• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    polymers with long branched chains and methods of producing them. a polymer that has a long chain branch content reaching a peak above about 20 long chain branches per million carbon atoms and a polydispersity index greater than about 10, where the long chain branch decreases to approximately zero in the highest molecular weight portion of the molecular weight distribution. a polymer that has a long chain branch content peaking above about 8 long chain branches per million carbon atoms, a polydispersity index greater than about 20, where the long chain branch decreases to approximately zero in the highest molecular weight portion of the molecular weight distribution. a polymer having a long chain branch content peaking above about 1 chain branch and a polydispersity index greater than about 10, where the long chain branch decreases to approximately zero in the highest molecular weight portion molecular weight distribution.
    公开号:BR112014013159B1
    申请号:R112014013159-7
    申请日:2012-11-14
    公开日:2020-09-29
    发明作者:Youlu Yu；Eric D Schwerdtfeger；Max P Mcdaniel；Alan L Solenberger；Kathy S. Collins
    申请人:Chevron Phillips Chemical Company Lp；
    IPC主号:
    专利说明:

    TECHNICAL AREA
    [0001] The present disclosure refers to the new polymer compositions and methods of production and use thereof. More specifically, the present disclosure relates to polymer compositions that have long chain branching. BACKGROUND OF THE INVENTION
    [0002] Polymeric compositions, such as polyethylene compositions, are used for the production of a wide variety of articles. The use of a specific polymer composition in a specific application will depend on the type of physical and / or mechanical properties exhibited by the polymer. Thus, there is a constant need to develop polymers that have new physical and / or mechanical properties and methods for producing these polymers. SUMMARY
    [0003] A polymer with a long chain branch content reaching a peak above about 20 long chain branches per one million carbon atoms and a polydispersity index (Mw / Mn) greater than about 10, in which the long chain branching decreases to approximately zero in the highest molecular weight portion of the molecular weight distribution.
    [0004] A polymer with a long chain branch content reaching a peak above about 8 long chain branches per million carbon atoms is also disclosed in this document, a polydispersity index greater than about 20, where the long chain branching decreases to approximately zero in the highest molecular weight portion of the molecular weight distribution.
    [0005] Also disclosed in this document is a polymer with a long chain branch content reaching a peak above about 1 chain branch and a polydispersity index greater than about 10, where the long chain branch decreases to approximately zero in the highest molecular weight portion of the molecular weight distribution.
    [0006] A method of polymerizing a monomer is also disclosed in this document, comprising the contact between the monomer and a chromium-supported catalyst under conditions suitable for the formation of a polymer; and polymer recovery, in which the chromium-supported catalyst comprises a silica support having a surface area of less than about 200 m2 / g and in which the polymer has a long chain branching content peaking above about 20 long chain ramifications for one million carbon atoms. BRIEF DESCRIPTION OF THE FIGURES
    [0007] Figures 1-7 are graphs of the long chain branching content as a function of the molecular weight for the sample samples. DETAILED DESCRIPTION
    [0008] New polymer compositions and methods of producing them are disclosed here. In one embodiment, the polymer compositions comprise designated long branched-chain polymers (LCBP). Hereinafter, the polymer refers to both the material collected and the product of a polymerization reaction and the polymeric composition comprising the polymer and one or more additives.
    [0009] LCBPs can be produced using catalysts comprising chromium and a low surface area support. From now on, such catalysts are called catalysts for the production of long branched-chain polymers and are called Cr-X. In one embodiment, an LCBP is prepared by a methodology that employs a Cr-X catalyst and at least one modification. In this document, a modification refers to a specified reagent and / or reaction conditions that are employed in the preparation of the polymer, as described in more detail here.
    [0010] In one embodiment, an LCBP is prepared by a methodology that employs a Cr-X catalyst and at least one Class A modification. In this document, a Class A modification refers to a change in the type of catalyst used in the reaction for the preparation of an LCBP. In one embodiment, the Class A modification comprises activating the Cr-X catalyst at a temperature below about 650 ° C. In one embodiment, the Class A modification involves adjusting the amount of Cr present in the support to provide a chromium distribution greater than about 2 chromium atoms per nm2 of support. In one embodiment, the Class A modification includes the incorporation of titanium to Cr-X.
    [0011] In one embodiment, the LCBP is prepared by a methodology that employs a Cr-X catalyst and at least one Class B modification. In this document, a Class B modification refers to a change in the type and / or quantity of reagents used in the reaction for the preparation of an LCBP. In one embodiment, the Class B modification involves providing a monomer concentration in the reactor that is less than about 1 mole / liter (mole / L). In one embodiment, the Class B modification comprises the application of a cocatalyst in the reaction for the production of LCBP. LCBPs and methodologies for preparing an LCBP are described in more detail in this document.
    [0012] In one embodiment, a Cr-X catalyst is used to prepare an LCBP of the type disclosed in this document. The Cr-X catalyst may comprise chromium and a catalyst support.
    [0013] In one embodiment, the support of the Cr-X catalyst may mainly include an inorganic oxide, such as silica, alumina, aluminum phosphates or mixtures thereof. In one embodiment, the support contains more than about 50 percent (%) silica, alternatively more than about 80% silica, by weight, of the support. The support may further include additional components that do not adversely affect the catalyst system, such as zirconia, alumina, boron, thorium, magnesia or mixtures thereof.
    [0014] In one embodiment, the support comprises precipitated silica. For example, the support can include precipitated or gelated silica. In this document, a precipitated or gelled silica contains a three-dimensional network of primary silica particles.
    [0015] In one embodiment, the support is a reinforced support. Such reinforced supports can be prepared by any appropriate methodology. For example, a reinforced support suitable for use in the present disclosure is prepared by aging the support material. For example, the support may have alkaline aging by contacting the support with an alkaline solution containing one or more basic compounds (for example, bases, buffer) having a pH of about 8 to 13, alternatively, of about 9 to 12 or, alternatively, from about 9 to about 10 at a temperature of about 60 ° C to about 90 ° C, or from about 70 ° C to about 85 ° C, or about 80 ° C. The alkaline solution can comprise all components that provide a solution pH in the disclosed ranges and are compatible with the other components of the composition. For example, the alkaline solution can include ammonium hydroxide, potassium hydroxide, sodium hydroxide, trialkylammonium hydroxide, sodium silicate and the like. Other suitable compounds and amounts effective to provide a solution in the disclosed pH ranges can be used.
    [0016] In an alternative modality, the support can be aged by contact with a neutral solution (neutral aging), having a pH of about 7 at a temperature of about 60 ° C to about 90 ° C, or about from 70 ° C to about 85 ° C, or about 80 ° C.
