40</td><td> 1,0</td><td> 135</td><td> 800</td>
<td> 13</td><td> 15</td><td> 1,5</td><td> 60</td><td> 245</td>
<td> 14</td><td> 10</td><td> 1,5</td><td> 200</td><td> 1 000</td>
<td> 15</td><td> 20</td><td> 1,5</td><td> 180</td><td> 1 000</td>
<td> 16</td><td> 10</td><td> 1,5</td><td> 60</td><td> 363</td>
<td> 17</td><td> 20</td><td> 1,5</td><td> 30</td><td> 375</td>
<td> 18</td><td> 20</td><td> 1,5</td><td> 60</td><td> 720</td>
<td> 19</td><td> 17,5</td><td> 1,5</td><td> 120</td><td> 1 005</td>
<td> 20</td><td> 80</td><td> 1,5</td><td> 27</td><td> 430</td>
<td> 21</td><td> 20</td><td> 1,5</td><td> 60</td><td> 650</td>
<td> 22</td><td> 40</td><td> 1,0</td><td> 22</td><td> 207</td>
<td> 23</td><td> 80</td><td> 1,0</td><td> 45</td><td> 207</td>
-32GB 293261 B6
Table III (continued)
Polymerization experiments
<td>Experiment no.</td><td>E (Ti)<sup>8</sup> [gPE / gTi / hr]</td><td>E (SiO<sub>2</sub>)<sup>9</sup> [gPE / gSiO<sub>2</sub>/ h]</td><td>E (A1)<sup>10</sup> [gPE / gAl / h]</td><td>Bulk density (g / cm<sup>3</sup>)</td>
<td> 1</td><td> 104 384</td><td> 471</td><td> 746</td><td> 0,05</td>
<td> 2</td><td> 43 394</td><td> 137</td><td> 457</td><td> 0,09</td>
<td> 3</td><td> 112 900</td><td> 344</td><td> 1 250</td><td> 0,13</td>
<td> 4</td><td> 152 997</td><td> 684</td><td> 1 102</td><td> 0,20</td>
<td> 5</td><td> 266 180</td><td> 1 470</td><td> 1 678</td><td> 0,24</td>
<td> 6</td><td> 186 848</td><td> 556</td><td> 2 157</td><td> 0,35</td>
<td> 7</td><td> 125 261</td><td> 337</td><td> 1 791</td><td> 0,33</td>
<td> 8</td><td> 193 111</td><td> 571</td><td> 2 256</td><td> 0,37</td>
<td> 9</td><td> 328 810</td><td> 1 204</td><td> 2 838</td><td> 0,38</td>
<td> 10</td><td> 78 288</td><td> 311</td><td> 622</td><td> 0,35</td>
<td> 11</td><td> 185 572</td><td> 938</td><td> 1 230</td><td> 0,41</td>
<td> 13</td><td> 340 988</td><td> 1 685</td><td> 2 292</td><td> 0,39</td>
<td> 14</td><td> 626 305</td><td> 1 547</td><td> 2 105</td><td> 0,43</td>
<td> 15</td><td> 247 947</td><td> 884</td><td> 1 149</td><td> 0,33</td>
<td> 16</td><td> 757 829</td><td> 1 959</td><td> 2 478</td><td> 0,31</td>
<td> 17</td><td> 782 881</td><td> 3 448</td><td> 5 703</td><td> 0,35</td>
<td> 18</td><td> 751 566</td><td> 3 310</td><td> 5 475</td><td> 0,38</td>
<td> 19</td><td> 599 493</td><td> 4 620</td><td> 7 643</td><td> 0,34</td>
<td> 20</td><td> 249 632</td><td> 735</td><td> 2 931</td><td> 0,33</td>
<td> 21</td><td> 678 497</td><td> 3 448</td><td> 4 483</td><td> 0,35</td>
<td> 22</td><td> 294 648</td><td> 1 497</td><td> 1 947</td><td> 0,36</td>
<td> 23</td><td> 72 025</td><td> 366</td><td> 476</td><td> 0,33</td>
Aluminum content on the applied catalyst component
Titanium content of the supported catalyst in pmol / g support (silica + MA0)
The molar ratio of aluminum to titanium in the supported catalyst pmol of titanium added to the reactor as a supported catalyst
Total polymerization pressure
Polymerization time
Grams of polymer produced <sup>8</sup> Catalytic efficiency expressed in grams of titanium in the supported catalyst <sup>9</sup> Catalytic efficiency expressed in grams of silica in the supported catalyst <sup>10</sup> Catalytic efficiency expressed in grams of aluminum in the supported catalyst
Example 20
Example 2 was repeated using 6.2 grams of SD 3216.30 silica and 68 grams of MAO solution to obtain 22.1 grams freely.
