CATALYTIC SYSTEM, METHOD FOR PREPARING THE CATALYTIC SYSTEM AND METHOD FOR POLYMERIZATION OF OLEFINS

专利摘要:
catalytic systems and methods for using them for the production of polyolefin products. the present invention relates to catalytic systems and methods for making and using them. the catalytic system may include a single site catalytic compound, a support comprising fluorinated alumina, and an aluminoxane. aluminoxane can be present in an amount of about 10 mmoles or less per gram of the support.
公开号:BR112012021122B1
申请号:R112012021122-6
申请日:2011-02-18
公开日:2020-01-07
发明作者:Kevin J. Cann；C. Jeff Harlan；Wesley R. Mariott；Lixin Sun；Daniel P. Zilker；F. David Hussein；Phuong A. Cao；John H. Moorhouse；Mark G. Goode
申请人:Univation Technologies, Llc；
IPC主号:

专利说明:

CATALYTIC SYSTEM, METHOD FOR PREPARING THE CATALYTIC SYSTEM AND METHOD FOR POLYMERIZATION OF OLEFINS.
Background of the Technique [0001] Numerous catalyst compositions containing single site catalysts are already used to prepare polyolefins, producing relatively homogeneous copolymers at satisfactory polymerization rates. Unlike traditional compositions with Ziegler-Natta catalysts, single site catalyst compositions, such as metallocene-based catalysts, are catalytic compounds in which each catalyst molecule contains one or only a few polymerization sites.
[0002] To obtain acceptable and economically viable polymerization activities with single site catalytic systems, a large amount of activator such as methylaluminoxane (MAO) is generally required. Such activators are generally expensive and the large amount of activator to produce an active single site catalyst for polymerization has been a major obstacle to the commercialization of single site catalysts for the production of polyolefins. Therefore, new compositions with single site catalysts are necessary for the polymerization of olefins and methods for making and using them.
Summary of the invention [0003] The present invention relates to catalytic systems and methods for making and using them. The catalytic system can include a single site catalytic compound, a support comprising fluorinated alumina, and an aluminoxane, preferably methylaluminoxane, modified methylaluminoxane, or a combination thereof. Aluminoxane can be present in an amount of about 10 mmoles or less per gram of the support.
Detailed Description of the Invention [0004] It was surprising and unexpectedly observed that when a support containing alumina is fluorinated, a high level of catalytic productivity is obtained by increasing the concentration of the transition metal component in
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2/71 single site catalytic compound. The catalytic system can include an activator, for example, one or more aluminoxanes, in an amount of about 10 mmoles or less per gram of support. It was also surprising and unexpectedly discovered that a high level of catalyst productivity is achieved with the use of a small amount of activator, that is, about 3 mmoles or less per gram of support, when the support is a support containing alumina that has been removed. fluorinated.
[0005] The transition metal component of the single site catalytic compound can be present in an amount ranging from as little as about 0.2% by weight, about 0.5% by weight, or about 0.7% in weight to as high as about 1% by weight, about 2% by weight, about 2.5% by weight, about 3% by weight, about 3.5% by weight, or about 4% by weight, based on the total weight of the catalytic system. Depending, at least in part, on the particular transition metal component the amount of the transition metal component of the single site catalyst can vary. For example, if the transition metal component is Hf, the transition metal component may be present in the single site catalytic compound in an amount of about 0.6% by weight or more, about 0.7% by weight or more, about 0.8% by weight or more, about 0.85% by weight or more, about 0.9% by weight or more, about 0.95% by weight or more, about 1% by weight or more, about 1.05% by weight or more, about 1.1% by weight or more, about 1.15% by weight or more, about 1.2% by weight or more, about 1.25% by weight or more, or about 1.3% by weight or more, based on the total weight of the catalytic system. In another example, the concentration of Hf in a single site catalytic compound containing Hf may be present in an amount of at least 0.8% by weight, at least 0.85% by weight, at least 0.9% by weight. at least 0.95% by weight, at least 1% by weight, at least 1.05% by weight, at least 1.1% by weight, at least 1.15% by weight, at least 1.2 % by weight, at least 1.25% by weight, or at least 1.3% by weight, based on the total weight of the catalytic system. In another example, if the transition metal component is
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Zr, the transition metal component can be present in the single site catalytic compound in an amount ranging from as little as about 0.2% by weight, about 0.25% by weight, about 0.3% by weight , or about 0.35% by weight to as high as about 0.4% by weight, about 0.8% by weight, about 1% by weight, about 1.2% by weight, or about 1.5% by weight, based on the total weight of the catalytic system. For the purposes of this report, the term “catalytic system” refers collectively to one or more single-site catalytic compounds, activators, and supports.
[0006] By increasing the amount of the transition metal component of the single site catalytic compound, when the support is a support containing fluorinated alumina, the catalyst productivity is increased. Therefore, the use of a support containing fluorinated alumina allows to increase the catalyst productivity by increasing the concentration of the transition metal component of the single site catalytic compound. For example, when using a fluorinated support, the catalyst productivity of the catalytic system can be increased by about 50%, about 60%, about 70%, about 80%, about 90%, about 100% , about 110%, about 120%, about 130%, or more by increasing the amount of the transition metal component of the single site catalytic compound, compared to the same catalytic system using a support containing unfluorinated alumina and a lower concentration of the transition metal component of the single site catalytic system. In other words, for two similar catalytic systems, for example, substantially similar activator concentrations, both including the same support containing fluorinated alumina, and the same single site catalytic compound, the catalyst productivity can be increased by increasing the amount of the transition metal component of the single site catalytic compound.
[0007] It has also been surprisingly and unexpectedly discovered that the catalytic system can be combined with ethylene and one or more organoaluminium compounds within a polymerization reactor in sufficient conditions to produce polyethylene with improved properties. For example, the presence
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4/71 of at least one organoaluminium compound can increase the melt flow rate (MFR) or (I21 / I2) of the polymer compared to using the same catalytic system, however in the absence of at least one organoaluminium compound. For example, the melt flow ratio (MFR) of a polymer can be increased by about 1%, about 3%, about 5%, about 8%, about 10%, about 13%, about 15%, about 18%, about 20%, about 23%, about 25%, about 27%, or about 30% by adding one or more organoaluminium compounds to the polymerization reactor compared to when one or more organoaluminium compounds are absent in the reactor. In another example, the melt flow rate (MFR) can be increased by about 10% to about 20%, or about 15% to about 25%, or about 15% to about 22%, or about 13% to about 25% by introducing at least one organoaluminium compound to the polymerization reactor. As used in this report, the terms MFR and I21 / I2 refer interchangeably to the ratio of the flow index (FI or I ₂₁ ) to the melting index (MI or I ₂ ). MI (I2) can be measured according to the ASTM D1238 standard (at 190 ° C, 2.16 kg in weight). FI (I ₂₁ ) can be measured according to ASTM D1238 (at 190 ° C, 21.6 kg in weight).
[0008] The amount of one or more organoaluminium compounds within the polymerization reactor can vary from about 1 ppmw to about 100 ppmw. For example, the one or more organoaluminium compounds may be present within the polymerization reactor in an amount of about 5 ppmw to about 15 ppmw, about 8 ppmw to about 14 ppmw, about 5 ppmw to about 60 ppmw, about 10 ppmw to about 40 ppmw, or about 5 ppmw to about 30 ppmw. In another example, the one or more organoaluminium compounds may be present within the polymerization reactor in an amount ranging from as little as about 1 ppmw, about 3 ppmw, about 5 ppmw, about 7 ppmw, or about from 10 ppmw to as high as about 15 ppmw, about 20 ppmw, about 25 ppmw, about 30 ppmw, about 40 ppmw, or about 50 ppmw. The one or more compounds
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5/71 organoaluminium can be introduced separately or independently of the catalytic system in the polymerization reactor. The one or more organoaluminium compounds can be combined with the catalytic system and introduced into the polymerization reactor as a mixture. For example, the catalytic system and organoaluminium compounds can be combined with each other and introduced as a sludge into the polymerization reactor.
[0009] The single site catalytic compound, the activator, and the support can be combined in any order or sequence to produce the catalytic system. The order or sequence of preparation of the catalytic system has negligible or no effect on catalyst productivity. For example, the one or more single site catalytic compounds and activators can be combined to produce a catalyst / activator mixture, and the support and catalyst / activator mixture can be added independently to a polymerization reactor. The support, the single site catalytic compound, and the activator can be combined and introduced as a single catalytic system into the polymerization reactor. Alternatively, the single site catalytic compound and the activator can first be combined to produce a catalyst / activator mixture and then the support can be added to the catalyst / activator mixture to produce the catalyst system. Alternatively, the single site catalytic compound and the activator can be combined to produce a catalyst / activator mixture and then the catalyst / activator mixture can be added to the support to produce the catalyst system. Alternatively, the support and the activator can first be combined to produce a catalyst / activator mixture and then the single site catalytic compound can be added to the catalyst / activator mixture to produce the catalyst system. The single site catalytic compound can be added to the catalyst / activator mixture prior to its introduction into the polymerization reactor or the single site catalytic compound and the catalyst / activator mixture can be independently introduced into the polymerization reactor and combined therein.
[0010] One or more thinners or carriers can be used to facilitate
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6/71 the combination of any two or more components of the catalytic system. For example, the single site catalytic compound and the activator can be combined in the presence of toluene or another non-reactive hydrocarbon or a mixture of hydrocarbons to provide the catalyst / activator mixture. In addition to toluene, other suitable diluents may include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof. The support, whether dry or mixed with toluene, can then be added to the catalyst / activator mixture or the catalyst / activator mixture can be added to the support.
[0011] The activator is preferably an aluminoxane, more preferably methylaluminoxane (MAO) or modified methylaluminoxane (MMAO) or a combination thereof. The amount of aluminoxane can be determined based on the amount of aluminum (A1) contained in the aluminoxane. Aluminoxane can be present in the catalytic system in an amount ranging from as little as about 0.1 mmoles to about 10 mmoles. For example, aluminoxane can be present in the catalytic system in an amount of about 9.5 mmoles or less, about 9 mmoles or less, about 8 mmoles or less, about 7.5 mmoles or less, about 7 mmoles or less, about 6.5 mmoles or less, about 6 mmoles or less, about 5.5 mmoles or less, about 5 mmoles or less, about 4.5 mmoles or less, about 4 mmoles or less, about 3.5 mmoles or less, about 3 mmoles or less, about 2.5 mmoles or less, or about 2 mmoles or less per gram of the support. For example, aluminoxane can be present in the catalytic system in an amount ranging from as little as about 0.1 mmoles, about 0.5 mmoles, about 1 mmoles, or about 1.5 mmoles to as high as about 3 mmoles, about 5 mmoles, about 6 mmoles, about 6.3 mmoles, about 6.5 mmoles, about 6.7 mmoles, about 7 mmoles, or about 8 mmoles per gram of the support, with suitable ranges comprising the combination of any lower amount and any higher amount. Preferably, aluminoxane is present in the
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7/71 catalytic system in an amount of about 3 mmoles or less, about 2.7 mmoles or less, about 2.5 mmoles or less, about 2.3 mmoles or less, or about 2 mmoles or less per gram of support. Aluminoxane can be present in the catalytic system in an amount ranging from as little as about 0.1 mmoles, about 0.5 mmoles, about 1 mmoles, or about 1.5 mmoles to as high as about 2 mmoles , about 2.5 mmoles, about 2.6 mmoles, about 2.7 mmoles, about 2.8 mmoles, about 2.9 mmoles, or about 3 mmoles per gram of the support, with suitable bands comprising the combination of any lower quantity and any upper quantity. Preferably, aluminoxane can be present in the catalytic system in an amount ranging from about 1 mmoles to about 3.5 mmoles per gram of support, about 1.5 mmoles to about 3 mmoles per gram of support, about 1.5 mmoles to about 2.8 mmoles per gram of support, about 2 mmoles to about 2.9 mmoles per gram of support, or about 1 mmoles to about 2.8 mmoles per gram of support, with suitable ranges comprising the combination of any lower amount and any higher amount.
[0012] The catalytic system having one or more aluminoxanes present in an amount of about 10 mmoles or less, about 9 mmoles or less, about 8 mmoles or less, or 7 mmoles or less, or 6.5 mmoles or less , per gram of the support can have a catalyst productivity of at least 7,000, at least 8,000, at least 9,000, at least 10,000, at least 1,000, at least 13,000, at least 14,000, at least 15,000, at least at least 16,000, or at least 17,000 grams of polymer per gram of catalytic system. For example, the catalytic system having one or more aluminoxanes present in an amount of about 8 mmoles or less per gram of support can have a catalyst productivity ranging from as little as about 7,000, about 8,000, or about 9,000 to as high as about 12,000, about 16,000, about 20,000, about 24,000, about 26,000, about 28,000, or about 30,000 grams of polymer per
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8/71 gram of catalytic system, with suitable ranges comprising the combination of any lower productivity and any higher productivity. In another example, the catalytic system having one or more aluminoxanes present in an amount of about 7 mmoles or less, per gram of support can have a catalyst productivity ranging from as little as about 5,000, about 6,000, about 7,000 or about 8,000 to as high as about 12,000, about 16,000, about 20,000, about 24,000, about 26,000, about 28,000, or about 30,000 grams of polymer per gram of catalytic system, with suitable ranges comprising the combination of any lower productivity and any higher productivity.
[0013] The catalytic system having one or more aluminoxanes present in an amount of about 3 mmoles or less, or 2.5 mmoles or less, or 2 mmoles or less, per gram of the support can have a catalytic activity productivity of at least at least 2,000, at least 2,500, at least 3,500, at least 4,000, at least 4,500, at least 5,000, at least 6,500, at least 6,000, at least 7,000, at least 7,500, at least 8,000, at least 8,500 at least 9,000, at least 9,500, or at least 10,000 grams of polymer per gram of catalytic system. For example, the catalytic system having one or more aluminoxanes present in an amount of about 3 mmoles or less per gram of support can have a catalyst productivity ranging from as little as about 3,000, about 6,000, or about 7,000 to as high as about 12,000, about 16,000, about 20,000, about 24,000, about 26,000, about 28,000, or about 30,000 grams of polymer per gram of catalytic system, with suitable ranges comprising the combination of any lower productivity and any higher productivity. Preferably, the catalytic system having one or more aluminoxanes present in an amount of about 2.5 mmoles or less, or 2 mmoles or less, per gram of support can have a catalyst productivity ranging from as little as about 2,000, about 3,000, or about 4,000 up to as high as about 8,000, about 10,000, about
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12,000, about 14,000, about 16,000, about 20,000, about 24,000, about 26,000, or about 30,000 grams of polymer per gram of catalytic system, with suitable ranges comprising the combination of any lower productivity and any higher productivity.
[0014] The catalytic system having MAO or MMAO or both present in an amount of about 1 mmoles to about 10 mmoles per gram of support and a metal concentration of the single site catalyst ranging from about 0.2% by weight to about 1.3% by weight based on the total weight of the catalytic system, when the support is a support containing alumina that has been fluorinated, it can have a catalyst productivity of at least 7,000, at least 8,000, at least 10,000, at least at least 11,000, at least 12,000, at least 13,000, at least 14,000, at least 15,000, at least 16,000, or at least 17,000 grams of polymer per gram of catalytic system. For example, the catalytic system having MAO or MMAO or both present in an amount of about 2 mmoles to about 7 mmoles per gram of support and a metal concentration of the single site catalyst, for example, Hf, ranging from about 0.9% by weight to about 1.2% by weight based on the total weight of the catalytic system, when the support is a support containing alumina that has been fluorinated, it can have a catalyst productivity ranging from as little as about 7,000 , about 8,000, about 9,000, or about 10,000 even as high as about 12,000, about 14,000, about 16,000, about 18,000, about 20,000, about 22,000, about 24,000, about 27,000, or about 30,000 grams of polymer per gram of catalytic system, with suitable ranges comprising the combination of any lower productivity and any higher productivity.