    [0017] Optional aging of the substrate (alkaline or neutral) can be performed for a period of time sufficient to reduce the surface area of the substrate to less than about 80% of the original value of the surface area of a material otherwise similar that has not been aged, alternatively to less than about 50%, 60% or 70%. In one embodiment, aging is carried out for a period of time from about 1 hour to about 24 hours, or from about 2 hours to about 10 hours or from about 3 hours to about 6 hours.
    [0018] In one embodiment, a method for preparing a reinforced support further comprises drying the support. The support can be dried to remove the solvent and form a dry support. Drying can be carried out in a temperature range of about 25 ° C to about 300 ° C, alternatively, from about 50 ° C to about 200 ° C or, alternatively, from about 80 ° C to about 150 ° C and for a period of time from about 0.1 min to about 10 hours, alternatively from about 0.2 min to about 5 hours or, alternatively, from about 30 min to about 1 hour . In one embodiment, a method for preparing a reinforced support further comprises alternatively the dry support to form a dry calcined support. For example, the dry support can be calcined in the presence of air at a temperature in the range of about 400 ° C to about 1,000 ° C, alternatively, from about 500 ° C to 900 ° C and for a period of time from about 1 hour to about 30 hours, alternatively from about 2 hours to about 20 hours or, alternatively, from about 5 hours to about 12 hours.
    [0019] In one embodiment, the reinforced support is prepared by hydrothermal treatment (steam) of the support to reduce the surface area. Alternatively, the reinforced support is prepared by thermal sintering the support. Alternatively, the reinforced support is prepared by chemical sintering of the support, such as using a flow agent, such as sodium ions or potassium ions, during heat treatment. Alternatively, the reinforced support is prepared by a methodology that involves a secondary deposition of silica on a silica, using, for example, sodium silicate or tetraethylorthosilicate or SiCl4, etc. Alternatively, the reinforced support is prepared by a combination of two or more of the disclosed methodologies. For example, the reinforced support can be prepared by alkaline aging and hydrothermal treatment.
    [0020] In one embodiment, the support is a low surface area support. In this document, a low surface area support has a surface area of less than about 250 m2 / g, alternatively, less than about 200 m2 / g, alternatively, less than about 150 m2 / g or, alternatively, less than about 125 m2 / g. In addition, the pore volume of the support can vary from about 0.5 cubic centimeters per gram (cm3 / g) to about 3.5 cm3 / g or, alternatively, from about 0.8 cm3 / g to about 3 cm3 / g. To maintain simplicity, the disclosure will refer to silica as the support, although other supports, as described in this document, can be contemplated.
    [0021] The amount of support present in the catalyst (for example, Cr-X) can vary from about 90% to about 99.9% by weight of the catalyst, alternatively, from about 95% to about 99.9 %, or about 97% to about 99.9%. In one embodiment, the support comprises the rest of the catalyst, when all other components are accounted for.
    [0022] In one embodiment, the catalyst comprises chromium. Chromium can be included in the Cr-X catalyst by contacting a chromium-containing compound with a support of the type described above. The chromium-containing compound may comprise a water-soluble chromium compound. Alternatively, the chromium-containing compound comprises a hydrocarbon-soluble chromium compound. Examples of water-soluble chromium compounds include, but are not limited to, chromium oxide, chromium trioxide, chromium acetate, chromium nitrate or combinations thereof. Examples of hydrocarbon-soluble chromium compounds include, but are not limited to, tert-butyl chromate, a chromium diarene compound (0), bisciclopentadienyl chromium (II), chromium acetylacetonate (III) or combinations thereof. In one embodiment, the chromium-containing compound can be a chromium (II) compound, chromium (III) compound or combinations thereof. Suitable chromium (III) compounds include, but are not limited to, chromium carboxylates, chromium naphthenates, chromium halides, chromium sulfate, chromium nitrate, chromium dionates or combinations thereof. Specific chromium (III) compounds include, but are not limited to, chromium (III) sulfate, chromium (III) chloride, chromium (III) nitrate, chromium bromide, chromium (III) acetylacetonate, chromium (III) acetate . Suitable chromium (III) compounds include, but are not limited to, chromium chloride, chromium bromide, chromium iodide, chromium (II) sulfate, chromium (II) acetate or combinations thereof.
    [0023] The amount of chromium present in the catalyst (for example, Cr-X) can vary from about 0.01% to about 10% by weight of the catalyst, alternatively, from about 0.5% to about 5 %, or about 1.0% to about 3%. In this document, the chromium percentage refers to the final chromium percentage associated with the support material by the total weight of the material after all the processing steps.
    [0024] In one embodiment, chromium is present in sufficient quantity to provide a distribution of chromium (VI) greater than about 2 chromium atoms per nm2 of support, alternatively greater than about 2.5 chromium atoms per nm2 of support , or alternatively, greater than about 3 chromium atoms per nm2 of support. In some embodiments, the chromium (VI) distribution is the average distribution based on the use of more than one type of catalyst. For example, a distribution of chromium within the values disclosed in this document can be achieved through the use of a catalyst with conventional Cr support and a Cr-X catalyst of the type disclosed in this document.
    [0025] In another embodiment, a method of preparing a Cr-X catalyst comprises contacting a support of the type disclosed in this document with a compound containing chromium to form Cr-silica. the chromium-containing compound can be a water-soluble compound or a hydrocarbon-soluble compound, such as those described in this document, and can be introduced into the support using any appropriate contact technique. For example, the chromium-containing compound can be brought into contact with the silica support using techniques such as ion exchange, incipient moisture, pore filling, impregnation, etc.
    [0026] Cr-silica can then be dried to remove the solvent at temperatures ranging from 25 ° C to about 300 ° C, alternatively from about 50 ° C to about 200 ° C or, alternatively, from about 80 ° C to about 150 ° C and for a period of time from about 0.1 min to about 10 hours, alternatively from about 0.2 min to about 5 hours, alternatively from about 30 min at about 1 hour, thus forming a dry Cr-silica.
    [0027] In one embodiment, dry Cr-silica is activated to produce an active catalyst, alternatively an active polymerization catalyst. The dry Cr-silica of the present disclosure can be activated using various types of activator equipment. Any container or apparatus can be used to activate dry Cr-silica including rotary calciners, for example, static pan driers or fluidized beds. Such equipment can operate in a static, batch, or continuous mode. For static or batch mode, a container or apparatus containing the catalyst bed can be subjected sequentially to various stages of the activation process. For continuous mode, the process steps can take place in a series of zones through which the dried Cr-silica passes on its way through the activation device.
    [0028] In one embodiment, the dry Cr-silica is activated in a fluidized bed activator. In a fluidized bed activator, gas can flow upward through a grid plate that contains several small holes in which the dried Cr-silica is placed. The gas can contain several compounds to create desirable process conditions. The dried Cr-silica can be mixed in the gas as it flows creating a fluid type flow. This is often referred to as fluidization or fluidization.