The flowable powder for which the aluminum content was 27.8 percent. 11 g of this support was suspended in toluene (75 ml) and 440 micromoles of MCpTi (6.16 ml of a 0.0714 M solution in hexane) was added. The mixture was stirred for 1 hour and then the solvent was removed under reduced pressure and the residue was heated at 150 ° C for two hours. The yield was 11 grams of free-flowing powder with an aluminum content of 28.2 percent. This material was suspended in toluene (100 mL) and stirred for 1 hour, filtered and the solid washed with two 50 mL portions of fresh toluene, then dried under vacuum at 100 ° C for for 1 hour. The product weight was 9 grams, the aluminum content was 24.8 percent and the titanium content was 40 micromoles / gram.
Example 21
The same procedure as in Example 6 was performed using 12.1 grams of SD 3216.30 silica and 327 grams of MAO solution to give a free-flowing powder. 9.1 g of the powder was heated at 150 ° C under vacuum for 2 hours to give a product with an aluminum content of 30.7 percent. 3.5 grams of this powder were suspended in toluene (35 mL), 140 micromoles of MCpTi (1.96 mL of a 0.0714 M solution in hexane) were added and the mixture was stirred for 1 hour. The mixture was filtered and the support was washed with six 50 ml portions of fresh toluene (at this point the washes were colorless) and dried under vacuum at 20 ° C for 1 hour. The weight of the product thus obtained was 22 grams and the titanium content was 30 micromoles / gram.
Example 22
Example 2 was repeated using 3.0 grams of SD 3216.30 silica and 82 grams of MAO solution to yield 10.5 grams of free-flowing powder. 4.85 g of this powder were suspended in toluene (50 ml) and the mixture was stirred for 1 hour. The mixture was filtered and the support was washed with two portions of 20 ml portions of fresh toluene, and then heated under vacuum at 150 ° C for two hours. The weight of this product was 2.1 grams and the aluminum content was 14.9 percent. MCpTi was added in the same manner as described in Example 19.
Example 23
A 250 ml flask was used to which 3.3 grams of SD 3216.30 silica was added. Toluene (80 ml) was added to the suspension, followed by 130 micromoles of MCpTi (1.82 ml of a 0.0714 M solution in hexane) and the mixture was stirred for two hours. 101 grams of MAO solution was added and the mixture was stirred for 16 hours. At this point, the solvent was removed under reduced pressure at 20 ° C to give a free-flowing powder.
The other polymerization processes were carried out in the same manner as in Example 19, in which the general procedure is shown, the specific conditions used in these individual embodiments and the results obtained are shown in Table IV below.
From the results in this table, it can be seen that the low catalytic efficiency is obtained when the metallocene is added prior to heat treatment at 150 ° C (see Example 20). An acceptable bulk density of the product is obtained when the metallocene is added after execution
293261 B6 of the heating step, but prior to the washing step (see Example 21). A good bulk density is obtained when the washing step is performed (see Example 22). An inactive catalyst is obtained when the metallocene is first added to the silica (see Example 23).