[0015] The catalytic system having MAO or MMAO or both present in an amount of about 3 mmoles or less per gram of support can have a catalyst productivity of at least 2,000, at least 4,000, at least 6,000, at least 8,000, or at least 10,000 grams of polymer per gram of catalytic system per hour. The catalytic system having MAO or MMAO
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10/71 or both present in an amount of about 3 mmoles or less per gram of support can have a catalyst productivity ranging from as little as about 2,000, about 3,000, about 4,000, about 5,000, about 7,000 , or about 8,000 to as high as about 12,000, about 16,000, about 18,000, about 20,000, about 22,000, about 24,000, about 26,000, about 28,000, or about 30,000 grams of polymer per gram catalytic system, with suitable ranges comprising the combination of any lower productivity and any higher productivity. Support [0016] As used in this report, the terms support and “vehicle are used interchangeably and refer to any support material, including a porous support material, such as talc, inorganic oxides, and inorganic chlorides. Other supports may include resinous support materials such as polystyrene, functionalized or cross-linked organic supports, such as polystyrene divinyl benzene polyolefins or other polymeric compounds, or any other organic or inorganic support material and the like, or mixtures thereof.
[0017] One or more single site catalytic compounds can be supported on the same support or on separate supports together with the activator, or the activator can be used in an unsupported form, or can be deposited on a support different from the catalytic compounds of single site, or any combination thereof. This can be done by any technique commonly used in the literature. There are several other methods in the literature for supporting a single site catalytic compound. For example, the single site catalyst compound may contain a polymer bound ligand as described, for example, in US Patents ^Nos 5,473,202 and 5,770,755. The single site catalytic compounds can be spray dried as described, for example, in US Patent No. 5,648,310. The support used with the single site catalytic compound can be functionalized, as described in EP 0 802 203, or at least one substituent or displaceable group is selected as described in
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US Patent No. 5,688,880.
[0018] The support can be or can comprise one or more inorganic oxides. The support may be an inorganic oxide that includes one or more metal oxides of elements of group 2, 3, 4, 5, 13, or 14. For example, the inorganic oxide may include, but is not limited to, alumina, silica, titania, zirconia, boron, zinc oxide, magnesia, or any combination thereof. Illustrative combinations of oxides may include, but are not limited to, alumina, silica-titania, alumina-silica-titania, alumina-zirconia, alumina-titania, among others. The support can be or can include alumina, silica, or a combination thereof.
[0019] Supports that include two or more inorganic oxides can have any proportion or quantity of each oxide, in relation to the others, can be used. For example, an alumina-silica support for catalysts can include from about 1 wt% alumina to about 99 wt% alumina, based on the total amount of alumina and silica. In one or more embodiments, an alumina-silica support for catalysts can have an alumina concentration ranging from as little as about 2% by weight, about 5% by weight, about 15% by weight, or about 25 % by weight to as high as about 50% by weight, about 60% by weight, about 70% by weight, or about 90% by weight, based on the total amount of alumina and silica. For example, the alumina concentration of the alumina-silica support for catalysts can be about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, about 50% by weight, about 55% by weight, about 60% by weight, about 70% by weight, about 80% by weight, or about 90% in weight. In another example, the aluminum concentration of the support can vary from as little as about 2% by weight, about 3% by weight, about 4% by weight or about 5% by weight to as high as about 10% by weight, about 20% by weight, about 30% by weight, about 40% by weight, or about 45% by weight, based on the weight of the support. In another example, the aluminum concentration of the support
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12/71 can range from about 2 wt% to about 12 wt%, about 3 wt% to about 10 wt%, about 4 wt% to about 8 wt% or about 3% by weight to about 7% by weight, based on the weight of the support. In another example, the aluminum concentration of the support can vary from as little as about 20% by weight, about 23% by weight, or about 25% by weight to as high as about 35% by weight, about 40% by weight, or about 45% by weight, based on the weight of the support.
[0020] Suitable commercially available silica supports may include, but are not limited to, ES757, ES70, and ES70W available from PQ Corporation. Suitable commercially available silica-alumina supports include, but are not limited to, SIRAL® 1, SIRAL® 5, SIRAL® 10, SIRAL® 20, SIRAL® 28M, SIRAL® 30, and SIRAL® 40, available from SASOL®.
[0021] A mixed inorganic oxide support for catalysts can be prepared using any suitable method. For example, a silica support for catalysts can be mixed, blended, contacted, or in any other way combined with one or more aluminum compounds to produce a mixture of silica support and aluminum compounds. The silica support for catalysts can be mixed with one or more aluminum compounds in an aqueous and / or alcoholic solution and dried to produce the mixture of silica support and aluminum compounds. Suitable alcohols may include, but are not limited to, alcohols having 1 to 5 carbon atoms, and mixtures or combinations thereof. For example, alcohol can be or can include methanol, ethanol, propan-1-ol, propan-2-ol, among others. Suitable aluminum compounds may include, but are not limited to, aluminum monoacetate ((HO) 2AlC2H3O2), aluminum diacetate (HOAl (C ₂ H ₃ O ₂ ) ₂ ), and aluminum triacetate (Al (C ₂ H ₃ O ₂ ) ₃ ), aluminum hydroxide (Al (OH) 3), aluminum diacetate hydroxide (Al (OAc) 2OH), aluminum triacetylacetonate, aluminum fluoride (AIF ₃ ), sodium hexafluoraluminate (Na3AlF6), or any combination of the same.
[0022] The support mixture of silica and aluminum compounds can be heated (calcined) in the presence of one or more inert, oxidizing gases,
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13/71 reducing agents, or in any order / combination thereof to produce an alumina-silica support for catalysts. As used in this report, the term oxidizer may include, but is not limited to, air, oxygen, ultra-zero air, oxygen / inert gas mixtures, or any combination thereof. Inert gases may include, but are not limited to, nitrogen, helium, argon, or combinations thereof. Reducing gases may include, but are not limited to, hydrogen, carbon monoxide, or combinations thereof.
[0023] The support mixture of silica and aluminum compounds can be heated to a first temperature in nitrogen gas or other inert gas. After heating to the first temperature, the nitrogen gas can be stopped, one or more oxidants can be introduced, and the temperature can be increased to a second temperature. For example, the support mixture of silica and aluminum compounds can be heated in an inert atmosphere to a temperature of about 200 ° C, the oxidizer can be introduced, and the mixture can then be heated to a temperature of about 450 ° C. ° C to about 1,500 ° C to produce an alumina-silica support for catalysts. The second temperature can range from as low as about 250 ° C, about 300 ° C, about 400 ° C, or about 500 ° C to as high as about 600 ° C, about 650 ° C, about 700 ° C, about 800 ° C, or about 900 ° C. For example, the second temperature can range from about 400 ° C to about 850 ° C, about 800 ° C to about 900 ° C, about 600 ° C to about 850 ° C, or about 810 ° At about 890 ° C. The support mixture of silica and aluminum compounds can be heated and maintained at the second temperature for a period of time ranging from about 1 minute to about 100 hours. For example, the support mixture of silica and aluminum compounds can be heated and maintained at the second temperature for a period of time ranging from as little as about 30 minutes, about 1 hour, or about 3 hours to as high as about 10 hours, about 20 hours, or about 50 hours. In one or more embodiments, the support mixture of silica and aluminum compounds can be heated from room temperature to the second temperature or a
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14/71 higher temperature without heating to an intermediate temperature or first temperature. The support mixture of silica and aluminum compounds can be heated in a nitrogen atmosphere or other inert atmosphere initially, which can be modified to include the one or more oxidants or the atmosphere can be or can include the one or more oxidants in the initial heating from room temperature.
[0024] The support can be mixed, blended, contacted, or in any other way combined with one or more sources of halide ions, sulfate ions, or a combination of anions to produce a mixture of inorganic oxide support for catalysts and anions, which can be heated or calcined to produce an activated support. For example, one or more halide ion sources, sulfate ion sources, metal ion sources, or any combination thereof, can be mixed dry, that is, mixed without the presence of an intentionally added liquid or liquid, with the inorganic oxide support. In another example, one or more sources of halide ions, sources of sulfate ions, sources of metal ions, or any combination thereof, may be mixed wetly, that is, in the presence of a liquid, with the support of inorganic oxide for catalysts. Illustrative liquids may include, but are not limited to, alcohols, water, or a combination thereof. Suitable alcohols may include, but are not limited to, alcohols having 1 to 5 carbon atoms, and mixtures or combinations thereof. The mixture, whether it is dry mixed or wet mixing, can be calcined to produce an activated support.
[0025] The activated support may include, but is not limited to, brominated alumina, brominated silica alumina, brominated silica, fluorinated alumina, fluorinated silica, fluorinated silica, fluorinated-zirconia alumina, fluorinated-zirconia silica, fluorinated-chlorinated alumina, alumina fluorine-chlorinated-silica, chlorinated alumina, chlorinated-silica alumina, chlorinated silica, sulfated alumina, sulfated-silica alumina, sulfated silica, or any combination thereof. The support can be treated with one or more metal ions in addition to or in place of one or more ion sources
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15/71 halide and / or sources of sulfate ions. Illustrative metal ions may include, but are not limited to, copper, gallium, molybdenum, silver, tin, tungsten, vanadium, zinc, or any combination thereof.
[0026] Illustrative fluorination agents or fluoridants may include, but are not limited to, ammonium hexafluorsilicate ((NH4) ₂ SiF ₆ ), fluorine (F2), fluoridic acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2 ), ammonium tetrafluorborate (NH4BF4), ammonium hexafluorphosphate (NH4PF6), ammonium (V) (NH4) 2TaF2, ammonium (IV) (NH4) 2GeF6, ammonium hexafluortitanate (IV) (NH4) 2TaF2, hexafluoride (2) ammonium (NH4) 2ZrF6, aluminum fluoride (AIF3), sodium hexafluoraluminate (Na3AlF6), molybdenum fluoride (VI) (MoF6), bromine pentafluoride (BF5), nitrogen trifluoride (NF3), ammonium acid fluoride (NF3) NHF2), C6F14 perfluorhexane, hexafluorbenzene (C6F6), fluoromethane (CH3F), trifluorethanol (C2H3F3O), freons, derivatives thereof, or any combination thereof. Illustrative chlorinating or chlorinating agents may include, but are not limited to, freons, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, hydrogen chloride, chlorine, derivatives thereof, or any combination thereof. Illustrative sulfating agents may include, but are not limited to, sulfuric acid, sulfate salts such as ammonium sulfate, or any combination thereof.
[0027] Illustrative freons may include, but are not limited to, trichlorofluoromethane (CCI3F), trichlorodifluoromethane (CCI2F2), chlorotrifluoromethane (CCIF3), chlorodifluoromethane (CHCIF2), dichlorofluoromethane (CHCl2F), chlorofluoromethane, chlorofluoromethane (CHCl2) , 2-trichloro 1,2,2-trifluoroethane (CI2FC-CCIF2), 1,1,1-trichloro-2,2,2-trifluoroethane (CI3C-CF3), 1,2dichloro-1,1,2,2-tetrafluoroethane (ClF2C-CClF2), 1-chloro-1,1, 2,2,2-pentafluorethane (ClF2C-CF3), 2-chloro-1,1,1,2-tetrafluoroethane (CHFCICF3), 1,1-dichloro- 1-fluorethane (CI2FC-CH3), 1-chloro-1,1-difluorethane (ClF2C-CH3), tetrachloro-1,2-difluorethane (CCl2FCCl2F), tetrachloro-1,1-difluorethane (CClF2CCl3), 1,1, 2- trichlorotrifluorethane (CCI2FCCIF2), 1-bromo-2-chloro-1,1,2-trifluorethane (CHClFCBrF2), 2-bromo-2Petition 870190090215, from 9/11/2019, p. 28/95
16/71 chloro-1,1,1-trifluorethane (CF ₃ CHBrCl), 1,1-dichloro-2,2,3,3,3-pentafluorpropane (CF3CF2CHCI2), 1,3-dichloro-1,2,2 , 3,3-pentafluorpropane (CCIF2CF2CHCIF).
[0028] The amount of the halide ion sources, the sulfate ion sources, and / or the metal ion sources mixed with the support can vary from as little as about 0.01% by weight, about 0.1% by weight, or about 1% by weight to as high as about 10% by weight, about 20% by weight, about 30% by weight, about 40% by weight, or about 50% by weight, based on the total weight of the mixture, that is, the support, the halide ion source, the sulfate ion source, and / or the metal ion source. For example, a fluorine agent in an amount of about 0.01 g to about 0.5 g can be combined per gram of inorganic oxide support for catalysts. In another example, the halide ion source may be a fluorine agent, the support may be silica-alumina, and the amount of fluoride in the support may vary from as little as about 2% by weight, about 3% by weight , about 3.5% by weight, about 4% by weight, about 4.5% by weight, or about 5% by weight up to as high as about 8% by weight, about 9% by weight , about 10% by weight, about 11% by weight, or about 12% by weight, based on the weight of the support. In another example, the halide ion source can be a fluorine agent, the support can be silica, calcined in the presence of an aluminum source, and the amount of fluoride in the support can vary from as little as about 1.5 wt%, about 2 wt%, or about 2.5 wt% to as high as about 3.5 wt%, about 4 wt%, about 4.5 wt%, or about 5% by weight, based on the weight of the support.
[0029] The mixture of the support and one or more sources of halide ions, sulfate ions, or a combination of anions can be heated (calcined) in the presence of one or more inert gases, oxidizers, reducing gases, in any order, any combination thereof, or any order / combination thereof to produce an activated support. For example, a fluorine agent / alumina-silica support mixture can be heated to a first temperature in a nitrogen gas purge or other inert gas or combination
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17/71 inert gases. After heating to the first temperature, the inert gas can be stopped, the one or more oxidants can be introduced, and the temperature can be increased to a second temperature. For example, the fluorine / alumina-silica support mixture can be heated in an inert atmosphere to a temperature of about 200 ° C, the oxidant can be introduced, and the mixture can be heated to a temperature of about 600 ° C. ° C or more to produce the activated support. The fluorine / alumina-silica support mixture can be heated to a second temperature ranging from as little as about 250 ° C, about 300 ° C, or about 400 ° C to as high as about 600 ° C , about 750 ° C, or about 900 ° C. The fluorine / alumina-silica support mixture can be heated and maintained at the second temperature for a period of time ranging from about 1 minute to about 100 hours. For example, the fluorine / alumina-silica support mixture can be heated and maintained at the second temperature for a period of time ranging from as little as about 30 minutes, about 1 hour, or about 3 hours to as high about 10 hours, about 20 hours, or about 50 hours.
[0030] One or more sources of halide ions, sources of sulfate ions, and / or sources of metal ions may be introduced during heating or calcination, in place of, or in addition to, combining the sources of halide ions, sources of ions sulfate, and / or sources of metal ions, and the support before heating. [0031] To one or more sources of halide ions, sources of sulfate ions, and / or sources of metal ions may be mixed, blended, contacted, or in any way combined with the mixture of silica support and aluminum compounds. The halide ion sources, sulfate ion sources, and / or metal ion sources, and the combined silica support mixture, and combined aluminum compounds can be heated together, rather than separately, to produce the activated support. For example, a fluoride source such as ammonium hexafluorsilicate ((NH4) 2SiF6) can be combined with the mixture of silica and aluminum compounds, which can then be calcined to produce a
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18/71 fluorinated-silica alumina support.
[0032] The activated catalyst support can have a surface area ranging from as little as about 1 m ² / g, about 50 m ² / g, or about 100 m ² / g to as high as about 400 m / g, about 500 m ² / g, or about 800 m ² / g. The activated catalyst support can have a pore volume ranging from as little as about 0.01 cm ³ / g, about 0.1 cm ³ / g, about 0.8 cm ³ / g, or about 1 cm ³ / g to as high as about 2 cm ³ / g, about 2.5 cm ³ / g, about 3 cm ³ / g, or about 4 cm ³ / g. The activated catalyst support can have an average particle size ranging from as little as about 0.1 pm, about 0.3 pm, about 0.5 μιτι, about 1 μιτι, about 5 μιτι, about 10 μιτ), or about 20 μιτι up to as high as about 50 μιτι, about 100 μιτι, about 200 μιτι, or about 500 μιτι. The average pore size of the activated catalyst support can vary from about 10 Å to about 1,000 Å, preferably from about 50 Å to about 500 Å, and more preferably from about 75 Å to about 350 Å.