    [0029] The activation can also include heating the dry silica to a desired temperature in one or more steps. As used here, the term "steps" refers to heating the dried Cr-silica to a desired temperature and maintaining the temperature for a period of time. One step can be performed when the dry Cr-silica is in a stationary position or by moving the dry Cr-silica through various locations and can comprise an elevation time to a desired temperature and maintaining the dry Cr-silica at that temperature for a certain time. retention time. For two or more stages, there will be two or more elevation times, two or more desired temperatures and two or more retention times. The lifting times can be the same or different, for example, the lifting time can be instantaneous (for example, preheated environment) up to less than about 3 hours.
    [0030] The temperature (s) at which the dried Cr-silica is activated can be adjusted to achieve a result desired by the user. For example, if the activation of dry Cr-silica is used to fulfill a condition for the preparation of an LCBP (for example, a Class A modification), the activation can be carried out by heating the dry Cr-silica to temperatures of less than about 650 ° C, alternatively less than about 625 ° C or, alternatively, less than about 600 ° C. In an alternative embodiment, the activation of dry Cr-silica is not used to fulfill a condition for the preparation of an LCBP. In such an embodiment, dry Cr-silica can be activated at temperature (s) in a range of about 400 ° C to about 1000 ° C, alternatively, from about 600 ° C to about 900 ° C, alternatively from about 750 ° C to about 900 ° C.
    [0031] Activation also causes oxidation of any of the trivalent forms of chromium (Cr (III)) to the hexavalent form (Cr (VI)) and then stabilization of the Cr (VI) form. As used here, the term "stabilization" refers to the activation process resulting in the Cr (VI) form of the catalyst. The activation process can convert from about 10 to about 100% of Cr (lll) to Cr (Vl), or from about 30 to about 80%, or from about 35 to about 65% and yield about 0.1 to about 5% Cr (VI), about 0.5 to about 3.0% or about 1.0 to about 3.0%, where the percentage refers percent weight of chromium (VI) based on the total weight of the catalyst. In one embodiment, the dried Cr-silica is activated as described in this document to form a Cr-X.
    [0032] In one embodiment, an LCBP is prepared using a Cr-X catalyst that contains titanium. The titanium-containing Cr-X catalyst may comprise chromium and a support, both of the type previously disclosed in this document. In addition, the titanium-containing Cr-X catalyst comprises titanium.
    [0033] The Cr-X silica-titanium catalyst is prepared by cogelification or by contacting a support of the type previously disclosed in this document with a solution or vapor containing a titanium compound. For example, one can use an aqueous solution comprising a compound containing trivalent titanium (Ti3 +) and / or a compound containing tetravalent titanium (Ti4 +). The compound containing Ti4 + can be any compound comprising tetravalent titanium, alternatively, the compound containing Ti4 + can be any compound that is soluble in aqueous solution and capable of releasing a species of Ti4 + in solution. Examples of compounds containing Ti4 + suitable for use in the present disclosure include, but are not limited to, titanyl nitrate. The compound containing Ti3 + can be any compound comprising trivalent titanium, alternatively, the compound containing Ti3 + can be any compound that is soluble in aqueous solution and capable of releasing a species of Ti3 + in solution. Examples of suitable compounds containing Ti3 + include, but are not limited to, TiCl3, (Ti) 2 (SO4) 3, Ti (OH) Cl2, TiBr3 and the like.
    [0034] In one embodiment, the support is placed in contact with the compound containing Ti3 + and / or compound containing Ti4 + by impregnation. The titanium-containing support can then be dried to remove the solvent and form a dry titanium-containing support. Drying can be carried out in a temperature range of about 25 ° C to about 300 ° C, alternatively, from about 50 ° C to about 200 ° C or, alternatively, from about 80 ° C to about 150 ° C and for a period of about 0.1 min to about 10 hours, alternatively, from about 0.2 min to about 5 hours, or alternatively, from about 30 min to about 1 hour . In some embodiments, drying is carried out in an inert atmosphere (for example, under vacuum, He, Ar or nitrogen gas).
    [0035] In an alternative embodiment, titanium can be applied to the support by vapor deposition or by impregnating a non-aqueous solution of titanium. Suitable titanium compounds used in this embodiment include, but are not limited to, titanium halides and alkoxides.
    [0036] The method may also comprise the calcination of the support containing dry titanium in the presence of air to oxidize Ti3 + to Ti4 + and attach the titanium to the support and form a calcined support containing dry titanium. For example, the support containing dry titanium can be calcined in the presence of air at a temperature in the range of about 400 ° C to about 1,000 ° C, alternatively, from about 500 ° C to 900 ° C and for a period time from about 1 hour to about 30 hours, alternatively, from about 2 hours to about 20 hours or, alternatively, from about 5 hours to about 12 hours.
    [0037] The method may further comprise the addition of a compound containing chromium to the calcined support containing dry titanium to form a Cr / Ti-silica. the chromium-containing compound can be a water-soluble compound or a hydrocarbon-soluble compound, such as those described in this document, and can be introduced into the calcined support containing dry titanium using any contact technique also described previously. The Cr / Ti-silica can be dried again to remove the solvent introduced by adding the chromium-containing compound at temperatures ranging from 25 ° C to about 300 ° C, alternatively from about 50 ° C to about 200 ° C or, alternatively, from about 80 ° C to about 150 ° C. In one embodiment, Cr / Ti-silica can then be activated through a second calcination step by heating in an oxidizing environment to produce a Cr-X containing titanium. Such activations can be carried out using procedures and equipment of the type previously disclosed in this document (for example, fluidized bed). For example, Cr / Ti-silica can be calcined in the presence of air at a temperature in the range of about 400 ° C to about 1,000 ° C, alternatively, from about 500 ° C to 850 ° C and for a time period of about 1 min to about 10 hours, alternatively, about 20 min to about 5 hours or, alternatively, about 1 to about 3 hours to produce Cr-X containing titanium.