Table IV
Polymerization experiments
<td>Experiment no.</td><td>Al<sup>1</sup> (wt%)</td><td>Ti<sup>2</sup> (pmol / g)</td><td>Al / Ti<sup>3</sup></td><td>[Ti] (pmol)</td>
<td> 20</td><td> 24,8</td><td> 40</td><td> 227</td><td> 40</td>
<td> 21</td><td> 22,0</td><td> 30</td><td> 272</td><td> 30</td>
<td> 22</td><td> 14,9</td><td> 40</td><td> 138</td><td> 40</td>
<td> 23</td><td> 26,6</td><td> 40</td><td> 246</td><td> 40</td>
<td>Experiment no.</td><td>Pressure<sup>5</sup> (MPa)</td><td>Time<sup>6</sup> (minutes)</td><td>Yield<sup>7</sup> (grams)</td>
<td> 20</td><td> 1,0</td><td> 25</td><td> 13</td>
<td> 21</td><td> 1,0</td><td> 60</td><td> 167</td>
<td> 22</td><td> 1,0</td><td> 60</td><td> 141</td>
<td> 23</td><td> 1,0</td><td> 30</td><td> 0</td>
Table IV (continued)
Polymerization experiments
<td>Experiment no.</td><td>E (Ti)<sup>8</sup> [gPe / gTi / hr]</td><td>E (SiO<sub>2</sub>)<sup>9</sup> [<sub>G</sub>PE / gSiO<sub>2</sub>/ h]</td><td>E (A1)<sup>10</sup> [gPE / gAl / h]</td><td>Bulk density (g / cm<sup>3</sup>)</td>
<td> 20</td><td> 16 284</td><td> 67</td><td> 126</td><td> —</td>
<td> 21</td><td> 116214</td><td> 317</td><td> 759</td><td> 0,28</td>
<td> 22</td><td> 73 591</td><td> 207</td><td> 946</td><td> 0,32</td>
<td> 23</td><td> 0</td><td> 0</td><td> 0</td><td> -</td>
Aluminum content on the applied catalyst component <sup>2</sup> Titanium content of the supported catalyst in pmol / g support (silica + MA0) <sup>3</sup> The molar ratio of aluminum to titanium in the supported catalyst <sup>4</sup> pmol of titanium added to the reactor as a supported catalyst <sup>5</sup> Total polymerization pressure <sup>6</sup> Polymerization time <sup>7</sup> Grams of polymer produced <sup>8</sup> Catalytic efficiency expressed in grams of titanium in the supported catalyst <sup>9</sup> Catalytic efficiency expressed in grams of silica in the supported catalyst <sup>10</sup> Catalytic efficiency expressed in grams of aluminum in the supported catalyst
-35GB 293261 B6
Example 24
The procedure was carried out in the same manner as in Example 1 except that after removing the solvent from the MAO / silica mixture under reduced pressure at 20 ° C, the individual portions of the powder thus obtained were subjected to a two hour heat treatment and optionally a washing treatment. These facts are summarized in the following table No. V. After these treatments, the supported catalyst components were extracted on the one hand with 90 ° C toluene to determine the percentage of extractable aluminum, and on the other hand were used to carry out the polymerization reactions. All washing and extraction steps were carried out with 1 gram of support per 10 ml of toluene, stirring for one hour, followed by filtration and washing, twice with 5 ml of toluene per gram of starting material. The supported catalysts were prepared in the same manner as described in the general procedure detailed in Example 19. All polymerization processes were carried out at a total pressure of 1.5 MPa and at a temperature of 80 ° C for one hour. The results obtained are shown in Table VI below. From the above results, it can be seen that all percentages of extractable aluminum were below 10 percent to give products with excellent bulk densities.
In process 1, using a heat treatment at 175 ° C without using a washing treatment, polymers with good bulk density could be obtained.
Table V
Extraction tests
<td>Experiment no.</td><td>Heat treatment (° C)</td><td>Toluene wash (20 ° C)</td><td>Aluminum content in catalytic support (%)</td>
<td> 1</td><td> 175</td><td>No</td><td> 29,8</td>
<td> 2</td><td> 175</td><td>Yes</td><td> 28,3</td>
<td> 3</td><td> 165</td><td>No</td><td> 30,5</td>
<td> 4</td><td> 164</td><td>Yes</td><td> 29,3</td>
<td> 5</td><td> 125</td><td>No</td><td> 30,1</td>
<td> 6</td><td> 75</td><td>Yes</td><td> 16,6</td>
<td>Experiment no.</td><td>Aluminum content after extraction (%)</td><td>Extracted aluminum (%)</td><td>Bulk density (g / cm<sup>3</sup>)</td>
<td> 1</td><td> 27,9</td><td> 6,4</td><td> 0,35</td>
<td> 2</td><td> 27,9</td><td> 5,0</td><td> 0,34</td>
<td> 3</td><td> 27,6</td><td> 10</td><td> 0,12</td>
<td> 4</td><td> 27,6</td><td> 5,8</td><td> 0,31</td>
<td> 5</td><td> 20,9</td><td> 33</td><td> 0,06</td>
<td> 6</td><td> 15,9</td><td> 4,2</td><td> 0,34</td>
-36GB 293261 B6
Table VI
Polymerization experiments
<td>Experiment no.</td><td>Ti<sup>2</sup> (pmol / g)</td><td>Al / Ti<sup>3</sup></td><td>[Ti]<sup>4</sup> (pmol)</td><td>Yield<sup>7</sup> (grams)</td>
<td> 1</td><td> 40</td><td> 276</td><td> 20</td><td> 415</td>
<td> 2</td><td> 40</td><td> 262</td><td> 20</td><td> 400</td>
<td> 3</td><td> 40</td><td> 282</td><td> 20</td><td> 330</td>