[0033] Suitable catalyst supports are discussed and described in Hlatky, Chem. Rev. (2000), 100, 1347 1376 and Fink et al, Chem. Rev. (2000), 100, 1377 1390, US Patent ^Nos: 4,701,432, 4,808,561, 4,912,075, 4,925,821,
4,937,217, 5,008,228, 5,238,892, 5,240,894, 5,332,706, 5,346,925, 5,422,325,
5,466,649, 5,466,766, 5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835,
5,625,015, 5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400, 5,723,402,
5,731,261,5,759,940, 5,767,032 and 5,770,664, and WO 95/32995, WO 95/14044, WO 96/06187, eWO 97/02297.
Activated r [0034] As used in this report, the terms activator and cocatalyst are used interchangeably and refer to any compound or combination of compounds, supported or unsupported, that can activate a single site catalytic compound or component, such as through the creation of a cationic species of the catalytic component. For example, this may include extracting at least one displaceable group (the “X” group in compounds
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19/71 single site catalysts described in this invention) of the metal center of the single site catalytic compound / component.
For example, the activator can include a Lewis acid or a non-coordinating ionic activator or an ionizing activator, or any other compound including Lewis bases, aluminum alkyls, and / or conventional type cocatalysts. In addition to the methylaluminoxane (MAO) and modified methylaluminoxane (MMAO) mentioned above, illustrative activators may include, but are not limited to, aluminoxane or modified aluminoxane, and / or ionizing compounds, neutral or ionic, such as tri (n-butyl) ammonium tetraquis (pentafluorfenil) boron, a metalloid precursor of trisperfluorfenil boron, a metalloid precursor of trisperfluornaftil boron, or any combination thereof.
[0035] Aluminoxanes can be described as aluminum oligomeric compounds having -AI (R) -O-subunits, where R is an alkyl group. Examples of aluminoxanes include, but are not limited to, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, isobutylaluminoxane, or a combination thereof. Aluminoxanes can be produced by hydrolysis of the respective trialkylaluminum compound. MMAO can be produced by hydrolysis of trimethylaluminum and a higher trialkylaluminium such as triisobutylalumin. MMAOs are generally more soluble in aliphatic solvents and more stable during storage. A variety of methods for preparing aluminoxane and modified aluminoxanes, non - limiting examples can be those discussed and described in US Patents ^Nos 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157. 137, 5 103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854. 166, 5,856,256, and 5,939,346, and EP 0 561 476, EP 0 279 586, EP 0 594-218, and EP 0 586 665, and in WO WO 94/10180 and WO 99/15534.
[0036] In one or more modalities, a visually clear MAO can be used. For example, a cloudy and / or gelled aluminoxane can be filtered to produce a clear aluminoxane or a clear aluminoxane can be decanted
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20/71 of a cloudy aluminoxane solution. In another embodiment, a cloudy and / or gelled aluminoxane can be used. Another aluminoxane may include a modified type 3A methyl aluminoxane (MMAO) (commercially available from Akzo Chemicals, Inc. under the trade name type 3A modified methylaluminoxane, discussed and described in US Patent No. 5,041,584). A suitable source of MAO can be a solution having from about 1 wt% to about 50 wt% MAO, for example. Commercially available MAO solutions may include 10% by weight and 30% by weight MAO solutions available from Albemarle Corporation, Baton Rouge, La.
[0037] As noted above, one or more organoaluminium compounds such as one or more alkylaluminium compounds can be used in conjunction with aluminoxanes. For example, the alkyl aluminum species that can be used are diethyl aluminum ethoxide, diethyl aluminum chloride, and / or diisobutyl aluminum hydride. Preferably the alkyl aluminum compound is a trialkyl aluminum compound. Examples of trialkyl aluminum compounds include, but are not limited to, trimethyl aluminum, triethyl aluminum (TEAL), tri-isobutyl aluminum (TiBAI), tri-n-hexyl aluminum, tri-n-octyl aluminum, tripropyl aluminum, tributyl aluminum, among others.
[0038] In at least one specific modality, the catalytic system can be free or substantially free of any intentionally added organoaluminium compound. In other words, in at least one modality, the use of organoaluminium compounds can be avoided or otherwise not intentionally added to the catalytic system.
[0039] In one or more modalities, one or more ionizing or stoichiometric activators, neutral or ionic, can be used in combination with aluminoxane or modified aluminoxane. For example, tri (n-butyl) ammonium tetrakis (pentafluorfenyl) boron, a metalloid precursor of trisperfluorfenyl boron or a metalloid precursor of trisperfluornaftil boron, polyhalogenated heteroborane anions (WO 98/43983), boric acid (US Patent No. 5,942. 459), or combinations thereof can be used. Activator examples
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21/71 neutral stoichiometrics may include tri-substituted boron, tellurium, aluminum, gallium, indium, or any combination thereof. Each of the three substituent groups can be independently selected from alkyl, alkenyl, halogen, substituted alkyl, aryl, aryl halide, alkoxy and halide. Neutral stoichiometric activators include trisperfluorfenil boron or trisperfluornaftil boron.
Catalytic Compound [0040] The single site catalytic compound can be or can include one or more metallocene-based catalysts and other single site catalysts. Other catalytic compounds that can be used include chromium based catalysts, Ziegler-Natta catalysts, transition metal based catalysts, and bimetallic catalysts. For example, the catalytic compound can comprise AICI3, cobalt, iron, chromium / chromium oxide or Phillips catalysts. Any catalyst can be used alone or in combination with others, that is, a "mixed" catalyst.
Catalytic compounds of the metallocene type [0041] Catalytic compounds of the metallocene type are described in general, for example, in 1 & 2 METALLOCENE-BASED POLYOLEFINS (John Scheirs & W. Kaminsky eds., John Wiley & Sons, Ltd. 2000) ; G. G. Hlatky in 181 COORDINATION CHEM. REV. 243-296 (1999) and in particular, for use in the synthesis of polyethylene in 1 METALLOCENE-BASED POLYOLEFINS 261-377 (2000). Catalytic compounds of the metallocene type may include compounds of the "half sandwich" and / or "whole sandwich" type having one or more Cp ligands (cyclopentadienyl and isolobal ligands to cyclopentadienyl) attached to at least one metal atom from group 3 to group 12, and one or more displaceable groups attached to at least one metal atom. As used in this report, all references to the Periodic Table of Elements and groups therein are in accordance with the New Notation published in HAWLEY'S CONDENSED CHEMICAL DICTIONARY, Thirteenth Edition, John Wiley & Sons, Inc., (1997) (reproduced with permission from IUPAC), except where reference is made to the Old form
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IUPAC indicated with Roman numbers (which also appears in it), or unless otherwise indicated.
[0042] Cp ligands are one or more rings or ring systems, at least a portion of them including π-bonded systems, such as cycloalkadienyl type ligands and heterocyclic analogs. The rings or ring systems typically comprise atoms selected from the group consisting of atoms from groups 13 to 16, and, in a particular exemplary embodiment, the atoms that make up the Cp ligands are selected from the group consisting of carbon, nitrogen, oxygen, silicon , sulfur, phosphorus, germanium, boron, aluminum, and combinations thereof, in which carbon constitutes at least 50% of the members of the rings. In a more particular exemplary embodiment, Cp ligands are selected from the group consisting of substituted and unsubstituted cyclopentadienyl ligands and isolobal ligands to cyclopentadienyl, non-limiting examples of them including cyclopentadienyl, indenyl, fluorenyl and other structures. Other non-limiting examples of such binders include cyclopentadienyl, cyclopentafenanthrene, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenantrindenyl, 3,4-benzofluorenyl, 9-phenylfluoren, 8-phenylfluoren, H-dibenzofluorenyl, indene [1, 2-9] anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated versions of them (eg 4,5,6,7-tetrahydroindenyl, or H ₄ Ind), substituted versions of them (such as discussed and described in more detail below), and heterocyclic versions thereof.
[0043] The metal atom M of the catalytic compound of the metallocene type can be selected from the group consisting of atoms from groups 3 to 12 and atoms from the lanthanide group in an exemplary embodiment; and selected from the group consisting of atoms from groups 3 to 10 in a more particular exemplary modality, and selected from the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os , Co, Rh, Ir, and Ni in an even more particular exemplary modality; and selected from the group consisting of atoms from groups 4, 5,
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23/71 and 6 in an even more particular exemplary modality, and Ti, Zr, Hf atoms in an even more particular exemplary modality, and Hf in an even more particular exemplary modality. The oxidation state of the metal atom M can vary from 0 to +7 in an exemplary embodiment; and in a more particular example, it can be +1, +2, +3, +4 or +5; and in an even more particular example, it can be +2, +3 or +4. The groups attached to the metal atom M are such that the compounds described below in the formulas and structures are electrically neutral, unless otherwise indicated. The Cp linkers form at least one chemical bond with the metal atom M to form the "catalytic compound of the metallocene type". Cp ligands are distinct from displaceable groups linked to the catalytic compound in the sense that they are not highly susceptible to substitution / extraction reactions.
[0044] The one or more catalytic compounds of the metallocene type can be represented by the formula (I):
CpACpBMXn (I) where M has the description given above; each X is chemically linked to M; each Cp group is chemically linked to M; and n is 0 or an integer from 1 to 4, and 1 or 2 in a particular exemplary embodiment.
[0045] The ligands represented by CpA and CpB in formula (I) may have the same or different ligands of the cyclopentadienyl type or isolobal ligands to cyclopentadienyl, one or both of which may contain heteroatoms and one or both of them may be substituted with an R group. at least one specific modality, Cp ^A and Cp ^B are independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each.
[0046] Regardless, each CpA and CpB in formula (I) can be unsubstituted or substituted with any of the substituent R groups or a combination of these. Non-limiting examples of substituent R groups used in structure (I) as well as ring substituents in Va-d structures, discussed and described below, include groups selected from the group consisting of
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24/71 in hydrogen radicals, alkyls, alkenyls, alkynyls, cycloalkyls, aryls, acyls, aroyls, alkoxies, aryloxies, alkylthioles, dialkylamines, alkylamides, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamyls, acylsylaminosyls, acylsylaminosyls, acylsylaminosyls, acylsylaminosyls, acylsylaminosyls, acylsylamines and combinations thereof. More particular non-limiting examples of alkyl substituents R associated with formulas (I) to (Va-d) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, and tertiary groups. butylphenyl among others, including all its isomers, for example, tert-butyl, isopropyl, among others. Other possible radicals include substituted alkyls and aryls such as, for example, fluoromethyl, fluorethyl, difluorethyl, iodopropyl, bromohexyl, chlorobenzyl, hydrocarbyl-substituted organometalloid radicals including trimethylasilyl, trimethylgermyl, methylldylethyl, and others, and halocarbonyl-halocarbon radicals. including tris (trifluormethyl) silyl, methylbis (difluormethyl) silyl, bromomethyldimethylgermylyl among others; and disubstituted boron radicals including dimethylboro, for example; and disubstituted group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, as well as group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methyl sulfide and ethyl sulfide. Other substituent R groups include, but are not limited to, olefins, such as olefinically unsaturated substituents including vinyl-terminated binders such as, for example, 3butenyl, 2-propenyl, 5-hexenyl among others. In an exemplary embodiment, at least two R groups (two adjacent R groups in a particular exemplary embodiment) are joined to form an annular structure having 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron and combinations thereof. Also, a substituent group R such as 1-butanyl can form a binding association to the M element.
[0047] Each X in formula (I) above and for formulas / structures (II) to (Va-d) below is independently selected from the group consisting of: a displaceable group, in an exemplary mode; halogen ions, hydrides, C1 to C12 alkyls, C2 to C12 alkenyls, Ce to C12 aryls, C7 to C20 alkylaryls, Ci to C12
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25/71 alkoxides, C ₆ to C ₁₆ aryloxy, C ₇ to C ₈ alkylaryloxis, C1 to C ₁₂ fluoralkyls, C ₆ to C ₁₂ fluoroyl, and Ci to C12 hydrocarbons containing hetero atoms and substituted derivatives thereof, in a more exemplary embodiment particular; hydride, halogen ions, C1 to C6 alkyl, C2 to C6 alkenyl, C7 to C18 alkylaryl, C1 to C ₆ alkoxy, C ₆ to C ₁₄ aryloxy, C ₇ to C ₁₆ alkylaryloxy, C1 to C ₆ alkylcarboxylate, Ci to C6 fluorinated alkylcarboxylates, C6 to C12 arylcarboxylates, C ₇ to C ₁₈ alkylarylcarboxylates, C1 to C ₆ fluoralkyls, C ₂ to C ₆ fluoralkenyls, and C ₇ to C18 fluoralkylylates in an even more particular exemplary embodiment; hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl, fluoromethyl and fluorophenyls, in an even more particular exemplary modality; C1 to C12 alkyls, C ₂ to C ₁₂ alkenyls, C ₆ to C ₁₂ aryls, C ₇ to C ₂₀ alkylaryls, substituted C1 to C12 alkyls, C6 to C12 substituted aryls, C7 to C20 alkylaryls substituted and C1 to C ₁₂ alkyls heteroatoms, C1 to C ₁₂ aryls containing heteroatoms, and C1 to C12 alkylaryls containing heteroatoms, in an even more particular exemplary modality; chloride, fluoride, C1 to C6 alkyls, C2 to C6 alkenyls, C7 to C18 alkylaryls, Ci to C6 halogenated alkyls, C2 to C6 halogenated alkenyls, and C ₇ to C ₁₈ halogenated alkyls, in an even more particular exemplary embodiment; fluoride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyls (mono-, di- and trifluoromethyls) and fluorphenyls (mono-, di-, tri-, tetra- and pentafluorfenyls), in an even more exemplary modality particular; and fluoride, in an even more particular exemplary modality. [0048] Other non-limiting examples of groups X include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (eg - C6F5 (pentafluorfenyl)), fluorinated alkylcarboxylates (by example, CF3C (O) O ^- ), hydrides, halogen ions and combinations thereof. Other examples of X linkers include alkyl groups such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy, phenoxy, bis (N-methylanilide), dimethylamide, dimethylphosphide radicals others. In an exemplary embodiment, two or more X's form a part of a ring
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26/71 cast or an annular system. In at least one specific embodiment, X may be a displaceable group selected from the group consisting of chloride ions, bromide ions, C1 to C ₁₀ alkyls, and C ₂ to C ₁₂ alkenyls, carboxylates, acetylacetonates, and alkoxides.
[0049] The metallocene-type catalytic compound includes those of formula (I) in which Cp ^A and Cp ^B are bridged to each other by at least one bridge group, (A), so that the structure is represented by formula (II):
Cp ^A (A) CpBMXn (II) [0050] These bridged compounds represented by formula (II) are known as bridged metallocenes ”. The elements Cp ^A , CpB, M, X and n in structure (II) have the definition given above for formula (I); wherein each Cp linker is chemically linked to M, and (A) is chemically linked to each Cp. The bridging group (A) can include divalent hydrocarbon groups containing at least one atom from group 13 to 16, such as, but not limited to, at least one among carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium, atom of tin, and combinations thereof; wherein the heteroatom can also be C1 to C12 alkyl or substituted aryl to satisfy the neutral valence. In at least one specific embodiment, the bridging group (A) can also include substituent R groups defined above (for formula (I)) including halogen and iron radicals. In at least one specific embodiment, the bridge group (A) can be represented by C1 to C6 alkylenes, C1 to C6 substituted alkylenes, oxygen, sulfur, R ' ₂ C =, R' ₂ Si =, = Si (R ' ) ₂ Si (R '2) =, R' ₂ Ge =, and R'P =, where = represents two chemical bonds, R 'is independently selected from the group consisting of hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, halocarbil substituted, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted group 15 atoms, substituted group 16 atoms, and halogen radical; and wherein two or more R 'can be joined to form a ring or ring system. In at least one specific embodiment, the bridged metallocene-type catalyst compound of formula (II) includes two or more bridging groups (A). In one or more
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27/71 modalities, (A) can be a divalent bridge group linked to both Cp ^A and CpB selected from the group consisting of Ci to C20 divalent hydrocarbons and C1 to C20 hydrocarbonyls containing hetero atoms, in which hydrocarbonyls containing hetero atoms one to three heteroatoms.