    [0038] In another embodiment, a method of preparing a Cr-X catalyst containing titanium comprises contacting a support with a compound containing chromium to form a composition with Cr support. the chromium-containing compound can be a water-soluble compound or a hydrocarbon-soluble compound, such as those described in this document, and can be introduced into the support using any contact technique also described previously. The Cr supported composition can be dried to remove the solvent at temperatures ranging from 25 ° C to about 300 ° C, alternatively from about 50 ° C to about 200 ° C or, alternatively, from about 80 ° C at about 150 ° C and for a period of time from about 0.1 min to about 10 hours, alternatively from about 0.2 min to about 5 hours, alternatively from about 30 min to about 1 hour hour, thus forming a composition with Cr support. the method may further comprise contacting the dry Cr supported composition with a compound containing Ti3 + and / or compound containing Ti4 + to form a Cr / Ti-silica. the compound containing Ti3 + can be brought into contact with the Cr seca supported composition using any of the contact techniques described earlier in this document. In one embodiment, the composition with Cr dry support is placed in contact with a compound containing Ti3 + by impregnation with an aqueous solution of Ti3 + "salt to form a Cr / Ti-silica. The method further comprises the activation of Cr / Ti-silica. silica by drying and / or calcining Cr / Ti-silica in the presence of air to oxidize Ti3 + to Ti4 + and attach titanium to silica. Such activations can be carried out using procedures and equipment of the type previously disclosed in this document (for example, fluidized bed) For example, Cr / Ti-silica can be heated in the presence of air at a temperature in the range of about 400 ° C to about 1,000 ° C, alternatively, from about 500 ° C to 850 ° C and for a period of time from about 1 min to about 10 hours, alternatively from about 20 min to about 5 hours or, alternatively, from about 1 hour to about 3 hours to produce the Cr-X catalyst containing titanium.
    [0039] In another embodiment, a method of preparing a catalyst comprises contacting with a carrier of the type disclosed here with a compound containing Ti3 + and / or compound containing Ti4 + and a compound containing chromium to form a metallized support. The contact of the support with the compound containing Ti3 + and / or compound containing Ti4 + and compound containing chromium can be simultaneous; alternatively, contact can be made sequentially (for example, Ti3 + and / or Ti4 + followed by Cr or vice versa). the compound containing Ti3 + and / or compound containing Ti4 + and compound containing chromium can be of the types described above and can be introduced into the support (for example, low surface area silica) using the contact techniques also previously described in this document to form a metallized silica. The metallized silica can be dried to remove the solvent at temperatures ranging from 25 ° C to about 300 ° C, alternatively from about 50 ° C to about 200 ° C or, alternatively, from about 80 ° C to about 150 ° C and for a period of time from about 0.1 min to about 10 hours, alternatively from about 0.2 min to about 5 hours, alternatively from about 30 min to about 1 hour, thus forming a dry metallized silica. In one embodiment, the dry metallized silica can then be activated through a calcination step by heating it in an oxidizing environment. Such activations can be carried out using procedures and equipment of the type previously disclosed in this document (for example, fluidized bed). For example, dry metallized silica can be heated in the presence of air at a temperature in the range of about 400 ° C to about 1,000 ° C, alternatively, from about 500 ° C to 850 ° C and for a period of time from about 1 min to about 10 hours, alternatively, from about 20 min to about 5 hours or, alternatively, from about 1 hour to about 3 hours to produce the titanium-containing Cr-X.
    [0040] In the modalities in which a Cr-X catalyst containing titanium is formed, the amount of titanium used may be sufficient to provide a titanium percentage of about 0.1% to about 10% by weight of the catalyst or, alternatively , from about 0.5% to about 8%, alternatively, from about 1% to about 5%. In this document, the percentage of titanium refers to the final percentage of titanium associated with the support material by total weight of the material after all processing steps.
    [0041] Alternatively, in modalities in which a Cr-X catalyst containing titanium is formed, the amount of titanium used may be sufficient to provide a titanium distribution greater than about 2 titanium atoms per nm2 of support, alternatively, higher at about 2.5 titanium atoms per nm2 of support or, alternatively, greater than about 3 titanium atoms 9 per nm of support.
    [0042] It is contemplated that the temperature (s) at which the composition comprising chromium, titanium and silica (e.g., Cr / Ti-silica, metallized silica) is activated to form an activated catalyst it can be adjusted to achieve a desired result by the user. For example, if the activation of the composition comprising chromium, titanium and silica is used to fulfill a condition for the preparation of an LCBP (for example, a Class A modification), the activation can be carried out by heating the catalyst comprising chromium, titanium and silica at temperatures of less than about 650 ° C, alternatively, less than about 625 ° C or, alternatively, less than about 600 ° C. In an alternative embodiment, if the activation of the composition comprising chromium, titanium and silica is used to fulfill a condition for the preparation of an LCBP (for example, a Class A modification), the activation can be carried out by heating the catalyst comprising chromium, titanium and silica at temperatures above about 700 ° C, alternatively above about 800 ° C or alternatively above about 850 ° C.
    [0043] In one embodiment, a catalyst for use in the preparation of an LCBP has a catalytic activity greater than about 750 grams of polymer product per gram of catalyst used (g / g), alternatively, greater than about 1000 g / g, alternatively, greater than about 1500 g / g or, alternatively, greater than about 2000 g / g-
    [0044] In one embodiment, an LCBP of the type disclosed in this document is prepared by a methodology that employs a Cr-X catalyst and a Class A modification. In one embodiment, the Class A modification comprises the activation of the Cr-X catalyst at a less than about 650 ° C, as described earlier in this document. In one embodiment, the Class A modification comprises adjusting the amount of Cr in the support (for example, low surface area silica) to provide a chromium distribution greater than about 2 chromium atoms per nm2 of support, as previously described in this document. In one embodiment, the Class A modification comprises the incorporation of titanium into the Cr-X catalyst to form a Cr-X catalyst containing titanium, as previously disclosed in this document.
    [0045] Class A modifications disclosed in this document result in catalysts that can be used properly in an olefin polymerization method. The catalysts of the present disclosure are suitable for use in any method of polymerizing olefins, using various types of polymerization reactors. In one embodiment, a polymer of the present disclosure is produced by any method of polymerizing olefins, using various types of polymerization reactors. As used herein, "polymerization reactor" includes any reactor capable of polymerizing olefin monomers to produce homopolymers and / or copolymers. Homopolymers and / or copolymers produced in the reactor can be referred to as resin and / or polymers. The various types of reactors include, among others, those that can be referred to as batch, mud, gas phase, solution, high pressure, tubular, autoclave, or other reactor and / or reactors. Gas phase reactors may comprise fluidized bed reactors or horizontal staged reactors. Mud reactors can comprise vertical and / or horizontal cycles. High pressure reactors may comprise autoclave and / or tubular reactors. Reactor types can include batch and / or continuous processes. Continuous processes can use intermittent and / or continuous product transfer or discharge. Processes may also include direct partial or complete recycling of the unreacted monomer, unreacted comonomer, catalyst and / or cocatalysts, diluents, and / or other polymerization process materials.
    [0046] Polymerization reactor systems of the present disclosure may comprise one type of reactor in a system or multiple reactors of the same or different type, operated in any suitable configuration. Production of polymers in multiple reactors can include several steps in at least two separate polymerization reactors, interconnected by a transfer system, making it possible to transfer the polymers resulting from the first polymerization reactor to the second reactor. Alternatively, polymerization in multiple reactors may include the transfer, manually or automatically, of polymer from one reactor to the reactor or subsequent reactors for further polymerization. Alternatively, multiple-stage or multiple-stage polymerization can take place in a single reactor, where conditions are changed so that a different polymerization reaction takes place.