<td> 4</td><td> 40</td><td> 271</td><td> 20</td><td> 312</td>
<td> 5</td><td> 40</td><td> 278</td><td> 20</td><td> 312</td>
<td> 6</td><td> 40</td><td> 151</td><td> 20</td><td> 130</td>
<td>Experiment no.</td><td>E (Ti)<sup>8</sup> [gPe / gTi / hr]</td><td>E (SiO 2)<sup>9</sup> [gPE / gSiOj / hr]</td><td>E (A1)<sup>10</sup> [gPE / gAl / h]</td><td>Bulk density (g / cm<sup>3</sup>)</td>
<td> 1</td><td> 433 194</td><td> 2 307</td><td> 2 785</td><td> 0,35</td>
<td> 2</td><td> 417 537</td><td> 2 040</td><td> 2 827</td><td> 0,34</td>
<td> 3</td><td> 344 468</td><td> 1 914</td><td> 2 164</td><td> 0,12</td>
<td> 4</td><td> 271 399</td><td> 1 403</td><td> 1 775</td><td> 0,31</td>
<td> 5</td><td> 325 678</td><td> 1 766</td><td> 2 073</td><td> 0,06</td>
<td> 6</td><td> 135 699</td><td> 404</td><td> 1 566</td><td> 0,34</td>
Titanium content of the supported catalyst in pmol / g support (silica + MAO) <sup>3</sup> The molar ratio of aluminum to titanium in the supported catalyst <sup>4</sup> pmol of titanium added to the reactor as a supported catalyst <sup>7</sup> Grams of polymer produced <sup>8</sup> Catalytic efficiency expressed in grams of titanium in the supported catalyst <sup>9</sup> Catalytic efficiency expressed in grams of silica in the supported catalyst <sup>10</sup> Catalytic efficiency expressed in grams of aluminum in the supported catalyst
Example 25
Example 2 was repeated using 5 grams of silica and 101 grams of MAO solution to give a free-flowing powder. The powder was heated at 100 ° C for eight hours under vacuum to give 12.5 g of material. The support was suspended in toluene (125 ml) at 90 ° C and the mixture was stirred for 1 hour. The mixture was filtered and the support was washed with two 50 ml portions of fresh toluene (90 ° C), then dried under vacuum at 100 ° C for 1 hour. The weight of this product was 11.1 grams and the measured aluminum content was 26.1 percent by weight. Next, the polymerization procedure was carried out in the same manner as in Example 19, using polymerization conditions including a total pressure of 1.5 MPa and a temperature of 80 ° C, and the polymerization was carried out for one hour. The amounts used and the results obtained are shown in Table VII below.
-37GB 293261 B6
Table Vil
Polymerization procedure
<td>Ti<sup>2</sup> [pmol / g]</td><td>Al / Ti<sup>3</sup></td><td>[Ti]<sup>4</sup> (pmol)</td><td>Yield<sup>7</sup> (grams)</td>
<td> 40</td><td> 242</td><td> 20</td><td> 365</td>
<td colspan="4"></td>
<td>E (Ti)<sup>8</sup> [gPe / gTi / hr]</td><td>E (SiO<sub>2</sub>)<sup>9</sup> [gPE / gSiO<sub>2</sub>/ h]</td><td>E (Al)<sup>10</sup> [gPE / gAl / h]</td><td>Bulk density (g / cm<sup>3</sup>)</td>
<td> 381 002</td><td> 1 662</td><td> 2 797</td><td> 0,33</td>
Titanium content of the supported catalyst in pmol / g support (silica + MA0)
The molar ratio of aluminum to titanium in the supported catalyst <sup>4</sup> pmol of titanium added to the reactor as a supported catalyst <sup>7</sup> Grams of polymer produced <sup>8</sup> Catalytic efficiency expressed in grams of titanium in the supported catalyst <sup>9</sup> Catalytic efficiency expressed in grams of silica in the supported catalyst <sup>10</sup> Catalytic efficiency expressed in grams of aluminum in the supported catalyst
Example 26
The procedure was carried out in the same manner as Example 5 of U.S. Pat. No. 5,240,894 to prepare a supported catalyst component. This procedure was carried out as follows: 0.58 pmol of MCpTi (8.1 mL of a 0.0714 M solution) was added to 35 mL of toluene. To this solution was added 75 mL of 10 wt% MAO in toluene and the mixture was stirred for 15 minutes. Silica (5 grams of SD 3216.30, which had been pretreated at 250 ° C for three hours) was then added and the mixture was stirred for 20 minutes. The mixture was heated at 65 ° C under vacuum for 75 minutes and the dried solid was washed with two 70 mL portions of pentane, filtered and dried under high vacuum to give a yellow solid (8 grams). ) in which the aluminum content was 18.1 percent by weight. Toluene extraction at 90 ° C followed by drying of the product gave a yellow solid with an aluminum content of 16.2 weight percent. The proportion of extractable aluminum was 10.5 percent by weight. After washing, there was some loss of MCpTi, which also occurred during hot toluene extraction, as determined by the yellow color of the supernatant. The polymerization experiments were carried out in the same manner as in Example 19, using a supported catalyst which had not been treated with hot toluene (Experiment 1) and a supported catalyst which had been treated with hot toluene (Experiment 2). The results obtained are shown in Table VIII below.