[0051] The bridging group (A) can include methylene, ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene, 1,2-dimethylethylene, 1,2-diphenylethylene, 1,1,2,2-tetramethylethylene, dimethylasilyl, diethylasilyl, methyl-ethylasilyl, trifluormethylbutylsilyl, bis (trifluormethyl) silyl, di (n-butyl) silyl, di (n-propyl) silyl, di (ipropyl) silyl, di (n-hexyl) silyl, dicyclohexylsilyl, diphenylasilyl, cyclohexyl hexylphenylasilyl, tbutylcyclohexylsilyl, di (t-butylphenyl) silyl, di (p-tolyl) silyl and the corresponding portions where the Si atom is replaced by a Ge atom or a C atom; as well as dimethylasilyl, diethylasilyl, dimethylgermila and diethylgermila.
[0052] The bridge group (A) can also be cyclic, having, for example, 4 to 10 members in the ring; in a more particular exemplary embodiment, the bridge group (A) can have 5 to 7 members in the ring. Ring members can be selected from the elements mentioned above, and, in a particular embodiment, they can be selected from one or more of B, C, Si, Ge, N and O. Non-limiting examples of ring structures that may be present as the bridging portion, or as part of the bridging portion, are cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene and the corresponding rings in which one or two carbon atoms are replaced by at least one of Si , Ge, N and O. In one or more modalities, one or two carbon atoms can be replaced by at least one of Si and Ge. The bridged arrangement between the ring and the Cp groups can be cis-, trans-, or a combination thereof.
[0053] Cyclic bridge groups (A) can be saturated or unsaturated and / or can carry one or more substituents and / or can be fused to one or more other ring structures. If present, the one or more substituents may, in at least one specific embodiment, be selected from the group consisting of hydrocarbyl (for example, alkyl, such as methyl) and halogen (for example,
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28/71 example, F, Cl). The one or more Cp groups to which the above cyclic bridge portions can optionally be fused can be saturated or unsaturated, and are selected from the group consisting of those having 4 to 10, more particularly 5, 6, or 7 members in the ring (selected from the group consisting of C, N, O, and S in a particular exemplary embodiment) such as, for example, cyclopentyl, cyclohexyl and phenyl. In addition, the ring structures themselves can be fused as, for example, in the case of a naphthyl group. In addition, these ring structures (optionally fused) can carry one or more substituents. Non-limiting illustrative examples of such substituents are hydrocarbyl groups (particularly alkyl) and halogen atoms.
[0054] The Cp ^A and Cp ^B ligands of formula (I) and (II) can be different from each other. The Cp ^A and Cp ^B linkers of formula (I) and (II) can be the same.
[0055] The catalytic metallocene-type compound may include bridged mono-ligand metallocene compounds (eg, monocyclopentadienyl catalytic components). Exemplary metallocene-type catalytic compounds are further described in US Patent No. 6,943,134.
[0056] We contemplate that the metallocene-based catalytic components discussed and described above include their structural or optical or enantiomeric isomers (racemic mixture), and, in an exemplary modality, may be a pure enantiomer. As used in this report, a single asymmetrically bridged metallocene-type catalytic compound having a racemic isomer and / or a meso isomer does not in itself constitute at least two metallocene-type catalytic components with different bridges.
[0057] As noted above, the amount of the transition metal component of the one or more catalytic compounds of the metallocene type in the catalytic system can vary from as little as about 0.2% by weight, about 3% by weight, about 0.5 wt%, or about 0.7 wt% to as high as about 1 wt%, about 2 wt%, about 2.5 wt%, about
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3% by weight, about 3.5% by weight, or about 4% by weight, based on the total weight of the catalytic system.
[0058] The "metallocene-type catalytic compound" may include any combination of any "modality" discussed and described in this report. For example, the metallocene-type catalytic compound may include, but is not limited to, bis (n-propylcyclopentadienyl) hafnium (CH ₃ ) ₂ , bis (n-propylcyclopentadienyl) hafnium F ₂ , bis (n-propylcyclopentadienyl) hafnium Cl ₂ , bis (n-butyl, methyl cyclopentadienyl) zirconium Cl ₂ , [(2,3,4,5,6 Me5C6N) CH ₂ CH ₂ ] ₂ NHZrBz ₂ , where Bz is a benzyl group, or any combination thereof.
[0059] In addition to the metallocene - type catalyst compounds discussed and described above, other catalysts suitable metallocene - type compounds can include, but without limitation, the metallocenes discussed and described in US Patent ^Nos: 7,741,417, 7,179,876, 7,169. 864, 7,157,531, 7,129,302, 6,995,109, 6,958,306, 6,884,748, 6,689,847, and in WO WO 97/22635, WO 00/699/22, WO 01/30860, WO 01 / 30861, WO 02/46246, WO 02/50088, WO 04/026921, and WO 06/019494.
[0060] Other catalytic compounds of the metallocene type that can be used are supported restricted geometry catalysts (sCGC) comprising (a) an ionic complex, (b) a transition metal compound, (c) an organometallic compound, and ( d) a support material. Such sCGC type catalysts are described in PCT Publication WO2011 / 017092. In some embodiments, the sCGC-type catalyst may comprise a borate ion. The borate anion is represented by the formula [BQ4- _Z '(Gq (T - H) _r ) z'] ^d ', where: B is boron in the valence state of 3; Q is selected from the group consisting of hydride, dihydrocarbyl starch, halide, hydrocarbyl oxide, hydrocarb, and substituted hydrocarbyl radicals; z 'is an integer in the range 1 to 4; G is a polyvalent hydrocarbon radical having r + 1 valences linked to the groups M 'er (T - H); q is an integer, 0 or 1; the group (T - H) is a radical in which T comprises O, S, NR, or PR, whose O, S, N or P atom is attached to the hydrogen atom H, where R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbyl radical
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30/71 germyl or hydrogen; r is an integer from 1 to 3; ed is 1. Alternatively the borate ion can be represented by the formula [BQ4-Z '(Gq (T - M ° R ^c x-1X ^to y) r) Z'] ^d -, where: B is boron in the state valence of 3; Q is selected from the group consisting of substituted hydride, dihydrocarbilamide, halide, hydrocarbyl oxide, hydrocarbyl, and hydrocarbyl radicals; z 'is an integer in the range 1 to 4; G is a polyvalent hydrocarbon radical having r + 1 valences linked to the B er groups (T - M ° R ^c x1X ^to y); q is an integer, 0 or 1; the group (T - M ° R ^c x-1X ^to _y ) is a radical in which T comprises O, S, NR, or PR, whose atom of O, S, N or P is attached to M °, in which R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a germyl or hydrogen trihydrocarbyl radical; M ° is a metal or metalloid selected from groups 1-14 of the Periodic Table of the Elements, each occurrence of R ^c is independently hydrogen or a group having from 1 to 80 different atoms of hydrogen which is hydrocarbyl, hydrocarbylsilyl, or hydrocarbylsilylhydrocarbyl; X ^a is a non-interfering group having from 1 to 100 different hydrogen atoms which is halo-substituted hydrocarbil, hydrocarbyl-substituted hydrocarbyl, hydrocarbyl-substituted hydrocarbyl, hydrocarbylamino, di (hydrocarbyl) amino, hydrocarbyloxy or halide; x is an integer other than zero that can vary from 1 to an integer equal to the valence of M °; y is zero or a non-zero integer that can vary from 1 to an integer equal to 1 less than the valence of M °; and x + y is equal to the valence of M °; r is an integer from 1 to 3; ed is 1. In some embodiments, the borate ion can have the formulas described above where z 'is 1 or 2, q is 1, r is 1.
[0061] The catalytic system can include other single site catalysts such as catalysts containing group 15 atoms. The catalyst system can include one or more second catalysts in addition to the single site catalyst compound such as chromium based catalysts, ZieglerNatta catalysts , one or more single site catalysts added such as metallocenes or catalysts containing group 15 atoms, bimetallic catalysts, and mixed catalysts. The catalytic system can also include AICI3, cobalt, iron, palladium, or any combination thereof.
Catalytic compounds containing group 15 atoms and metals
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The catalytic system may include one or more catalytic compounds containing group 15 metals. The catalytic compound containing group 15 metals generally includes a group 3 to 14 metal atom, preferably a group metal atom 3 to 7, more preferably from group 4 to 6, and even more preferably from group 4, attached to at least one displaceable group and also attached to at least two atoms in group 15, at least one of them also being attached to an atom of group 15 or 16 through another group.
[0063] In one or more embodiments, at least one of the atoms in group 15 is also attached to an atom in group 15 or 16 via another group which may be a C1 to C20 hydrocarbon group, a group containing heteroatoms, silicon, germanium, tin, lead, or phosphorus, where the atom of group 15 or 16 can also be attached to anything or a hydrogen, a group containing an atom of group 14, a halogen, or a group containing hetero atoms, and in which each of the two atoms in group 15 is also linked to a cyclic group and may optionally be linked to a hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a group containing hetero atoms.
[0064] Compounds containing group 15 metals can be described more particularly by formulas (VI) or (VII):
R ⁵ (VII.)
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32/71 wherein M is a transition metal from group 3 to 12 or a main group metal from group 13 or 14, preferably a metal from group 4, 5, or 6, and more preferably a metal from group 4, and even more preferably zirconium, titanium or hafnium; each X is independently a displaceable group, preferably an anionic displaceable group, and more preferably hydrogen, a hydrocarbyl group, a heteroatom or a halogen, and even more preferably an alkyl; y is 0 or 1 (when y is 0 the group L 'is absent); n is the oxidation state of M, preferably +3, +4, or +5, and more preferably +4; m is the formal charge of linker YZL or linker YZL ', preferably 0, -1, -2 or -3, and more preferably -2; L is an element in group 15 or 16, preferably nitrogen; L 'is an element of the group 15 or 16 or a group containing an atom of the group 14, preferably carbon, silicon or germanium; Y is a group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen; Z is a group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen; R ¹ and R ² are independently a C1 to C20 hydrocarbon group, a group containing heteroatoms having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus, preferably a C2 to C20 alkyl, aryl or aralkyl group, more preferably a C2 to C20 linear, branched or cyclic alkyl group, even more preferably a C2 to Ce hydrocarbon group. R ¹ and R ² can also be interconnected to each other; R ³ is absent or is a hydrocarbon group, hydrogen, a halogen, a group containing hetero atoms; preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably R ³ is absent, is hydrogen or an alkyl group, and even more preferably hydrogen; R ⁴ and R ⁵ are independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or a multi-ring system, preferably having up to 20 carbon atoms, more preferably between 3 and 10 carbon atoms, and even more preferably a C1 to C20 hydrocarbon group, a C1 to C20 group
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33/71 aryl or a group a group C 1 to C ₂ the aralkyl, or a group containing hetero atoms, and / or R ⁴ and R ⁵ can be interconnected to each other; R ⁶ and R ⁷ are independently absent, or are independently hydrogen, an alkyl group, a halogen, a heteroatom, or a hydrocarbyl group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, and more preferably is absent, and R * is absent, or is hydrogen, a group containing atoms of group 14, a halogen, or a group containing hetero atoms.
[0065] Formal charge of ligand YZL or YZL '”means the charge of the entire ligand in the absence of the metal and the displaceable groups X (“ absent the metal and the leaving groups X ”). By R ¹ and R ² can also be interconnected it is understood that R ¹ and R ² can be directly linked to each other or can be linked to each other through other groups. By R ⁴ and R ⁵ can also be interconnected it is understood that R ⁴ and R ⁵ can be directly linked to each other or can be linked to each other through other groups. An alkyl group can be linear or branched alkyl radicals, alkenyl radicals, alkynyl radicals, cycloalkyl radicals, aryl radicals, acyl radicals, arroxy radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbon radicals alkyl- or dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals, straight, branched or cyclic alkylene radicals, or combinations thereof. An aralkyl group is defined as a substituted aryl group.
[0066] In one or more modalities, R ⁴ and R ⁵ are independently a group represented by the following formula (VII):
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34/71 where R ⁸ to R ¹² are each independently hydrogen, a Ci to C40 alkyl group, a halide, a hetero atom, a group containing hetero atoms containing up to 40 carbon atoms, preferably a Ci to C _{2 group} o linear or branched alkyl, preferably a methyl, ethyl, propyl or butyl group, any two R groups which may form a cyclic group and / or a heterocyclic group. Cyclic groups can be aromatic. In a preferred embodiment R ⁹ , R ¹⁰ and R ¹² are independently a methyl, ethyl, propyl or butyl group (including all isomers), in a preferred embodiment R ⁹ , R ¹⁰ and R ¹² are methyl groups, and R ⁸ and R ¹¹ are hydrogen.
[0067] In one or more modalities, R ⁴ and R ⁵ are both a group represented by the following formula (VIII):
CH;
wherein M is a group 4 metal, preferably zirconium, titanium or hafnium, and even more preferably zirconium; each of L, Y, and Z is nitrogen; each of R ¹ and R ² is -CH2-CH2-; R ³ is hydrogen; and R ⁶ and R ⁷ are absent.
[0068] The group 15 metal-containing catalytic compound can be represented by the following formula (IX):
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where Ph is equal to phenyl. Metal - containing compounds of group 15 representative and the preparation thereof may be those discussed and described in US Patents ^Nos 5,318,935, 5,889,128, 6,333,389, 6,271,325, and 6,689,847, in WO Publications WO 99 / 01460, WO 98/46651, WO 2009/064404, WO 2009/064452, and WO 2009/064482, and in EP 0 893 454; and EP 0 894 005.
Chromium-based catalysts [0069] Suitable chromium-based catalysts can include disubstituted chromates, such as CrO ₂ (OR) 2; where R is triphenylasilane or a tertiary polyalicyclic alkyl. The chromium-based catalytic system can also include CrO ₃ , chromocene, silyl chromate, chromyl chloride (CrO ₂ CI ₂ ), chromom-2-ethylhexanoate, chromium acetylacetonate (Cr (AcAc) s), among others.
Illustrative Zieqler-Natta Catalysts [0070] Catalytic Ziegler-Natta compounds are described in Ziegler Catalysts 363-386 (G. Fink, R. Mulhaupt & H.H. Brintzinger, eds., SpringerVerlag 1995); or in documents EP 103 120, EP 102 503, EP 0 231 102, EP 0 703 246, RE 33,683, US 4,302,565, US 5,518,973, US 5,525,678, US 5,288,933, US 5,290,745, US 5,093,415 and US 6,562,905. Examples of such catalysts include those comprising group 4, 5 or 6 transition metal oxides, alkoxides and halides, or titanium, zirconium or vanadium oxides, alkoxides and halides; optionally in combination with a magnesium compound, internal and / or external electron donors (alcohols, ethers, siloxanes,
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36/71 etc.), aluminum or boron alkyl and alkyl halides, and inorganic oxide supports.
Transition metal-based catalysts [0071] Transition metal-based catalysts of the conventional type are the traditional Ziegler-Natta catalysts that are well known in the literature. These transition metal based catalysts of the conventional type can be represented by the formula: MR _X , where M is a metal from groups 3 to 17, or a metal from groups 4 to 6, or a metal from group 4, or titanium ; R is a halogen or a hydrocarbiloxy group; ex is the valence of metal M. Examples of R include alkoxy, phenoxy, bromide, chloride and fluoride. Examples of transition metal based catalysts of the conventional type where M is titanium include TiCU, TiBr ₄ , Ti (OC ₂ H ₅ ) ₃ CI, Ti (OC ₂ H ₅ ) CI ₃ , Ti (OC ₄ H ₉ ) ₃ CI, Ti (OC ₃ H ₇ ) ₂ CI ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , TiCI ₃ / AICI ₃ and Ti (OCI ₂ H ₂₅ ) CI ₃ .