    [0047] The desired polymerization conditions in one of the reactors may be the same or different from the operating conditions of any other reactors involved in the general polymer production process of the present disclosure. Multiple reactor systems can include any combination including, without limitation, multiple cycle reactors, multiple gas phase reactors, a combination of gas phase and cycle reactors, multiple high pressure reactors or a combination of high pressure reactors with reactors cycle and / or gas. The multiple reactors can be operated in series or in parallel. In one embodiment, any arrangement and / or any combination of reactors can be employed to produce the polymer of the present disclosure.
    [0048] According to one embodiment, the polymerization reactor system may comprise at least one cycle sludge reactor. Such reactors are common and can comprise vertical or horizontal cycles. Monomer, diluent, catalyst system and, optionally, any comonomer can be continuously fed to a cycle sludge reactor, where polymerization takes place. Generally, continuous processes may comprise the continuous introduction of a monomer, a catalyst, and / or a diluent into a polymerization reactor and the continuous removal of a suspension comprising polymer particles and the diluent from that reactor. Effluent from the reactor can be abruptly evaporated to remove liquids that comprise the polymer diluent, monomer and / or solid comonomer. Various technologies can be used for this separation step, including, but not limited to, sudden evaporation which may include any combination of heat addition and pressure reduction; separation by cyclonic action in a cyclone or hydrocyclone; centrifugation separation; or another appropriate method of separation.
    [0049] Typical sludge polymerization processes (also known as particle-shaped processes) are disclosed in US Patent Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191 and 6,833,415, for example; each of which is incorporated herein by reference in its entirety.
    [0050] Suitable diluents used in sludge polymerization include, among others, the monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons, such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane and n-hexane. Some cycle polymerization reactions can occur under mass conditions, where no diluents are used. An example is polymerization of propylene monomer as disclosed in U.S. Patent No. 5,455,314, which is incorporated herein by reference in its entirety.
    [0051] According to yet another modality, the polymerization reactor can comprise at least one gas phase reactor. Such systems can employ a continuous recycling stream that contains one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycling stream can be removed from the fluidized bed and recycled back to the reactor. Simultaneously, polymer product can be removed from the reactor and new or fresh monomer can be added to replace the polymerized monomer. Such gas phase reactors can comprise a process for a multi-stage gas phase olefin polymerization, in which olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones, while feeding a polymer containing catalyst formed in a first polymerization zone to a second polymerization zone. One type of gas phase reactor is disclosed in U.S. Patent Nos. 4,588,790, 5,352,749 and 5,436,304, each of which is incorporated herein by reference in its entirety.
    [0052] According to yet another modality, a high pressure polymerization reactor can comprise a tubular reactor or an autoclave reactor. Tubular reactors can have several zones where fresh monomer, initiators or catalysts are added. The monomer can be entrained in an inert gas stream and introduced into a zone of the reactor. Primers, catalysts and / or catalyst components can be entrained in a gaseous flow and introduced into another zone of the reactor. Gas streams can be intermixed for polymerization. Heat and pressure can be used appropriately to obtain optimum polymerization reaction conditions.
    [0053] According to yet another modality, the polymerization reactor may comprise a solution polymerization reactor, in which the monomer is brought into contact with the catalyst composition by proper stirring or other means. A carrier that comprises an excess organic diluent or monomer can be employed. If desired, the monomer can be placed, in the vapor phase, in contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a polymer solution in a reaction medium. Stirring can be used to achieve better temperature control and to maintain uniform polymerization mixes throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.
    [0054] Polymerization reactors suitable for the present disclosure may further comprise any combination of at least one feedstock feed system, at least one feedstock for catalyst or catalyst components, and / or at least one feedstock recovery system polymer. Reactor systems suitable for the present invention may further comprise systems for purification of raw material, storage and preparation of catalyst, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, unloading, laboratory analysis and process control.
    [0055] Conditions that are controlled for polymerization efficiency and to provide polymer properties include, among others, temperature, pressure, type and amount of catalyst or cocatalyst, and the concentrations of various reagents. The polymerization temperature can affect catalyst productivity, the molecular weight of polymers and the molecular weight distribution. Suitable polymerization temperatures can be any temperature below the depolymerization temperature, according to the Gibbs Free Energy Equation. Typically, this includes from about 60 ° C to about 280 ° C, for example, and / or from about 70 ° C to about 110 ° C, depending on the type of polymerization reactor and / or polymerization process.
    [0056] Adequate pressures will also vary according to the reactor and polymerization process. The pressure for liquid phase polymerization in a cycle reactor is typically less than 1000 psig (6.89 MPa). The pressure for polymerization of the gas phase is generally about 200 - 500 psig (1.38 - 3.45 MPa). High pressure polymerization in tubular or autoclave reactors is generally performed at about 20,000 to 75,000 psig (137.09 - 517.11 MPa). Polymerization reactors can also be operated in a supercritical region, generally occurring at higher temperatures and pressures. Operating above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages.
    [0057] In one embodiment, the LCBP is prepared by a methodology that employs a Cr-X catalyst and at least one Class B modification. In one embodiment, the Class B modification comprises providing that the monomer concentration present in the reactor is less than about 1 mole / liter (mol / L), alternatively, less than about 0.75 mol / L or, alternatively, less than about 0.5 mol / L. Examples of suitable monomers for use in the present disclosure include, but are not limited to, mono-olefins containing from 2 to 8 carbon atoms per molecule, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene. In one embodiment, the monomer comprises ethylene. In embodiments where the monomer is a gas (for example, ethylene), the polymerization or oligomerization reaction can be carried out under a pressure of monomer gas. When the polymerization or oligomerization reaction produces polyethylene or alpha-olefins, the reaction pressure can be the pressure of ethylene monomer. In some embodiments, the ethylene pressure can be greater than 0 psig (0 KPa); alternatively, greater than 50 psig (344 KPa); alternatively, greater than 100 psig (689 KPa); or, alternatively, greater than 150 psig (1.0 MPa). In other embodiments, the ethylene pressure can vary from 0 psig (0 KPa) to 5,000 psig (34.5 MPa); alternatively, 50 psig (344 KPa) to 4,000 psig (27.6 MPa); alternatively, 100 psig (689 KPa) to 3,000 psig (20.9 MPa); or, alternatively, 150 psig (1.0 MPa) to 2,000 psig (13.8 MPa). In some cases when ethylene is the monomer, inert gases can form part of the total reaction pressure. In cases where inert gases form part of the reaction pressure, the ethylene pressures referred to above can be partial ethylene pressures applicable to the polymerization or oligomerization reaction. In the situation where the monomer supplies all or part of the pressure of the polymerization or oligomerization reaction, the pressure of the reaction system may decrease as the gaseous monomer is consumed. In this situation, additional gaseous monomer and / or inert gas can be added to maintain a desired polymerization or oligomerization reaction pressure. In embodiments, additional gaseous monomer can be added to the polymerization or oligomerization reaction at a fixed rate (for example, for a continuous flow reactor), at different speeds (for example, to maintain a determined system pressure in a batch reactor ). In other embodiments, the pressure of the polymerization or oligomerization reaction may be allowed to decrease without the addition of any additional gaseous monomer and / or inert gas.