From the above results, it can be seen that the catalyst not treated with toluene (which had 10.5 weight percent extractable aluminum) had a poor bulk density. In the case where the supported catalyst was subjected to hot toluene extraction, the bulk density improved considerably (Experiment 2).
-38GB 293261 B6
Table VIII
<td>Experiment no.</td><td>Al (%)</td><td>Time (minutes)</td><td>Yield (grams)</td><td>Bulk density (g / cm<sup>J</sup>)</td>
<td> 1</td><td> 18,1</td><td> 60</td><td> 175</td><td> 0,10</td>
<td> 2</td><td> 16,2</td><td> 60</td><td> 50</td><td> 0,30</td>
Example 27
A 1000 ml flask was used to which 508 grams of 10 weight percent MAO solution in toluene and 25 grams of Sylopol 2212 silica having a water content of 3.5 percent were added at a rate of 10% by weight. simultaneous mixing. The mixture was stirred for an additional two hours and the solvent was removed under reduced pressure at 20 ° C to give a free-flowing powder. The powder was then heated at 175 ° C for two hours under vacuum. The resulting powder was resuspended in toluene (700 mL) and the mixture was refluxed for one hour. The mixture was then filtered and the support was washed with two 200 ml portions of fresh toluene at 100 ° C. The support was dried under vacuum at 120 ° C for one hour. 63.9 grams of carrier material having an aluminum content of 26.4 percent were obtained. A sample of this support was suspended in toluene, stirred for one hour, and then the particle size distribution was measured using a Malvem Mastersizer X instrument. A d (v, 0.5) of about 12 microns was found in this measurement. In this manner, other supported catalytic components having a slightly different aluminum content were prepared.
The weighed amount of the carrier component was suspended in hexane and the mixture was stirred for 16 hours before the MCpTi component (experiments 1-3) or {(tert-butylamido) (tetramethyl-n) was added.<sup>5</sup>-cyclopentadienyl) (dimethyl) silane} titanium D<sup>4</sup>-1,3-pentadiene (referred to herein as MCpTi (II) in Experiment 4). MCpTi or MCpTi (II) were then added in the amounts indicated in the following Table IX (added to vlsopar E ™). The supported catalysts were then slurried at 80 ° C using the general procedure of Example 19. Further conditions and results are shown in Table IX. From these results, it can be seen that using a longer dispersion period prior to the addition of the transition metal compound will increase the catalytic efficiency (as compared to Table III).