[0072] Catalysts derived from Mg / Ti / CI / THF can be used. An example of the general method of preparation of such a catalyst includes the following: dissolve TiCl4 in THF, reduce the compound to TICI ₃ using Mg, add MgCl _2, and remove the solvent. Specific examples of catalysts other conventional - type transition metal based are discussed in more detail in US Patent ^Nos 4.1 15,639, 4,077,904, 4,482,687, 4,564,605, 4,721,763, 4,879,359, and 4,960,741 . catalytic compounds to the transition metal based on the conventional type complexes based on donor electrons magnesium / titanium are described for example in US Patents ^Nos 4,302,565 and 4,302,566.
Mixed catalytic system [0073] The catalytic system can include a mixed catalyst, which can be a composition of bimetallic catalysts or a composition of multiple catalysts. As used in this report, the terms "bimetallic catalyst composition" and "bimetallic catalyst" include any composition, mixture or system that includes two or more different catalytic components, each having a different metal group. The terms
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37/71 composition of multiple catalysts ”and“ multicatalysts ”include any composition, mixture or system that includes two or more different catalytic components regardless of metals. Accordingly, the terms composition of bimetallic catalysts "," bimetallic catalyst ", composition of multiple catalysts" and "multicatalysts" will be collectively referred to in this report as "mixed catalyst" unless specifically noted to the contrary. In a preferred embodiment, the mixed catalyst includes at least one metallocene-type catalytic compound and at least one non-metallocene-type compound.
Continuity additive / Static control agent [0074] In the processes disclosed in this invention, it may also be desirable to additionally use one or more static control agents to help regulate static levels in the reactor. As used in this report, a static control agent is a chemical composition that, when introduced into a fluidized bed reactor, can influence or induce the static charge (negatively, positively or to zero) in the fluidized bed. The specific static control agent used may depend on the nature of the static charge, and the choice of static control agent may vary depending on the polymer being produced and the single site catalytic compounds being used. For example, the use of static control agents is disclosed in European Patent No. 0229368 and in US Patents ^Nos 4,803,251, 4,555,370, and 5,283,278, and references cited therein.
[0075] Control agents such as aluminum stearate can also be employed. The static control agent used can be selected in terms of its ability to receive the static charge in the fluidized bed without adversely affecting productivity. Other suitable static control agents may also include aluminum distearate, ethoxylated amines, and antistatic compositions such as those provided by Innospec Inc. under the trade name OCTASTAT. For example, OCTASTAT 2000 is a mixture of a polysulfone copolymer, a polymeric polyamine, and sulfonic acid
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38/71 oil soluble.
[0076] Any of the control agents mentioned above, as well as those described, for example, in WO 01/44322, listed under the title Metal Carboxylate Salt and including the related chemicals and compositions as antistatic agents can be employed either alone or in combination with a control agent. For example, the metal carboxylate salt can be combined with an amine-containing control agent (for example, a metal carboxylate salt with any member of the family belongs to the KEMAMINE® (available from Crompton Corporation) family or ATMER® (available) at ICI Americas Inc.).
[0077] Other useful continuity additives include ethyleneimine-type additives useful in the embodiments described in this invention may include polyethyleneimines having the following general formula:
- (CH2 - CH2 - NH) n where n cannot vary from about 10 to about 10,000. Polyethyleneimines can be linear, branched, or hyper-branched (that is, forming dendritic or arborescent polymeric structures). They can be a homopolymer or a copolymer of ethyleneimine or mixtures thereof (hereinafter called polyethyleneimines). Although linear polymers represented by the chemical formula - [CH2 CH2 NH] - can be used as polyethyleneimine, materials having primary, secondary and tertiary branches can also be used. Commercial polyethyleneimine can be a compound having branches of the ethyleneimine polymer. Suitable polyethyleneimines are commercially available from BASF Corporation under the trade name Lupasol. These compounds can be prepared as widely known for molecular weights and product activities. Examples of commercial polyethyleneimines marketed by BASF suitable for use in the present invention include, but are not limited to, Lupasol FG and Lupasol WF. Another useful continuity additive may include a mixture of aluminum distearate and an ethoxylated amine compound, for example, IRGASTAT AS-990, available from Huntsman (formerly Ciba
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Specialty Chemicals). The mixture of aluminum distearate and ethoxylated amine type compound can be suspended in mineral oil, for example, Hydrobrite 380. For example, the mixture of aluminum distearate and ethoxylated amine type compound can be suspended in mineral oil in order to give a total suspension concentration ranging from about 5 wt% to about 50 wt% or about 10 wt% to about 40 wt%, or about 15 wt% to about 30 wt%. Other useful static control agents and additives are described in US Patent Application Publication No. 2008/0045663.
[0078] Continuity additives or static control agents can be added to the reactor in an amount ranging from 0.05 to 200 ppm, based on the weight of all feeds made to the reactor, except recycle, more preferably in an amount varying from 2 to 100 ppm; more preferably from 4 to 50 ppm in still other embodiments.
Oolimerization process [0079] The catalytic system can be used to polymerize one or more olefins to produce one or more polymeric products from them. Any polymerization process including, but not limited to, high pressure, solution, suspension and / or gas phase processes can be used. Preferably, a continuous gas-phase process using a fluidized bed reactor is used to polymerize ethylene and one or more optional comonomers to give a polyethylene.
[0080] The term polyethylene refers to a polymer having at least 50% by weight of ethylene-derived units, preferably at least 70% by weight of ethylene-derived units, more preferably at least 80% by weight of derived units ethylene, or 90% by weight of ethylene-derived units, or 95% by weight of ethylene-derived units, or 100% by weight of ethylene-derived units. The polyethylene can therefore be a homopolymer or a copolymer, including a terpolymer, having one or more other monomer units. A polyethylene described in this invention can, for example, include at least one or more other olefins and / or comonomers.
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Suitable comonomers can contain 3 to 16 carbon atoms in one embodiment; from 3 to 12 carbon atoms in another mode; from 4 to 10 carbon atoms in another mode; and from 4 to 8 carbon atoms in yet another embodiment. Illustrative comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methylpent-l-ene, 1-decene, 1-dodecene, 1-hexadecene, among others .
[0081] A suitable fluidized bed reactor can include a reaction zone and a zone called a speed reduction zone. The reaction zone can include a bed of developing polymer particles, polymer particles formed and a small amount of catalyst particles fluidized by the continuous flow of the gaseous monomer and diluent to remove the heat of polymerization through the reaction zone. Optionally, a portion of the recirculated gases can be cooled and compressed to form liquids that increase the heat removal capacity of the circulating gas stream when readmitted to the reaction zone. An adequate gas flow rate can be easily determined by simple experimentation. The recovery of gaseous monomer into the circulating gas stream can be at a rate equal to the rate at which the particulate polymer produced and the monomer associated with it are removed from the reactor and the composition of the gas passing through the reactor can be adjusted to maintain the gas composition in essentially steady state within the reaction zone. The gas leaving the reaction zone can be taken to the speed reduction zone where the trapped particles are removed. The finer trapped particles and dust can be removed in a cyclone and / or in a fine filter. The gas can be passed through a heat exchanger where at least some of the heat of polymerization can be removed, compressed in a compressor, and then returned to the reaction zone. Further details of the reactor and means for operating the reactor are described, for example, in US Patents ^Nos 3,709,853, 4,003,712, 4.01, 1.382, 4,302,566, 4,543,399, 4,882,400, 5,352,749, and 5,541,270, EP 0802202, and in Belgian Patent No. 839,380.
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41/71 [0082] The reactor temperature for the fluid bed process can vary from 30 ° C or 40 ° C or 50 ° C to 90 ° C or 100 ° C or 110 ° C or 120 ° C or 150 ° C . In general, the reactor temperature can be operated at the highest possible temperature taking into account the sintering temperature of the polymer produced inside the reactor. Regardless of the process used to make the polyolefins, the polymerization temperature, or the reaction temperature, must be lower than the melting or "sintering" temperature of the polyolefins to be formed. Therefore, the upper limit of the temperature in a modality is the melting temperature of the polyolefin produced in the reactor.
[0083] Hydrogen gas can be used in the polymerization of olefins to control the final properties of the polyolefin, as described in Polypropylene Handbook, pages 76-78 (Hanser Publishers, 1996). With the use of certain catalytic systems, increasing concentrations (partial pressures) of hydrogen can increase the flow index (FI) of the generated polyolefin. The flow rate can therefore be influenced by the concentration of hydrogen. The amount of hydrogen in the polymerization can be expressed as a molar ratio to the total polymerizable monomer, for example, ethylene, or a blend of ethylene and hexane or propylene. The amount of hydrogen used in the polymerization process can be an amount needed to obtain the desired flow rate of the final polyolefin resin. In one embodiment, the molar ratio of hydrogen to total monomer (H2: monomer) can be in a range above 0.0001 in one mode, and above 0.0005 in another mode, and above 0.001 in yet another mode, and below 10 in yet another mode, and below 5 in yet another mode, and below 3 in yet another mode, and below 0.10 in yet another mode, in which a desirable range can include any combination of the upper limit of the molar ratio with any lower limit of the molar ratio described in this invention. In other words, the amount of hydrogen in the reactor at any one time can vary up to 5,000 ppm, and up to 4,000 ppm in another mode, and up to 3,000 ppm in yet another mode, and between 50
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42/71 ppm and 5,000 ppm in yet another mode, and between 50 ppm and 2,000 ppm in another mode. The amount of hydrogen in the reactor can vary from as little as about 1 ppm, about 50 ppmw, or about 100 ppm to as high as about 400 ppm, about 800 ppm, about 1,000 ppm, about 1,500 ppm , or about 2,000 ppm. In yet another embodiment, the ratio of hydrogen to total monomer (H2: monomer) can range from about 0.00001: 1 to about 2: 1, about 0.005: 1 to about 1.5: 1, or about 0.0001: 1 to about 1: 1.
[0084] The one or more pressures of the reactor in a gas phase process (either in a single stage or in two or more stages) can vary from 690 kPa (100 psig) to 3,448 kPa (500 psig), and in the range of 1,379 kPa (200 psig) to 2.759 kPa (400 psig) in another mode, and in the range of 1.724 kPa (250 psig) to 2.414 kPa (350 psig) in yet another mode.
[0085] The gas phase reactor may be capable of producing from about 10 kg of polymer per hour (25 lbs / h) to 90,900 kg / h (200,000 lbs / hr), and more than 455 kg / h (1,000 lbs) / h) in another mode, and more than 4,540 kg / h (10,000 lbs / h) in yet another mode, and more than 11,300 kg / h (25,000 lbs / h) in yet another mode, and more than 15,900 kg / h (35,000 lbs / h) in yet another modality, and more than 22,700 kg / h (50,000 lbs / h) in yet another modality, and from 29,000 kg / h (65,000 lbs / h) to 45,500 kg / h (100,000 lbs / h) in yet another mode.
[0086] A suspension polymerization process can also be used. A suspension polymerization process generally uses pressures in the range of about 101 kPa (1 atmosphere) to about 5.070 kPa (50 atmospheres) and even higher and temperatures in the range of about 0 ° C to about 120 ° C, and more particularly from about 30 ° C to about 100 ° C. In a suspension polymerization, a suspension of solid and particulate polymer can be formed in a liquid polymerization diluent medium to which ethylene and comonomers and generally hydrogen together with a catalyst are added. The suspension including thinner can be intermittent or continuously removed
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43/71 of the reactor in which the volatile components are separated from the polymer and recycled, optionally after a distillation step, to the reactor. The liquid diluent used in the polymerization medium can be an alkane having 3 to 7 carbon atoms, such as, for example, a branched alkane. The medium used must be liquid under the conditions of polymerization and relatively inert. When a propane-type medium is used, the process must be operated above the critical temperature and pressure of the reaction diluent. In one embodiment, a hexane, isopentane, or isobutane type medium can be employed.
[0087] Polyethylene can have a melt index ratio (I21 / I2) ranging from about 5 to about 300, more preferably from about 10 to less than about 250, and from about 15 to about 200 The FI (I21) can be measured according to ASTM D1238 (190 ° C, 21.6 kg). MI (I ₂ ) can be measured according to ASTM D1238 (at 190 ° C, 2.16 kg in weight). FI (I5) can be measured according to the ASTM D1238 standard (at 190 ° C, 5.0 kg in weight).
[0088] The density can be determined according to the ASTM D792 standard. The density is expressed in grams per cubic centimeter (g / cm ³ ) unless otherwise indicated. Polyethylene can have a density ranging from as little as about 0.89 g / cm ³ , about 0.90 g / cm ³ , or about 0.91 g / cm ³ to as high as about 0.95 g / cm ³ , about 0.96 g / cm ³ , or about 0.97 g / cm ³ . The polyethylene can have a mass density, measured according to ASTM D1895 method B, from about 0.25 g / cm ³ to about 0.5 g / cm ³ . For example, the mass density of polyethylene can vary from as little as about 0.30 g / cm ³ , about 0.32 g / cm ³ , or about 0.33 g / cm ³ to as high as about 0.40 g / cm ³ , about 0.44 g / cm ³ , or about 0.48 g / cm ³ .
[0089] Polyethylene may be suitable for articles such as films, fibers, non-woven and / or braided fabrics, extruded articles, and / or molded articles. Examples of films include blown or cast films formed by coextrusion or lamination useful as contractile films, sticky films, extensible films, sealing films, oriented films, packaging for snacks,
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44/71 reinforced bags, food bags, cooked and frozen food packaging, medical packaging, industrial coatings, membranes, etc. in food contact and non-food contact applications, films and agricultural blades. Examples of fibers include melt spinning, solution spinning and fiber blowing melting for use in braided or unbraided form to make filters, diaper fabrics, hygiene products, medical clothing, geotextiles, etc. Examples of extruded articles include piping, medical piping, coatings for metal wires and cables, pipes, geomembranes, and linings for swimming pools. Examples of molded articles include single layer and multilayer constructions in the form of bottles, tanks, large hollow articles, rigid containers for food and toys, etc.
EXAMPLES [0090] For a better understanding of the preceding discussion, we offer the following non-limiting examples. All parts, proportions and percentages are given by weight unless otherwise indicated. Preparation of Activated Supports [0091] In Examples 1,3, 8, 9, 26, and 27 and in comparative example C10 a silica support impregnated with an aluminum compound, supplied by PQ Corporation, was combined with ammonium hexafluorsilicate to give a support mix. In Examples 2, 4-7, 11-19, 24, 28, and 29 and in comparative example C8 a silica-aluminum support was combined with ammonium hexafluorsilicate to give a support mixture. In Examples 10, 20-23, and 25 and in comparative examples C1-C7, C9, and C11 another silica support impregnated with an aluminum compound, supplied by PQ Corporation was combined with ammonium hexafluorsilicate to give a support mixture . In all examples, the resulting support mixtures were loaded into a vertically hinged tubular single zone oven and heated to convert the support mix into a fluorinated or activated support.
[0092] To activate the support, a flow of nitrogen gas at a speed
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45/71 between 0.03 m / sec and 0.06 m / sec (0.10 ft / sec and 0.2 ft / sec) was started. The oven was heated from room temperature to 200 ° C to 50 ° C per hour and maintained at 200 ° C for 2 hours. After 2 hours the nitrogen flow was stopped and air was introduced at approximately the same speed, that is, between 0.03 m / sec and 0.06 m / sec (0.10 ft / sec and 0.2 ft / Mon). The oven was then heated to 600 ° C at a rate of 50 ° C per hour and maintained at 600 ° C for 3 hours. After 3 hours the oven was allowed to cool to room temperature. At approximately 195 ° C the air flow was interrupted and the flow of nitrogen gas was restarted. The furnace was purged with nitrogen gas for at least 30 minutes before removing the activated catalyst. The activated catalyst support is transferred to an oven dried bottle.