    [0058] In one embodiment, the Class B modification comprises the application of a cocatalyst in the reaction for the production of the LCBP. Generally, the cocatalyst can be any organometallic compound capable of activating the catalyst (for example, Cr-X) to polymerize or oligomerize olefins. Suitable cocatalysts include, but are not limited to, monomeric or oligomeric metal alkyls, metallic aryls, metallic alkyl-aryls comprising at least one of the metals selected from the group consisting of B, Al, Be, Mg, Ca, Sr, Ba, Li, Na, K , Rb, Cs, Zn, Cd and Sn. In modalities, the cocatalyst can be selected from the group consisting of organoaluminium compounds, organoboro compounds, organolithium compounds or mixtures thereof. In some embodiments, the cocatalyst may be an organoaluminium compound. Applicable organoaluminium compounds include, but are not limited to, trialkylaluminiums, alkaline aluminum halides, alumoxanes or mixtures thereof. In some embodiments, the organoaluminium compound can be trimethylaluminum, triethylaluminium, diethylaluminium chloride, diethylaluminium ethoxide, diethylaluminium cyanide, diisobutylaluminium chloride, triisobutylalumin, ethylaluminoxane (MAO), methylalumoxane (MAO), methylated aluminum oxaloxane (MAO), methylated aluminum oxide , t-butylalumoxanes or mixtures thereof. In other embodiments, organoaluminium compounds may include, but are not limited to, methylalumoxane (MAO), modified methylalumoxane (MMAO), isobutylalumoxanes, t-butylalumoxanes or mixtures thereof. In other embodiments, the cocatalyst may be methylalumoxane, modified methylalumoxane or mixtures thereof. In still other embodiments, the cocatalyst may be methylalumoxane; alternatively, modified methylalumoxane; isobutylalumoxane (IBAO); or, alternatively, partially hydrolyzed trialkylaluminium.
    [0059] In one embodiment, the cocatalyst comprises a compound represented by the general formula A1R3 or BR3. Alternatively, the cocatalyst is triethylboro (TEB). The cocatalyst can be present in the reactor in an amount greater than about 1 ppm, alternatively, greater than about 5 ppm or, alternatively, greater than about 8 ppm, based on the weight of the solvent or diluent in systems using such solvent or thinner. When no solvent or diluent is used, the catalyst (eg, Cr-X) can be impregnated with the cocatalyst in an amount that provides a mol ratio between cocatalyst and chromium in the range of about 0.1: 1 to about 100: 1, alternatively, from about 0.5: 1 to about 50: 1 or from about 1: 1 to 10: 1.
    [0060] In one embodiment, a method of producing an LCBP of the type disclosed in this document comprises the use of a Cr-X catalyst and at least one Class A modification, alternatively, Cr-X catalyst and at least one Class B modification or alternatively, a Cr-X catalyst, at least one Class A modification and at least one Class B modification. For example, a method of producing an LCBP of the type disclosed in this document may comprise the use of a Cr-X catalyst, in that the Cr-X catalyst was activated at a temperature of less than about 650 ° C.
    [0061] Alternatively, a method of producing an LCBP of the type disclosed in this document may comprise the use of a Cr-X catalyst, in which the Cr-X catalyst was activated at a temperature of less than about 650 ° C and the amount of Cr present in the reactor was adjusted to provide a chromium distribution greater than about 2 chromium atoms per nm2 of support.
    [0062] Alternatively, a method of producing an LCBP of the type disclosed in this document may comprise the use of a Cr-X catalyst, in which the Cr-X catalyst was activated at a temperature of less than about 650 ° C, the amount of Cr present in the reactor was adjusted to provide a chromium distribution greater than about 2 chromium atoms per nm2 of support and titanium was incorporated into the Cr-X catalyst.
    [0063] Alternatively, a method of producing an LCBP of the type disclosed in this document may comprise the use of a Cr-X catalyst, in which the Cr-X catalyst was activated at a temperature of less than about 650 ° C, the amount of Cr present in the reactor was adjusted to provide a chromium distribution greater than about 2 chromium atoms per nm2 of support, titanium was incorporated in the Cr-X catalyst, and the concentration of monomer present in the reactor is less than about 1 mole / liter (mol / L).
    [0064] Alternatively, a method of producing an LCBP of the type disclosed in this document may comprise the use of a Cr-X catalyst, in which the Cr-X catalyst was activated at a temperature of less than about 650 ° C, the amount of Cr present in the reactor was adjusted to provide a chromium distribution greater than about 2 chromium atoms per nm2 of support, titanium was incorporated into the Cr-X catalyst, the concentration of monomer present in the reactor is less than about 1 mol / L, and a cocatalyst is present in the reaction.
    [0065] Alternatively, a method of producing an LCBP of the type disclosed in this document may comprise the use of a Cr-X catalyst, in which the Cr-X catalyst was activated at a temperature of less than about 650 ° C and a cocatalyst comprising TEB present in the amounts previously disclosed in this document. In one embodiment, the methodologies disclosed in this document are used to produce an LCBP of the type disclosed in this document.
    [0066] In one embodiment, an LCBP of the type described in this document is characterized by a density of about 0.90 g / cm3 to about 0.97 g / cm3, alternatively, from about 0.93 g / cm3 to about 0.97 g / cm3 or, alternatively, from about 0.92 g / cm3 to about 0.965 g / cm3 or, alternatively, from about 0.93 g / cm3 to about 0.96 g / cm3 , as determined in accordance with ASTM D1505.
    [0067] In one embodiment, an LCBP produced using a catalyst of the type described here has a fluidity index, MI, in the range of about 0 dg / min to about 100 dg / min, alternatively, about 0.1 dg / min to about 10 dg / min, or, alternatively, from about 0.1 dg / min to about 3.0 dg / min, or, alternatively, from about 0.2 dg / min to about 2.0 dg / min. The melt index (MI) refers to the amount of a polymer that can be forced through an extrusion rheometer hole of 0.0825 inches in diameter when subjected to a force of 2160 grams in ten minutes at 190 ° C, as determined according to ASTM D1238.