Table IX
<td>Experiment no.</td><td>Transition metal compound</td><td>Al</td><td>Ti</td><td>Al / Ti</td>
<td> 1</td><td>MCpTi</td><td> 27,5</td><td> 120</td><td> 85</td>
<td> 2</td><td>MCpTi</td><td> 26,4</td><td> 80</td><td> 122</td>
<td> 3</td><td>MCpTi</td><td> 27,5</td><td> 100</td><td> 102</td>
<td> 4</td><td>MCpTi</td><td> 25,7</td><td> 40</td><td> 238</td>
<td>Experiment no.</td><td>[Ti] (pmol)</td><td>Time (minutes)</td><td>Yield (grams)</td>
<td> 1</td><td> 30</td><td> 79</td><td> 950</td>
<td> 2</td><td> 20</td><td> 85</td><td> 1 020</td>
<td> 3</td><td> 30</td><td> 60</td><td> 1 000</td>
<td> 4</td><td> 20</td><td> 56</td><td> 900</td>
-39GB 293261 B6
Table IX (continued)
<td>Experiment no.</td><td>E (Ti) [gPe / g Ti / h]</td><td>E (SiO<sub>2</sub>) [gPE / gSiO<sub>2</sub>/ h]</td><td>E (A1) [gPE / gAl / h]</td><td>Bulk density (g / cm<sup>3</sup>)</td>
<td> 1</td><td> 502 101</td><td> 7052</td><td> 10 495</td><td> 0,37</td>
<td> 2</td><td> 751 566</td><td> 6653</td><td> 10 909</td><td> 0,35</td>
<td> 3</td><td> 695 894</td><td> 8145</td><td> 12 121</td><td> 0,27</td>
<td> 4</td><td> 1 006 561</td><td> 4036</td><td> 4504</td><td> 0,32</td>
Example 28
A 3-liter autoclave was added to which a portion of 1-octene was added, as indicated in Table X below, followed by an addition of Isopar ™ E in an amount sufficient to provide a total volume of 1500 milliliters. 10,300 milliliters of hydrogen gas were then introduced and the reactor contents heated to the desired temperature. Ethylene was then added in sufficient quantity to increase the system pressure to 3.0 MPa. The supported catalyst was then added to initiate polymerization, and ethylene was fed to the reactor in a continuous manner as needed. After the desired polymerization time had passed, the ethylene feed was stopped and the reactor contents were discharged to a sample tank. The polymer was then dried overnight and weighed to determine the catalytic activity. The results obtained are summarized in Table X, with the molecular weight distribution (M<sub>w</sub>/ M<sub>n</sub>) was obtained by gel permeation chromatography method and melt index I<sub>2</sub> was determined by the method of ASTM D-1238-65T (at 190 ° C and 2.16 kilogram load).
The following supported catalysts were used in the polymerization experiments. A support containing 23.8 percent aluminum on SD 3216.30 dehydrated silica was prepared as described in Example 10. In experiments 1-3, 0.075 g of support was suspended in Isopar ™, and the mixture was stirred for 25 minutes . An aliquot of the MCpTi solution (0.0714 M) was then added in sufficient quantity to achieve a titanium fraction of 20 pmol / g. The mixture was stirred for a few minutes and transferred to the polymerization reactor. In experiments 4 to 6, 0.3 g of support material and the same proportion of titanium were used.
Table X
<td>Experiment no.</td><td>1-octene (ml)</td><td>Time (minutes)</td><td>Yield (grams)</td><td>Average temperature (° C)</td>
<td> 1</td><td> 302</td><td> 20</td><td> 69</td><td> 81</td>
<td> 2</td><td> 382</td><td> 20</td><td> 55</td><td> 80</td>
<td> 3</td><td> 456</td><td> 17</td><td> 35</td><td> 80</td>
<td> 4</td><td> 455</td><td> 20</td><td> 244</td><td> 133</td>
<td> 5</td><td> 455</td><td> 20</td><td> 217</td><td> 143</td>
<td> 6</td><td> 457</td><td> 20</td><td> 200</td><td> 152</td>
-40GB 293261 B6
<td>Experiment no.</td><td>Efficiency (gPE / gTi)</td><td>AND<sup>2</sup> (g / 10 minutes)</td><td>Density (g / cm<sup>J</sup>)</td><td>M<sub>w</sub>/ M<sub>n</sub></td>
<td> 1</td><td> 960 334</td><td> 0,25</td><td> 0,882</td><td> 2,18</td>
<td> 2</td><td> 765 484</td><td> 0,25</td><td> 0,873</td><td> 2,09</td>
<td> 3</td><td> 487 126</td><td> 0,41</td><td> 0,870</td><td> 2,09</td>
<td> 4</td><td> 848 990</td><td> 1,30</td><td> 0,877</td><td> 2,44</td>
<td> 5</td><td> 755 045</td><td> 0,47</td><td> 0,882</td><td> 2,88</td>
<td> 6</td><td> 695 894</td><td> 0,33</td><td> 0,880</td><td> 2,99</td>
When using supported catalysts in solution polymerization processes, the supported catalysts showed good performance and the polymers and polymers had a narrow molecular weight distribution.