Preparation of catalytic systems [0093] Each catalytic system contained a catalytic compound of the metallocene type, MAO, and one of the three supports of fluorinated silica-alumina described above. For examples 1-22 and 26-29 and for comparative examples C1-C9 and C11, the metallocene-type catalytic compound was bis (n-propylcyclopentadienyl) hafnium (CH ₃ ) ₂ . For examples 23, 24, and C10, the catalyst was bis (n-butyl, methyl cyclopentadienyl) zirconium Cl ₂ . For example 25, the catalyst was [(2,3,4,5,6 Me ₅ C ₆ ) CH ₂ CH ₂ ] ₂ HZrBz ₂ , where Bz is a benzyl group. One of two methods was used to prepare the catalytic systems.
Method 1: To prepare the supported catalytic systems, a 10% by weight to 30% by weight MAO solution in toluene and additional toluene (dried and degassed) was placed in a mixer at room temperature and stirred slowly. The metallocene-type catalytic compound was dissolved in 100 g of toluene and introduced into the mixer containing the mixture of MAO and toluene. The stirring speed was increased to 130 rpm and continued for 1 hour at room temperature. The activated support (fluorinated silica alumina) was then introduced into the mixer and stirred for 1 hour at room temperature. A vacuum was applied to remove the free liquid. After the material had passed through the “mud phase”, that is, there was no visible free liquid, a nitrogen gas purge was
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46/71 introduced into the mixer. During the mixing of the activated support, metallocene-based catalyst, and MAO, the temperature of the mixture was increased to a final temperature of about 78 ° C to 80 ° C and mixed for about 2 hours. The mixture was then cooled to room temperature and stored in an oven-dried container in an atmosphere of nitrogen.
Method 2: The metallocene-based catalyst was added to 10% by weight MAO to 30% by weight toluene. This mixture was added to a mixer containing a suspension of the support and toluene. The mixture was dried with vacuum and heat.
[0094] The supports for examples 1 and 3 were prepared at 600 ° C using 800 grams of PQ ES70W silica treated with an aluminum compound and 44 grams of ammonium hexafluorsilicate. The catalytic systems for examples 1 and 3 were prepared by method 1 above employing 14.22 g of Hf compound, 361 g of 30% by weight MAO, 1.812 g of toluene, and 625 g of support. The support for example 2 was prepared at 600 ° C using 1,000 grams of Sasol Siral 40 alumina / silica (a surface area of about 500 m ² / g, a pore volume of about 0.9 cm ³ / g, and a particle size of about 38 pm) and 55 grams of ammonium hexafluorsilicate. The catalytic system for example 2 was prepared by method 1 above employing 13.54 g of the Hf compound, 344 g of 30% MAO, 1.725 g of toluene and 595 g of support. The catalytic systems for comparative examples C1 and C2 were prepared by method 1, with the difference that a higher amount of MAO was used and the support was silica PQ ES-757 (a surface area of about 300 m ² / g , a pore volume of about 1.5 cm ³ / g, and a particle size of about 25 µm) dehydrated at 875 ° C.
Fluidized bed gas polymerization process - Series of Examples I [0095] A fluidized bed gas polymerization reactor of the UNIPOL ™ process design having a nominal diameter of 35.56 cm (14 inches) was used for the continuous production of low linear polyethylene
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47/71 density (LLDPE) and high density polyethylene (HDPE). In these cases, the cycle gas blower was positioned above the cycle gas heat exchanger in the gas recirculation circuit but the two could have been inverted to reduce the gas temperature to the point where it entered the heat exchanger. The cycle tube was about 5.08 cm (2 inches) in diameter and its flow rate was manipulated by a spherical valve on the cycle line to control the surface velocity of the gas in the fluid bed at the desired rate. The monomers and gaseous components were added upstream of the refrigerator before the blower, in the blower rotor or after the blower. The catalytic system was added continuously in small, discrete aliquots via a 3.18 mm (0.125 inch) tube directly to the fluidized bed at a height of about 0.1 to 2 m above the dispensing plate and even more preferably in the about 0.2 to 1.2 m using a stream of carrier nitrogen gas at a location about 15% to about 50% of the reactor diameter. A continuity aid, an ethyleneimine copolymer, was also added (LUPASOL by BASF). The polymer produced was periodically removed from the reactor through a discharge isolation tank in aliquots of about 0.2 kg to 5 kg to maintain a desired approximate average fluidized bed level or weight.
[0096] In Examples 1 and 2 and C1 LLDPEs were produced. In Examples 3 and C2, HDPEs were produced. The catalytic systems for comparative examples C1 and C2 used a silica support. Table 1 summarizes the results of the polymerization below.
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Table 1 Examples Ex. 1 Ex. 2 C1 Ex. 3 C2 Polymer type LLDPE LLDPE LLDPE HDPE HDPE mmol MAO / g support 3 3 6.25 3 6.25 Hf (% by weight, based on the total weight of the catalytic system) 0.813 0.907 0.785 0.813 0.785 F (% by weight, based on the total weight of the support) 3.19 3.54 - 3.19 - Al (% by weight, based on the total weight of the support) 4.4 27.67 - 4.4 - Al (% by weight, based on the total weight of the catalytic system) 9.77 35.17 - 9.77 - Reaction conditions 12,789 14,905 14,151 13.62 14,982 Production rate (kg / h (lb / h)) (28.17) (32.83) (31.17) (30) (33) Residence time (h) 3.1 2.8 3.03 3 2.861.517 1.5181.515 1.516 Partial pressure of C2 (MPa (psia)) (220.09) (220.31) 1.518 (220.28) (219.74) (220.01) H2 (ppm) 318 388 338 620 637 C6 / C2 concentration ratio 0.0145 0.0151 0.0161 0.002 0.0021 Isopentane (mol%) 8.27 8.05 8.09 8.2 8.892,399 2.401 2.402 2.402 2.402 Pressure (gauge MPa (psig)) (348.43) (348.29) (348.4) (348.39) (348.44) Temperature (° C) 77 77 79 95 95 Gas speed (m / s (ft / sec)) 0.637 0.64 0.618 0.63 0.637
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Table 1 Examples Ex. 1 Ex. 2 C1 Ex. 3 C2(2.09) (2.1) (2.03) (2.07) (2.09) Fluid mass density 0.267 0.181 0.301 0.259 0.241 (g / cm ³ (lb / ft ³ )) (16.71) (11.36) (18.81) (15.86) (15.09) Continuity additive concentration (ppmw of product) 6 5.1 5.4 5.6 5.1 Product propertiesmelting index (dg / min) (I ₂ ) 0.856 0.896 0.9 45,415 42,317 flow index (I5) 2,449 2.59 2,667 119,164 112,616 flow index (I ₂₁ ) 24.11 26,246 27,543 871,004 828,425 MFR (I21 / I2) 28.2 29.3 30.6 19.2 19.6 MFR (I21 / I5) 9.8 10.1 10.3 7.3 7.4 Density (g / cm ³ ) 0.9155 0.9179 0.9176 0.9536 0.9546 Fluid mass density (g / cm ³ ) 0.44 0.42 0.48 0.37 0.410.117 0.081 0.073 0.091 0.066 APS sieve (cm (in)) (0.0462) (0.0319) (0.0287) (0.036) (0.0261) LT No 120 sieve fines (wt%) 0.15 1.08 0.15 0.11 0.19 Catalyst productivityCatalyst productivity (Hf ICPES) 17,674 7,887 13,534 9,915 9,345
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50/71 [0097] Examples 1 and 3 showed higher catalyst productivity than comparative examples C1 and C2, respectively, although using significantly less MAO. More particularly, the amount of MAO has been reduced from the 6.25 mmoles of MAO / g of support used in Examples C1 and C2 to just 3.0 mmoles of MAO / g of support for examples 1-3, which is more than 50 % reduction. The catalyst productivity for the example was 8.02 kg (17.674 pounds) of polyethylene per 0.45 kg (per pound) of catalytic system (PE pound / pound of catalytic system) whereas the comparative example C1 showed only a catalyst productivity of 6.14 kg (13.534 pounds) of PE / 0.45 kg (pounds) of catalytic system. Therefore, Example 1, which had only 3.0 mmoles of MAO / g of support, showed an increase in catalyst productivity of about 30.6% over comparative example C1 which used 6.25 mmoles of MAO / support g. The catalyst productivity for example 3 was 4.5 kg (9.915 pounds) of PE / 0.45 kg (pound) of catalytic system whereas comparative example C1 showed only a catalyst productivity of 4.24 kg (9.345 pounds) of PE / 0.45 kg (pounds) of catalytic system. Therefore, Example 3, which had only 3.0 mmoles of MAO / g of support, showed an increase in catalyst productivity of about 6% over comparative example C2 which used 6.25 mmoles of MAO / g of Support.
Fluidized bed gas phase polymerization process - Series of Examples II [0098] Another series of examples was prepared using the same fluidized bed gas phase polymerization reactor and the same conditions as those used in Examples Series I, except that in comparative example C3 and Example 4, the continuity additive was exchanged for a mixture of aluminum distearate and an ethoxylated amine type compound (IRGASTAT AS990, available from Huntsman (formerly Ciba Specialty Chemicals)) which is suspended in mineral oil (Hydrobrite 380) to give a total suspension concentration of approximately 20% by weight. The continuity additive
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51/71 for comparative example C4 and for Example 5 was an ethyleneimine copolymer. The concentration of the continuity additive shown in Table 2 for each example is based on the rate of production of the polymer.
[0099] The catalytic systems for comparative examples C3 and C4 were prepared in the same way as comparative examples C1 and C2, that is, 6.25 mmoles of MAO and the support is made of PQ ES-757 silica dehydrated at 875 ° C . The catalytic system used in Example 4 was prepared using method 2 with less Hf and MAO. The support used for this example was Siral 40 activated at 600 ° C with sufficient ammonium hexafluorsilicate to give a final composition of about 26.59% by weight of Al and about 5.68% by weight of F, based on support weight. The catalytic system used in Example 5 was prepared using method 1. The support used for this example was Siral 40 activated at 600 ° C with sufficient ammonium hexafluorsilicate to give a final composition of about 23.27% by weight of Al is about 4.96% by weight of F, based on the weight of the support. Table 2 summarizes the results of the polymerization below.
Table 2 Examples C3 Ex. 4 C4 Ex.5 Polymer type LLDPE LLDPE HDPE HDPE mmol MAO / g support 6.25 2 6.25 2.5 Hf (% by weight, based on the total weight of the catalytic system) 0.8 0.57 0.83 0.86 Al (% by weight, based on the total weight of the support) 11.43 31.8 11.15 32.23 Al (% by weight, based on the total weight of the support) - 26.59 - 23.27 F (% by weight, based on the total weight of the support) - 5.68 - 4.96 Reaction conditions Production rate (kg / h (lb / h)) 17,669(38.92) 19,068(42) 15,131(33.33) 15,631(34.43) STY (kg / h / m ³ (lb / n / ft ³ )) 105.1590(6.5574) 105.6241(6.5864) 69.6554(4.3435) 76.92(4.7965) Residence time (h) 2.43 2.52 1.518(3.18) 1.519(2.53)
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Table 2 Examples C3 Ex. 4 C4 Ex.5 Partial pressure of C2 1.517 1.517 1.518 1.519 (MPa (psia)) (220) (220) (220.16) (220.32) Reason for concentrationC6 / C2 (ppm) 280 292 243 273 Reason for concentrationC6 / C2 (m / m) 0.0167 0.0152 0.0155 0.0139 Isopentane and (mol%) 7.15 7.13 7.78 7.56 Pressure (MPa 2,398 2,398 2,398pressure gauges (psig)) (347.77) (347.78) (347.8) 2,398 (347.79) Temperature (° C) 77.7 77.7 78.01 78 Gas speed (m / s 0.622 0.567 0.637(ft / s)) (2.04) (1.86) (2.09) 0.664 (2.18)43.091 48,080 48,080Bed weight (kg (lbs)) (95) (106) (106) 39,462 (87) Mass density of 0.257 0.267 0.223fluid (g / cm ³ / (lb / ft ³ )) (16.04) (16.69) (13.92) 0.197 (12.3) Continuity additive concentration (ppmw of product) 28.9 26.8 6.2 6 Product properties Melting index (dg / min) (I2) 0.922 0.819 0.613 0.554 Flow index (I ₅ ) 2.85 2,396 1.816 1,564 Flow index (I ₂₁ ) 30.61 24,232 20.05 14,588 MFR (I21 / I2) 33.2 29.6 32.6 26.3 MFR (I21 / I5) 10.7 10.1 11 9.3 Density (g / cm3) 0.9191 0.9188 0.9178 0.9172 Mass density 0.457 0.441 0.445(g / cm ³ / (lb / ft ³ )) (28.52) (27.55) (27.8) 0.418 (26.1)0.061 0.081 0.067 0.099 APS sieve ((cm (in)) (0.0241) (0.0322) (0.0263) (0.0391) APS (micron) 612 817 668 994 Fines in the sieve LT No120 (wt%) 0.46 0.47 0.46 0.29 Catalyst productivity Catalyst productivity (Hf ICPES) 7.207 8,507 8,947 15,636
[0100] Examples 4 and 5 showed higher catalyst productivity than comparative examples C3 and C4, respectively, although using
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53/71 significantly less MAO. More particularly, the amount of MAO has been reduced from the 6.25 mmoles of MAO / g of support used in comparative examples C3 and C4 to only 2 mmoles of MAO / g of support for example 4 and 2.5 mmoles of MAO / g support for example 5, which is a 68% and 60% reduction in the amount of MAO, respectively. The catalyst productivity for example 4 was 3.86 kg (8.507 pounds) of polyethylene per 0.45 kg (pound) of catalytic system (PE pound / 0.45 kg (pound) of catalytic system) whereas the comparative example C3 showed only a catalyst productivity of 3.27 kg (7.207 pounds) of PE / 0.45 kg (pound) of catalytic system and required 68% more MAO. Thus, Example 4, which had only 2 mmoles of MAO / g of support, showed an increase in catalyst productivity of about 18% over comparative example C1 which used 6.25 mmoles of MAO / g of support or 68% more than MAO. The catalyst productivity for example 5 was 7.09 kg (15.636 pounds) of PE / 0.45 kg (pound) of catalytic system whereas comparative example C4 showed only a catalyst productivity of 4.06 kg (8.947 pound) of PE / 0.45 kg (pound) of catalytic system. As such, Example 4, which had only 2.5 mmoles of MAO / g of support, showed an increase in catalyst productivity of about 75% over comparative example C4 which used 6.25 mmoles of MAO / g of support or 60% more MAO.
Fluidized bed gas phase polymerization process - Series of Examples III [0101] Another series of examples was prepared using the same fluidized bed gas phase polymerization reactor and the same conditions as those used in Examples Series I. A The only difference in the polymerization conditions was that the continuity additive was replaced by a mixture of aluminum distearate and an ethoxylated amine compound (IRGASTAT AS990, available from Huntsman (formerly Ciba Specialty Chemicals)) which is suspended in mineral oil (Hydrobrite 380) to give a concentration of
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[0102] The catalytic system for comparative example C5 was prepared in the same way as for comparative examples C1 and C2, that is, 6.25 mmoles of MAO and the support was of PQ ES-757 silica dehydrated at 875 ° C. The catalytic systems used in Examples 6 and 7 were prepared using method 1 with higher levels of MAO. The support used for this preparation was Siral 40 activated at 600 ° C with sufficient ammonium hexafluorsilicate to give a final composition of 25.32% Al and 4.88% F for example 6 and 26.19% Al and 6.43% F for example 7, based on the weight of the support.
[0103] The catalytic systems used in Examples 8 and 9 and in comparative example C6 were prepared using method 2. The support used for comparative example C6 was the same as that of comparative examples C1 and C2. The support used for examples 8 and 9 was PQ ES-70W with Al. Table 3 summarizes the polymerization results below.