    [0068] The LCBP molecular weight distribution (MWD) can be characterized by the weighted average molecular weight (Mw) to average molecular weight (Mn) number, which is also referred to as the polydispersity index (PDI) or, more simply, as polydispersity. The number of the average molecular weight, Mn, is the common average of the molecular weights of individual polymers calculated by measuring the molecular weight of polymer molecules n, adding the weights and dividing by n. The weighted average molecular weight, Mw, describes the molecular weight distribution of a polymer composition and is calculated according to Equation 1:
    where Ni is the number of molecules of molecular weight Mi. An LCBP of the type disclosed in this document can be characterized by a wide molecular weight distribution, such that the PDI is equal to or greater than about 10, alternatively, greater than about 15, alternatively, greater than about 20 or, alternatively, greater than about 25.
    [0069] An LCBP of the type disclosed in this document can be characterized by the degree of long chain branching (LCB) present in the polymer. LCB was measured using the molecular exclusion chromatography technique coupled to multi-angle light scattering (SEC-MALS). Methods for determining long chain branching and distribution of long chain branching are described in an article by Yu et al. entitled "SEC-MALS method for the determination of long-chain branching and long-chain branching distribution in polyethylene," Polymer (2005) Volume: 46, Edition: 14, Pages: 5165-5182, which is incorporated into this document for reference at its entirety.
    [0070] In one embodiment, an LCBP of the type disclosed in this document has a peak LCBP content that is determined as the number of LCBs per one million carbon atoms that is designated À. In one embodiment, À is greater than about 8 LCB per one million carbon atoms (LCB / 106 carbons), alternatively, greater than about 15 LCB / 106 carbons or, alternatively, greater than about 30 LCB / carbons 106 carbons. In this document, peak LCB content refers to the maximum concentration of LCB as a function of molecular weight. The number of LCBs per 106 total carbons is calculated using the formula 1,000.OOO * Mo * B / M, where B is the number of LCBs per chain, Mo is the molecular weight of the repeating unit, that is, the methylene group , -CH2-, for PE; and M is the molecular weight of a SEC slice where all macromolecules in the same SEC slice are assumed to have the same molecular weight. B is calculated according to the following equation:
    where g is defined as the ratio between the mean square radius of rotation of a branched polymer and that of a linear polymer with the same molecular weight. Both the radius of rotation and the molecular weight were determined using SEC-MALS.
    [0071] In one embodiment, an LCBP of the type disclosed in this document has a peak LCB content that is determined as the number of LCBs per chain. In one embodiment, for an LCBP of the type disclosed in this document, B is greater than about 1.0 LCB / chain, alternatively, greater than about 1.3, alternatively, greater than about 1.5 or, alternatively, greater than about 2.0.
    [0072] In one embodiment, an LCBP of the type disclosed in this document exhibits an LCB content that is characterized by a decrease in the amount of LCB to approximately zero in the highest molecular weight portion of the molecular weight distribution. In this document, the highest molecular weight portion of the molecular weight distribution refers to a higher molecular weight at about 10 million kg / mol.
    [0073] In one embodiment, a methodology of the type disclosed in this document is used to produce an LCBP characterized by a long chain branch content reaching a peak above about 20 long chain branches per one million carbon atoms and a molecular weight / PDI distribution greater than about 10 wherein the long chain branch decreases to approximately zero in the highest molecular weight portion of the molecular weight distribution.
    [0074] In one embodiment, a methodology of the type disclosed in this document is used to produce an LCBP characterized by a long chain branch content reaching a peak above about 20 long chain branches per one million carbon atoms and one highest molecular weight distribution at about 15 where the long chain branch decreases to approximately zero in the highest molecular weight portion of the molecular weight distribution.
    [0075] In one embodiment, a methodology of the type disclosed in this document is used to produce an LCBP characterized by a long chain branch content reaching a peak above about 20 long chain branches per one million carbon atoms, content long chain branch peaking above about 1.0 long chain branches per chain and a higher molecular weight distribution to about 10 where the long chain branch decreases to high molecular weight distribution.
    [0076] In one embodiment, a methodology of the type disclosed in this document is used to produce an LCBP characterized by a long chain branch content reaching a peak above about 25 long chain branches per one million carbon atoms and one highest molecular weight distribution at about 15 where the long chain branch decreases to approximately zero in the highest molecular weight portion of the molecular weight distribution.
    [0077] In one embodiment, a methodology of the type disclosed in this document is used to produce an LCBP characterized by a long chain branch content reaching a peak above about 30 long chain branches per one million carbon atoms and one highest molecular weight distribution at about 15 where the long chain branch decreases to approximately zero in the highest molecular weight portion of the molecular weight distribution.
    [0078] In one embodiment, a methodology of the type disclosed in this document is used to produce an LCBP characterized by a long chain branch content reaching a peak above about 8 long chain branches per one million carbon atoms and one highest molecular weight distribution at about 20 where the long chain branch decreases to approximately zero in the highest molecular weight portion of the molecular weight distribution.
    [0079] In one embodiment, a methodology of the type disclosed in this document is used to produce an LCBP characterized by a long chain branch content reaching a peak above about 1 long chain branch and a higher molecular weight distribution at about 10 in which the long chain branch decreases to approximately zero in the highest molecular weight portion of the molecular weight distribution.
    [0080] Polymer resins produced as disclosed in this document (ie, LCBPs) can be formed into articles of manufacture or end-use articles using techniques known in the art, such as extrusion, blow molding, injection molding, fiber spinning , thermoforming and casting. For example, a polymer resin can be extruded onto a sheet, which is then thermoformed into an end-use article, such as a container, glass, tray, palette, toy or component from another product. Examples of other end-use articles in which polymer resins can be formed include tubes, films, bottles, fibers and so on. EXAMPLES
    [0081] The following examples are given as particular forms of disclosure and to demonstrate the practice and benefits of it. It is understood that the examples are given by way of illustration and are not intended to limit the description or the following claims in any way.
    [0082] Cr-X catalysts of the type disclosed in this document have been prepared and used in the formation of an LCBP of the type disclosed in this document. Chromium in the form of chromium acetate was impregnated with a low surface area silica of methanol for a load of approximately 1.2 Cr / nm2. The low surface area silicas used were SYLOX SD or SM500, which are commercially available from W.R. Grace. SYLOX SD has a surface area of approximately 100 m2 / g and a pore volume of 1.2 ml / g. SYLOX SD is reported to be a "hybrid" between silica gel and precipitated silica. In another experiment, a precipitated silica, SM500, was used. SM500 had an area of 102 m2 / g and a pore volume of 1.1 ml / g. The chromium-impregnated silica was then dried in a vacuum oven at 100 ° C for 12 hours. Cr / silica-titania catalysts were made first by drying the SYLOX SD silica impregnated with Cr at 200 ° C overnight, then impregnating dry heptane titanium tetraisopropoxide to a level of 3% by weight of Ti and then evaporating the solvent. Finally, each dry catalyst was sized using a 35 mesh (0.5 mm) screen.