Example 29
Continuous polymerization experiments were carried out. These experiments were carried out using a supported catalyst prepared by a procedure similar to that of Example 27. The support material contained 25 weight percent aluminum. In all experiments, the MCpTi fraction was 40 pmol / gram.
Isopentane, ethylene, 1-butene, hydrogen and the supported catalyst were fed continuously to a 10 liter jacketed, continuously stirred tank reactor, and the slurry was collected continuously. The total pressure in all polymerization experiments was 1.5 MPa. The suspended suspension was introduced into a flash tank to remove the diluent used to obtain a dry, free-flowing polymer powder. Table IX summarizes the conditions and properties of the product produced. The melt flow index was measured by the method of ASTM D1238-65T (at a temperature of 190 ° C and a load of 21.6 kilograms, the abbreviation for this melt flow index being I21). The butene content of the polymer was determined by infrared spectroscopy. From these results, it can be seen that the high bulk density of the polymer powder can be obtained over a wide range of densities while maintaining the morphology of the particles.
Table XI
<td>Experiment no.</td><td>Isopentane flow rate (g / h)</td><td>Ethylene flow rate (g / h)</td><td>Flow rate of butene (g / h)</td><td>Hydrogen flow rate (1 / h)</td>
<td> 1</td><td> 2500</td><td> 1600</td><td> 195</td><td> 0,54</td>
<td> 2</td><td> 2500</td><td> 1000</td><td> 80</td><td> 0,30</td>
<td> 3</td><td> 2500</td><td> 800</td><td> 80</td><td> 0,30</td>
<td> 4</td><td> 2500</td><td> 1150</td><td> 125</td><td> 0,30</td>
<td> 5</td><td> 2500</td><td> 850</td><td> 100</td><td> 0,30</td>
<td> 6</td><td> 2500</td><td> 650</td><td> 100</td><td> 0,30</td>
<td> 7</td><td> 2500</td><td> 550</td><td> 160</td><td> 0,50</td>
-41 GB 293261 B6
<td>Experiment no.</td><td>Temperature (° C)</td><td>Li (g / 10 minutes)</td><td>Density (g / cm<sup>3</sup>)</td><td>Butene content in polymer (wt%)</td><td>Bulk density (g / cm<sup>3</sup>)</td>
<td> 1</td><td> 60</td><td> 1.28</td><td> 0,9305</td><td> 1,94</td><td> 0,34</td>
<td> 2</td><td> 60</td><td> 0.38</td><td> 0,9136</td><td> 5,58</td><td> 0,34</td>
<td> 3</td><td> 55</td><td> 0,28</td><td> 0,9190</td><td> 6,34</td><td> 0,38</td>
<td> 4</td><td> 55</td><td> 0.18</td><td> 0,9112</td><td> 8,54</td><td> 0,39</td>
<td> 5</td><td> 55</td><td> 0,21</td><td> 0,9050</td><td> 10,18</td><td> 0,37</td>
<td> 6</td><td> 55</td><td> 0.45</td><td> 0,9035</td><td> 11,64</td><td> 0,38</td>
<td> 7</td><td> 35</td><td> 0.40</td><td> 0,8958</td><td> 14,60</td><td> 0,23</td>
PATENT CLAIMS
Contents26
4 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4
76 members in 27 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 34098994 | United States of America | A | |
| 34098994 | United States of America | A | |
| 1994340989 | – | – | – |
| US19940340989 | – | – | – |
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2 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
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|---|---|---|
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| Pending as of 2000-06-30 in czech republicPD00 | PD00 |
Numbers
- Publication, DOCDB
- 293261
- Publication, EPODOC
- CZ293261
- Application
- 19971522
- Application, DOCDB
- 152297
- Application, EPODOC
- CZ19970001522
Titles2
- Czech
- Nanesená katalytická komponenta, nanesený katalyzátor, způsob jejich přípravy a jejich použití
- English
- Supported catalyst component, supported catalyst, process of their preparation and use
Classification
- CPC, 7
- C08F10/00
- C08F4/61912
- C08F4/61916
- C08F4/6192
- C08F10/02
- C08F110/02
- C08F210/16
- IPC, 9
- C08F4 642
- B01J31 38
- C08F4 602
- C08F4 619
- C08F4 6192
- C08F10 00
- C08F10 02
- C08F110 02
- C08F210 16