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Table 3 Examples C5 Ex. 6 Ex. 7 C6 Ex. 8 Ex.9 Polymer type LLDPE LLDPE LLDPE LLDPE LLDPE LLDPE mmol MAO / g support 6.25 6.25 6.25 6.25 6.25 4.7 Hf (% by weight, based on the total weight of the catalytic system) 0.785 1,043 1.05 0.74 1.08 1.05 Al (% by weight, based on the total weight of the support) 11.7 32.7 33.1 11.6 13.53 12 F (% by weight, based on the total weight of the support) - 4.88 6.43 - 2.96 3.23 Reaction conditions Production rate (kg / h (lb / h)) 19,249(42.4) 17,978(39.6) 19,721(43.44) 17,351(38.22) 18,614 (41.00) 18,614 (41.00) STY (kg / h / m ³ (lb / h / ft ³ )) 115.9501(7.2303) 106.8461(6.6626) 110.9098(6,916) Residence time (h) 2.38 2.54 2.44 2.54 2.38 2.51 Partial pressure of C2 (MPa (psia)) 1.517(220.07) 1.515(219.81) 1.517(220.08) 1.517(220.07) 1.517(219.98) 1.514(219.58) H2 concentration (ppm) 320 267 276 326 303 292 Concentration ratio C6 / C2 (m / m) 0.0157 0.0145 0.014 0.0154 0.0130 0.0130 Isopentane (mol%) 7.69 7.64 7.14 8.19 8.22 8.55 Pressure (gauge Mpa (psig)) 2,398(347.85) 2,399(347.95) 2,398(347.82) 2.403(348.59) 2.403(348.55) 2.4(348.18) Temperature (° C) 79.25 77.72 77.70 78.00 78.00 78.00 Gas speed (m / s (ft / s)) 0.616(2.02) 0.622(2.04) 0.597(1.96) 0.737(2.42) 0.731(2.40) 0.737(2.42)
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Table 3
Examples C5 Ex. 6 Ex. 7 C6 Ex. 8 Ex.945,813 45,359 48,080 43,998 43,998 46.72 Bed weight (kg (lb)) (101) (100) (106) (97) (97) (103) Fluid mass density 0.277 0.272 0.272 0.292 0.31 0.32 (g / cm ³ (lb / ft ³ )) (17.3) (17) (17.01) (18.25) (19.39) (20.03) Continuity additive concentration (ppmw of product) 26.5 28.4 25.9 29.4 27.4 29.3 Product properties Melting index (dg / min) (I ₂ ) 1,033 1,022 1,071 0.888 0.959 1,028 Flow index (I5) 2.979 2.93 3,032 2,584 2,613 2,838 Flow index (I21) 29,713 27,442 27,263 25.89 21.63 24,059 MFR (I21 / I2) 28.8 26.9 25.5 29.2 22.6 23.4 MFR (I21 / I5) 10 9.4 9 10 8.3 8.5 Density (g / cm ³ ) 0.9169 0.9185 0.9187 0.9183 0.9168 0.9181 Mass density (g / cm ³ (lb / ft ³ )) 0.472 0.424 0.425 0.474 0.424 0.422 (29.46) (26.48) (26.57) (29.57) (26.5) (26.37)0.061 0.122 0.133 0.059 0.121 0.112 APS sieve (cm (in)) (0.0243) (0.0481) (0.0526) (0.0235) (0.0477) (0.0441) APS (micron) 616 1221 1335 Fines in the strainer LT No 120 (% by weight) 0.12 0.13 0.07 0.74 0.18 0.31 Catalyst productivity Catalyst productivity (Hf ICPES) 7.336 14,486 15,672 10,423 19,265 13,150
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57/71 [0104] Examples 6 and 7 showed higher catalyst productivity than comparative examples C5 using the same amount of MAO, that is, about 6.25 mmoles / g of support, but increasing the amount of the transition metal (Hf) component present in the catalyst from about 0.785 wt% to about 1.043 wt% and about 1.05 wt%, respectively. The catalyst productivity for example 6 was about 6.57 kg (14.486 pounds) of polyethylene per 0.45 kg (pound) of catalytic system (pound of PE / pound of catalytic system) whereas comparative example C5 showed only a catalyst productivity of about 3.33 kg (7.336 pounds) of PE / 0.45 kg (pounds) of catalytic system. Therefore, Example 6, which contained about 32.9% more Hf than CE 5, showed an increase in catalyst productivity of about 97.5% over comparative example C5. The catalyst productivity for example 7 was about 7.11 kg (15.672 pounds) of PE / 0.45 kg (pound) of catalyst system whereas the comparative example C5 showed only a catalyst productivity of about 3, 33 kg (7.336 pounds) of PE / 0.45 kg (pounds) of catalytic system. Therefore, Example 7, which contained about 33.7% more Hf than comparative example C5, showed an increase in catalyst productivity of about 114% over comparative example C5.
[0105] Examples 8 and 9 also showed a surprising and unexpected increase in catalyst productivity. Example 9 used the same amount of MAO, that is, about 6.25 mmoles / g of support, but increased the amount of Hf in the catalytic system from about 0.8% by weight to about 1.08% in weight, and produced a 114% increase in catalyst productivity. Example 9 used about 24.8% less MAO (about 4.7 mmoles / g of support versus about 6.25 mmoles / g of support) than comparative example C6, but increased the amount of Hf in the catalyst from about 0.8% by weight to about 1.05% by weight, and produced an increase in catalyst productivity of about 66.4%.
Gas phase polymerization process with fluidized bed - Series of
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Examples IV [0106] In Comparative Example C7 and Example 10 shown in Table 4 the catalyst was bis (n-propylcyclopentadienyl) hafnium (CH3) 2 and a silica support (PQ ES-757 silica having a surface area of about 300 m ² / g, a pore volume of about 1.5 cm ³ / g, and a particle size of about 25 pm) was mixed with an aluminum compound and ammonium hexafluorsilicate (ratio 18) and then calcined . The supports for comparative example C7 and Example 10 had an aluminum content of about 8.5% by weight, a silicon content of about 30% by weight, and a fluoride content of about 4% in Weight. The catalysts were prepared by method 2. In Comparative Example C8 and Example 11 the catalytic systems were prepared in the same manner as in Example 4 above.
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Table 4 Examples C7 Ex. 10 C8 Ex. 11 Polymer type LLDPE LLDPE LLDPE LLDPE mmol MAO / g catalyst 1.55 1.55 1.8 1.8 Hf (% by weight, based on the total weight of the catalytic system) 0.887 0.887 0.89 0.89 Al (% by weight, based on the total weight of the catalytic system) 8,457 8,457 30.57 30.57 Al (% by weight, based on the total weight of the support) 4.43 4.43 27.98 27.98 F (% by weight, based on the total weight of the support) 3.26 3.26 5.48 5.48 Triethyl aluminum (ppmw) - 11.34 - 11.59 Reaction conditions Production rate 14,174 16,421 15.967 16,039 (kg / h (lb / h)) (31.22) (36.17) (35.17) (35.33) STY (kg / h / m ³ (lb / n / ft ³ )) 78,422 89,388 89,769 90,150 (4.8902) (5,574) (5.2236) (5.6215) Residence time (h) 3.33 2.91 3 3.05 Partial pressure of C2 (MPa 1.519 1.518 1.522 1.518 ⁽ p ^asia)) (220.45) (220.25) (220.78) (220.13) Reason for concentrationC6 / C2 (m / m) 0.0137 0.0155 0.0142 0.0157 H2 concentration (ppm) 262 253 306 280 Pressure (MPa 2,397 2,397 2,397 2,397 pressure gauges (psig)) (347.8) (347.8) (347.64) (347.8) Temperature (° C) 77.99 77.98 76.98 77 Gas speed (m / s 0.661 0.658 0.646(ft / s)) (2.17) (2.16) (2.12) 0.64 (2.1)47,174 47,627 48,080 48,988 Bed weight (kg (lb)) (104) (105) (106) (108) Mass density of 0.267 0.261 0.253 0.277 fluid (g / cm ³ / (lb / ft ³ )) (16.41) (16.33) (15.79) (17.3) Continuity Additive Lupasol Lupasol Lupasol Lupasol Continuity additive concentration (ppmw of product) 6.6 5.7 5.9 5.8 Product properties Melting index (dg / min) (I ₂ ) 0.613 0.531 0.723 0.848 Flow index (I ₅ ) 1,755 1,572 2,077 2,548 Flow index (I ₂₁ ) 17,172 17,823 20.15 27.87 MFR (I21 / I2) 28 33.6 27.9 32.9
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MFR (I21 / I5) 9.8 11.3 9.7 10.9 Density (g / cm ³ ) 0.9182 0.9181 0.9169 0.9186 Mass density 0.456 0.455 0.423 0.438 (g / cm ³ (lb / ft ³ )) (28.5) (28.45) (26.4) (27.37)0.076 0.068 0.061 0.114 APS sieve ((cm (in)) (0.0299) (0.0271) (0.0409) (0.045) APS (micron) 759 687 1039 1142 Fines in the sieve LT No 120(% by weight) 0.7 0.61 0.58 0.33 Catalyst productivity Catalyst productivity (Hf ICPES) 9,966 13,239 11,978 18,804
[0108] The polymers produced in Examples 10 and 11 which included the addition of triethyl aluminum to the polymerization reactor had an increased MFR compared to comparative examples C7 and C8, respectively. As for Example 10, triethyl aluminum in an amount of about 11.34 ppmw was introduced into the polymerization reactor and the polymer's MFR increased from about 28.0 (C7) to about 33.6, which was an increase of about 20% in MFR. In addition, the hydrogen to ethylene ratio (H2 / C2) and the hexene to ethylene ratio were adjusted to maintain a similar density and melt index (I2). As for Example 11, triethyl aluminum in an amount of about 11.59 ppmw was introduced into the polymerization reactor and the polymer's MFR increased from about 27.9 (C8) to about 32.9, which was an increase of about 18% in MFR. Similar to Example 10, the amounts of hydrogen and hexene were adjusted to maintain a similar density and melt index (I2). In addition, the catalyst productivity for examples 10 and 11 increases by about 40% and about 56%, respectively, with the addition of triethyl aluminum.
[0109] Examples 10 and 11 show that additional control over the polymer's MFR can be obtained if the catalytic systems discussed and described in this invention are used together with one or more organoaluminum compounds, for example, triethyl aluminum. Increasing the MFR can provide a polymeric product that can be easier to process to form products.
Suspension polymerization process - Series of Examples V
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61/71 [0110] Examples 12-19 and comparative example C9 were prepared by a laboratory suspension process. Either triisobutylaluminium (TiBAl) or triethylaluminium (TEAL) was added to the reaction mixture. For the examples having TiBAl, the ratio of TiBAl to the total molar amount of metal in the catalyst was about 150: 1. For the examples having TEAL, the TEAL ratio to the total molar amount of metal in the catalyst was about 30: 1. TiBAl or TEAL was added to sequester impurities contained in the reactor or in the catalytic system that can render the catalyst ineffective.
[0111] For all Examples 12-19 and C9, the metallocene-based catalyst was bis (n-propylcyclopentadienyl) hafnium Me2. The catalytic systems for examples 12-19 included an alumina-silica support (Siral 40) which was mixed with ammonium hexafluorsilicate and calcined. The ammonium hexafluorsilicate / support ratio was about 18 for examples 14, 15, and 18. The ammonium hexafluorsilicate / support ratio was about 12 for examples 12, 13, 16, 17, and 19. The supports for examples 12-19 had an aluminum content of about 27% by weight, a silicon content of about 18% by weight, and a fluorine content of about 3.7-5.0% by weight. Weight. The catalysts were prepared according to method 2. The catalyst systems in Examples 12-19 had an Hf loading of about 0.8% by weight.
[0112] The catalytic system of comparative example C9 is the same catalytic system as that employed in C1 and C2. Catalytic activity was measured in grams of polyethylene (PE) per gram of catalytic system in one hour (gPE / g of catalytic system-h). Catalytic activity was also measured in grams of polyethylene per gram of catalyst (the metallocene-based catalyst) in one hour (gPE / gCat-h).
[0113] A 1.5 liter autoclave reactor in a nitrogen purge was loaded with a catalyst, followed by 10 ml of hexene and 400 cm ³ of isobutane diluent. The reactor was heated to 90 ° C and from about 40 mg to about 60 mg, depending on the particular example of each catalytic system, they were then introduced into the reactor. For each example, ethylene [1.38 MPa (200 psig)] was
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62/71 introduced into the reactor to give a total reactor pressure of 2.99 MPa (434 psig). The reactor temperature was maintained at 90 ° C and the polymerization was allowed to proceed for 21 to 70 minutes, depending on the particular example, and the reactor was then cooled. The ethylene was removed and the polymer was dried and weighed to obtain the yield of the polymer. The results of the polymerization are summarized below in Table 5.
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Table 5 Example Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Ex. 19 C9 Addition ofcocatalyst / scavenger TiBAl TEAL TiBAl TiBAl TiBAl TEAL TiBAl TiBAl TiBAl Catalytic system weight (g) 0.04 0.04 0.05 0.05 0.05 0.05 0.05 0.05 0.056 MAO mmol / g support 1 1 1.5 2 2 2 3 3 6.25 Al (% by weight, based on the total weight of the catalytic system) 29.9 29.9 29.9 29.9 29.3 29.3 28 29.1 11.1 Hf (% by weight, based on the total weight of the catalytic system) 0.8 0.8 0.8 0.81 0.85 0.85 0.78 0.81 0.83 Al (% by weight, based on the total weight of the support) 26.14 26.14 30.39 27.67 26.14 26.14 24.9 26.14 - F (% by weight, based on the total weight of the support) 5.12 5.12 3.08 3.54 5.12 5.12 3.54 5.12 - Catalyst weight (mg) 0.89 0.88 1.01 1 1.07 1.09 1.04 1.08 1.1 Polymer yield 265 268 230 215 279 289 254 280 221 Catalytic activity (g PE / g catalytic-h) 5.932 6.086 4,551 4,265 8,934 11,784 4.885 10.066 3.967 Mass density (g / cm ³ ) 0.37 0.37 0 0.34 0.39 0.4 0.36 0.36 0.33 Catalytic activity (g PE / g Cat-h) 297,258 304,977 228,020 215,330 447,541 589,195 244,231 502,348 201,255
63/71
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64/71 [0114] Examples 12-19 showed a higher catalytic activity than comparative examples C9, based on the amount of MAO present in the catalytic system. For example, comparative example C9 used about 6.25 mmoles of MAO per gram of support and a catalytic activity of about 3.967 grams of polymer per gram of catalytic system per hour was observed. Example 19 used less than half of MAO than C8, that is, about 3 mmoles per gram of support versus 6.25 mmoles per gram of support, and a catalytic activity of about 10.066 grams of polymer per gram of catalytic system was observed. Therefore, in Example 19 the amount of MAO was reduced by more than 50% while increasing the catalytic activity by more than 153%.
[0115] Examples 20-22 shown in Table 6 were prepared similarly to Examples 12-19. In Examples 20-22, the catalyst was bis (npropylcyclopentadienyl) hafnium (CH3) 2, and instead of fluorinated an aluminasyl support, a silica support (PQ ES-757 silica having a surface area of about 300 m ² / g, a pore volume of about 1.5 cm ³ / g, and a particle size of about 25 pm) was mixed with an aluminum compound and ammonium hexafluorsilicate (18 ratio) and then calcined. The supports for examples 20-22 had an aluminum content of about 5% by weight, a silicon content of about 30% by weight, and a fluoride content of about 4% by weight. The catalytic systems were prepared using method 2.
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Table 6 Example Ex. 20 Ex. 21 Ex. 22 C9 Addition ofcocatalyst / scavenger TiBAl TiBAl TiBAl TiBAl Catalytic system weight (g) 0.054 0.057 0.049 0.056 MAO mmol / g support 2.9 1.75 1 6.25 Al (% by weight, based on the total weight of the catalytic system) 10.7 8.47 6.8 11.1 Hf (% by weight, based on the total weight of the catalytic system) 0.85 0.89 0.84 0.83 Al (% by weight, based on the total weight of the support) 3.71 4.41 3.71F (% by weight, based on the total weight of the support) 3.17 3.15 3.17Catalyst weight (mg) 1.08 1.14 0.98 1.1 Polymer yield (g) 282 281 181 221 Catalytic activity (g PE / g catalytic-h) 6.227 5.688 3,662 3.967 Mass density (g / cm ³ ) 0.4 0.41 0.4 0.33 Catalytic activity (g PE / g Cat-h) 313,633 284,413 184,224 201,255
[0117] Catalytic systems having fluorinated-silica alumina supports showed higher catalytic activity compared to the catalytic system without fluorinated-silica alumina support. Example 20, having only about 2.9 mmoles of MAO per gram of support, showed a catalytic activity of about 6.227 g PE / g catalytic-h. Comparative example C9, having more than twice the amount of MAO at about 6.25 mmoles per gram of support showed a catalytic activity of only about 3.967 g PE / g catalytic system per h, which is about 36% any less. [0118] In Examples 23, 24 and C10, the catalyst was bis (n-butyl, methyl cyclopentadienyl) zirconium Cl2. In Example 25, the catalyst was [(2,3,4,5,6 Me5C6) CH2CH2] 2 HZrBz2, where Bz is a benzyl group. The supports for examples 23 and 25 were the same as those used in Examples 20-22 and were also prepared by method 2. The support for example 24 was Siral 40 activated at 600 ° C with ammonium hexafluorsilicate and was prepared by the method 1. The
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66/71 support for the CIO comparative example was silica PQ ES70 (a surface area of about 300 m2 / g, a pore volume of about 1.5 cm3 / gm, and a particle size of about 48 pm) dehydrated at 600 ° C and was prepared by method 2. The results of the polymerization are summarized below in Table 7 below.
i.
Table 7 Example Ex. 23 Ex. 24 Ex. 25 C10 Addition ofcocatalyst / scavenger TiBAl TiBAl TiBAl TiBAl Catalytic system weight (g) 0.08 0.07 0.04 0.11 MAO mmol / g support 2.9 2.9 2.9 6.25 Al (% by weight, based on the total weight of the catalytic system) 9.5 30.2 9.4Zr (% by weight, based on the total weight of the catalytic system) 0.35 0.35 0.37 0.35 (target) Al (% by weight, based on the total weight of the support) - 26.8 - - F (% by weight, based on the total weight of the support) 2.91 4.09 - - Catalyst weight (mg) 1.1 1.02 1 2 Polymer yield 280 179 204 173 Catalytic activity (g PE / g catalytic-h) 4,190 2,410 4.909 1.524 Mass density (g / cm3)0.41 0.3 0.45 Catalytic activity (g PE / g Cat-h) 305,455 175,108 204,220 86,590
[0119] Catalytic activity for all three Examples 23-25 showed surprisingly and unexpectedly higher catalytic activity while using less MAO, compared to comparative example C10. For example, in Example 25, using the catalyst [(2,3,4,5,6 Me5C6N) CH2CH2] 2 HZrBz2, where Bz is a benzyl group, used only about 2.90 mmoles MAO per gram of support and had a catalytic activity of about 4,190 gPE / g of catalytic system h. Comparative Example C10, having more than twice the amount of MAO at about 6.25 mmoles per gram of support had only
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67/71 a catalytic activity of about 1.524 g PE / g catalytic system-per h. Example 25 also showed a catalytic activity comparable to Examples 14, 15, and 18.
[0120] The catalytic activity for examples 23-24 showed a higher catalytic activity although using less MAO, compared to comparative example C10. Examples 23 and 24 had a catalytic activity of 4,190 g of PE / g of catalytic system-per h and 2,410 g of PE / g of catalytic system-per h, respectively, whereas comparative example C10 (having more than double of the amount of MAO to about 6.25 mmoles per gram of support) had only a catalytic activity of about 1.524 g of PE / g of catalytic system-per h. Example 25, which used the catalyst [(2,3,4,5,6 Me5C6N) CH2CH2] 2 HZrBz2, where Bz is a benzyl group, only about 2.90 mmoles MAO per gram of support was used and showed a catalytic activity of about 4,190 gPE / g of catalytic-h system. The catalytic activity shown in Example 25 was comparable to that of Examples 14, 15, and 18. Laboratory gas phase polymerization process - Series of Examples VI [0121] Additional examples using catalysts employing higher levels of MAO were conducted in a reactor of 1.5 liter agitated gas phase with a 400 g salt bed (NaCl). The reactor was operated on about 1.38 MPa (220 psi) of ethylene, about 400-450 ppm of hydrogen, and a hexane / ethylene charge ratio of about 0.026 to about 85 ° C for one hour. The catalyst was charged under reduced pressure and about 5 grams of a mixture of MAO on silica (about 6.5 mmoles MAO per gram of silica) was previously loaded as a scavenger.
[0122] The catalytic systems used in Examples 26 and 27 and in comparative example C11 were prepared by method 2 with higher levels of MAO. The supports used for examples 26 and 27 were the same as those used in Example 1 (PQ ES-70W with Al) with sufficient ammonium hexafluorsilicate added for a final composition of about 3.23% by weight of F for the example 26 and about 4.24% by weight of Al and 2.96% by weight of F for the
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68/71 example 27, based on the weight of the support. The support used for comparative example C11 was PQ ES-757 silica (a surface area of about 300 m ² / g, a pore volume of about 1.5 cm ³ / g, and a particle size of about 25 pm) dehydrated at 875 ° C.
[0123] The catalytic systems used in Examples 28 and 29 were prepared by method 2 with higher levels of MAO, i.e., about 6.25 mmoles of MAO / g of support. Example 29, compared to Example 28, had a higher concentration of the transition metal component of the catalyst, i.e., about 1.02% by weight versus about 0.83% by weight based on the total weight of the catalyst system . The supports used for examples 28 and 29 were Siral 40 activated at 600 ° C with sufficient ammonium hexafluorsilicate to give a final composition of 26.03% by weight of Al and 5.24% by weight of F, based on weight support. For examples 25-29 and C11, the metallocene-type catalytic compound was bis (n-propylcyclopentadienyl) hafnium (CHs) 2. The polymerization results are summarized below in Table 8.
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Tabe to 8 Example C11 Ex. 26 Ex. 27 Ex. 28 Ex. 29 mmol MAO / g support 6.25 4.7 6.25 6.25 6.25 Hf (% by weight, based on the total weight of the catalytic system) 0.8 1.03 1.08 0.83 1.02 Al (% by weight, based on the total weight of the catalytic system) 12 11.4 11.55 34.5 34.1 Al (% by weight, based on the total weight of the support) - 4.2426.03 26.03 F (% by weight, based on the total weight of the support) 0 3.23 2.96 5.24 5.24 Catalytic system weight (g) 0.0062 0.0061 0.0061 0.0109 0.0084 Polymer yield (g) 43 87 90 117 124 Catalytic activity (g PE / g catalytic-h) 6,935 14,262 14,754 10,733 14,762
69/71
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70/71 [0124] Increasing the Hf load when using a fluorinated support greatly increases catalyst productivity. Example 26 used about 24.8% less MAO (about 4.7 mmoles / g of support versus about 6.25 mmoles / g of support) than comparative example C11, but increased the amount of Hf in the catalyst about 0.8% by weight to about 1.03% by weight, and produced an increase in catalyst productivity of about 106%. Example 27 used the same amount of MAO, that is, about 6.25 mmoles / g of support, but increased the amount of Hf in the catalytic system from about 0.8% by weight to about 1.08% in weight, and produced an increase in catalyst productivity of about 113%.
[0125] Example 29, compared to Example 28, also shows a surprising and unexpected increase in catalytic activity that only the amount of the transition metal component, ie Hf, was increased with the composition of the substrate and the amount of MAO remaining the same. More particularly, the MAO concentration and the particular support for both examples were the same, i.e., about 6.25 mmoles MAO and fluorinated Siral 40. Example 28 had an Hf concentration of about 0.83% by weight based on the total weight of the catalytic system and showed a catalytic activity of about 10.733 g PE / g catalytic system per hour. Example 29, however, having an increased concentration of Hf, that is, about 1.02% by weight, compared to Example 26, which contained only about 0.83% by weight, showed a catalytic activity of about 14.762 g PE / g catalytic system per hour, which is a 37% increase in catalytic activity.
[0126] All numerical values are "about" or approximately the indicated value, and take into account experimental errors and variations that are expected by the person skilled in the art.
[0127] Several terms have been defined above. Whenever a term used in any claim is not defined above, it must have the broadest definition given by experts in the relevant technique already reflected in at least one printed publication or patent granted. In addition, all patents,
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71/71 test procedures, and other documents cited in this application are hereby incorporated in their entirety by reference to the extent that such description is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.
[0128] Although the above description is concerned with modalities of the present invention, additional additional modalities of the invention can be created without departing from its basic scope, and its scope is determined by the claims that follow.

权利要求:
Claims (30)
[1]
1. Catalytic system, characterized by the fact of understanding:
- a single site catalytic compound;
- a support comprising fluorinated alumina; and
- an aluminoxane, in which the aluminoxane is present in an amount of 7 mmoles or less per gram of the support.
[2]
2. Catalytic system, according to claim 1, characterized by the fact that the support has a fluoride concentration ranging from 1% by weight to 10% by weight, based on the weight of the support and an aluminum concentration varying from 3% by weight to 40% by weight based on the weight of the support.
[3]
3. Catalytic system according to claim 1, characterized in that the single site catalytic compound has a metal concentration ranging from 0.2% by weight to 1.3% by weight, based on the total weight of the system catalytic.
[4]
4. Catalytic system, according to claim 1, characterized by the fact that aluminoxane is present in an amount of 3 mmoles or less per gram of the support.
[5]
5. Catalytic system according to claim 1, characterized in that the support additionally comprises silica.
[6]
6. Catalytic system according to claim 1, characterized in that the single site catalytic compound comprises a metallocene catalyst.
[7]
7. Catalytic system, according to claim 6, characterized by the fact that the metallocene catalyst has the formula:
Cp ^A Cp ^B MXn or Cp ^A (A) Cp ^B MXn, where M is an atom of group 4, 5 or 6; each of Cp ^A and Cp ^B is linked to M and are independently selected from the group consisting of cyclopentadienyl-type ligands, substituted cyclopentadienyl-type ligands, cyclopentadienyl isolobal ligands and substituted cyclopentadienyl isolobal ligands; (A) is a divalent group bonded bridge Cp ^A and Cp ^B selected from the group consisting of C 1 to C ₂₀ divalent hidrocarbilas and C1 to _C20 heteroatom - containing hidrocarbonilas, wherein the hetero comprise hidrocarbonilas
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2/5 one to three heteroatoms; X is a displaceable group selected from the group consisting of chloride ions, bromide ions, Ci to Cw alkyls, and C ₂ to Ci ₂ alkenyls, carboxylates, acetylacetonates, and alkoxides; and n is an integer from 1 to 3.
[8]
8. Catalytic system according to claim 1, characterized in that the single site catalytic compound comprises a compound having the formula:

wherein M is a transition metal from group 3 to 12 or a major group metal from group 13 or 14; each X is independently an anionic displaceable group; y is 0 or 1; n is the oxidation state of M; m is the formal charge of the ligand represented by YZL or YZL '; L is a member of group 15 or 16; L 'is a group containing an element of group 15 or 16 or containing atoms of group 14; Y is a member of group 15; Z is a member of group 15; R ¹ and R ² are independently a C ₁ to C ₂ hydrocarbon group, a group containing hetero atoms having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus; R ¹ and R ² can be interconnected to each other; R ³ is absent, it is a hydrocarbon group, hydrogen, a halogen, or a group containing hetero atoms; R ⁴ and R ⁵ are independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group, a multiple ring system; R ⁴ and R ⁵ can be interconnected to each other; R ⁶ and R ⁷ are independently absent, they are hydrogen, a
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3/5 alkyl group, a halogen, a heteroatom, or a hydrocarbyl group; and R * is absent, is hydrogen, a group containing an atom of Group 14, a halogen, or a group containing hetero atoms.
[9]
9. Catalytic system, according to claim 1, characterized in that the catalytic system further comprises one or more second catalysts selected from a metallocene, a Ziegler-Natta catalyst, a chromium catalyst, a transition metal catalyst, a catalyst containing atoms of Group 15, or any combination thereof.
[10]
10. Catalytic system, according to claim 1, characterized by the fact that it also comprises one or more organoaluminium compounds.
[11]
11. Method for preparing the catalytic system, as defined in the claim
1, characterized by the fact of understanding:
- combining the single site catalytic compound, the support comprising fluorinated alumina, and the aluminoxane, in which the aluminoxane is present in an amount of 7 mmoles or less per gram of the support.
[12]
12. Method according to claim 11, characterized in that it further comprises combining one or more organoaluminium compounds with the single site catalytic compound and the support.
[13]
13. Method according to claim 11, characterized in that the fluorinated alumina is prepared by calcining a silica-aluminum support at a temperature of 200 ° C to 1000 ° C, in the presence of a fluorine source.
[14]
14. Method according to claim 11, characterized in that the fluorinated alumina is prepared by calcining a silica support at a temperature of 200 ° C to 1000 ° C, in the presence of an aluminum source and a source of fluorine.
[15]
15. Method according to claim 11, characterized in that the fluoride source comprises ammonium hexafluorsilicate, ammonium bifluoride, ammonium tetrafluoroborate, or any combination thereof.
[16]
16. Method according to claim 11, characterized in that the single-site catalytic compound and aluminoxane are combined to
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4/5 produce a first mixture.
[17]
17. Method according to claim 11, characterized in that the single site catalytic compound and aluminoxane are combined in a diluent.
[18]
18. Method according to claim 16, characterized in that the support is combined with the first mixture.
[19]
19. Method according to claim 16, characterized in that the first mixture and the support are independently added to the polymerization reactor.
[20]
20. Method according to claim 11, characterized in that the support and the aluminoxane are combined to produce a first mixture.
[21]
21. Method according to claim 20, characterized in that the first mixture is combined with the single site catalytic compound outside a polymerization reactor.
[22]
22. Method according to claim 20, characterized in that the first mixture is combined with the single site catalytic compound within a polymerization reactor.
[23]
23. Method for polymerization of olefins, characterized by the fact that it comprises:
- contacting ethylene and at least one comonomer comprising one or more C4 to C8 alpha olefins with the catalytic system, as defined in claim 1 in a polymerization reactor under conditions sufficient to produce a polyethylene.
[24]
24. Method according to claim 23, characterized in that it further comprises adjusting the concentration of one or more alpha olefins C4 to C8 within the polymerization reactor to control at least one between density and melt index (I2) of the polyethylene .
[25]
25. Method, according to claim 23, characterized by the fact that it also comprises introducing one or more organoaluminium compounds in the polymerization reactor.
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5/5
[26]
26. Method according to claim 25, characterized in that the organoaluminium compound is added to the reactor in an amount sufficient to increase the melt flow ratio (MFR) of the polyethylene.
[27]
27. Method, according to claim 23, characterized by the fact that it also comprises adjusting the hydrogen concentration within the reactor to control at least one between density and melting index (I2) of the polyethylene.
[28]
28. Method according to claim 23, characterized in that the ethylene is contacted with the catalytic system under gas phase conditions.
[29]
29. Method according to claim 23, characterized in that the catalytic system has a productivity of at least 2,000 grams of polyethylene per gram of the catalytic system.
[30]
30. Method according to claim 23, characterized in that the catalytic system has a productivity of at least 8,000 grams of polyethylene per gram of the catalytic system.

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-16| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-11-12| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-01-07| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/02/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US30674910P| true| 2010-02-22|2010-02-22|

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US61/306,749|2010-02-22|

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PCT/US2011/025405|WO2011103402A1|2010-02-22|2011-02-18|Catalyst systems and methods for using same to produce polyolefin products|

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