    [0083] To activate the catalyst, about 10 grams were placed in a 4.5 cm quartz tube equipped with a sintered quartz disk at the bottom. While the catalyst was supported on the disc, the dry air was blown through the disc at a linear speed of 3.0 cm / s. An electric furnace around the quartz tube was then started and the temperature was raised at a rate of 400 ° C / h to the desired temperature, usually 800 ° C. At such a temperature, the silica was allowed to fluidize for three hours in dry air. Then, the catalyst was collected and stored under dry nitrogen, where it was protected from the atmosphere until it was ready for testing.
    [0084] Comparative experiments were also carried out using the Cr-silica catalyst HA30W whose support has a surface area of 500 m2 / g and a pore volume of 1.6 mL / g or 969 MPI, which is also a Cr-silica catalyst with a support surface area of 300 m2 / g and a pore volume of 1.6 mL / g.
    [0085] Polymerization operations were carried out in a 2.2 liter stainless steel reactor equipped with a marine agitator rotating at 500 rpm. The reactor was surrounded by a stainless steel jacket through which a flow of hot water was distributed, which allowed precise temperature control within half a degree Celsius, with the help of electronic control instruments. Unless otherwise indicated, a small amount (usually 0.05 to 0.25 g) of the solid catalyst was first charged under nitrogen in the dry reactor. Then, 1.2 liters of liquid isobutane were added and the reactor heated to the set temperature of 80 ° C. During the addition of isobutane, triethyl aluminum was added to equal 0.5 ppm of the isobutane (except in experiment 4, where 10 ppm of triethyl aluminum or triethylboro was used). Finally, ethylene was added to the reactor to equal the desired pressure, usually 2.76 MPa, which was maintained during the experiment. The slurry was stirred for the specified time, usually about an hour, and the rate of polymerization was observed by recording the flow of ethylene in the reactor to maintain the opening pressure. After the allotted time, the flow of ethylene was stopped and the reactor slowly depressurized and opened to recover a granular polymer powder. The dry polymer powder was then removed and weighed. The activity was determined from this weight and the measured time. Example 1
    [0086] Catalyst A was a Cr / silica catalyst prepared using SYLOX-SD silica obtained from W.R. Grace. This silica is described as a hybrid between precipitated and gelled silica and as being "reinforced". It has a surface area of approximately 105 m2 / g and a pore volume of about 1.2 ml / g. This silica was then impregnated with an aqueous solution of chromium acetate to have a chromium distribution of 1.2 Cr / nm2. It was then calcined at 550 ° C and in a separate experiment at 800 ° C. These catalysts were used to polymerize ethylene at 80 ° C, 400 psig (2.76 MPa) and 0.5 ppm triethyl aluminum, as described above. The first catalyst (550 ° C) produced an activity of 0.6 kg PE / g / h and the second (800 ° C) produced an activity of 1.6 kg PE / g / h. The polyethylene polymer was analyzed using SEC-MALS measurements which are shown in Figure 1. Figure 1 demonstrates the wide distribution of molecular weight and also the high content of LCB, also as measured by million carbons, or per chain. Polydispersity (ie weighted average molecular weight (Mw) divided by the number of average molecular weight Mn or Mw / Mn) was 12.2 when the catalyst was calcined at 800 ° C and 26.6 when the catalyst was calcined at 550 ° C.
    [0087] Catalyst B was a Cr / silica-titania catalyst made first by drying the SYLOX SD silica impregnated with Cr at 200 ° C overnight, then impregnating titanium tetraisopropoxide from a dry heptane solution to a level of 3 % by weight of Ti and then evaporating the solvent. Finally, the dry catalyst was dimensioned through a 35 mesh (0.5 mm) screen. The titanium-containing Cr-silica catalyst had SYLOX-SD as the support and a chromium distribution of 1.2 Cr / nm2. Catalyst B was first activated at 800 ° C and tested for polymerization of ethylene, as described above, using the same conditions (80 ° C, 400 psig (2.76 MPa), 0.5 ppm TEA). It produced an activity of 2.8 kg of PE / g / h. Another sample of c = Catalyst B was also activated at 550 ° C and then tested for polymerization activity under similar conditions. This yielded an activity of 1.6 kg of PE / g / h. SEC-MALS measurements were performed on both polymers and are shown in Figure 2. The molecular weight distribution of samples produced using Catalyst B was increased by titanium producing a polydispersity of 21.7 when the catalyst was calcined at 800 ° C and 27.6 when the catalyst was calcined at 550 ° C. These results demonstrate that the effect of including titanium in the catalyst is to reinforce the LCB content and expand the molecular weight distribution.
    [0088] Catalyst Ceo Catalyst D are comparative Cr-silica catalysts. Catalyst C was prepared using Grace SM500 precipitated silica as a support, having a surface area of about 100 m2 / g, which was impregnated with sufficient chromium to provide a chromium distribution of 1.2 Cr / nm2 and was calcined at 700 ° C. Catalyst D was the 969MPI Cr-silica catalyst, having a surface area of about 300 m2 / g, which contained 0.4 Cr / nm2 and was calcined at 850 ° C. Each catalyst was then used to polymerize ethylene at (80 ° C, 300 psig (2.07 MPa), 0.5 ppm TEA) with ethylene concentrations ranging from 0.9 mol / L. Catalyst C produced an activity of 0.1 kg dθ PE / g / h and polymer having a polydispersity of 10.9, while Catalyst D produced an activity of 0.5 kg PE / g / h and polymer having a polydispersity of 9 , 4. SEC-MALS measurements are shown in Figure 3 for both polymers. A comparison of Figure 3 with Figure 1 and Figure 2 demonstrates the broadest molecular weight distributions observed for catalysts having a highly reinforced support with the low surface area. Example 2
    [0089] The effect of the silica surface area on the catalyst in LCB was further investigated. Catalyst E was a Cr-silica catalyst prepared using SYLOX-SD, having a pore volume of about 1.2 mL / g and a surface area of about 105 m2 / g, as the support that was impregnated with sufficient chromium to provide a 1.2 Cr / nm2 chromium distribution. Catalyst F used grade 952 W.R. Grace, having a pore volume of 1.6 mL / g and a surface area of 300 m2 / g, impregnated with a similar amount of chromium. Catalyst G used HA30W W.R. Grace, having a pore volume of 1.6 mL / g and a surface area of 500 m2 / g, also impregnated with a similar amount of chromium. Catalyst F is similar to Catalyst D. Catalysts E, F and G were calcined at 800 ° C and tested for polymerization activity. Polymers were prepared using these Cr-X catalysts of the type disclosed in this document (ie Catalyst E) at 80 ° C, 400 psig (2.76 MPa) and 0.5 ppm TEA. Catalyst E produced polymers having a polydispersity of 12.2 and Catalyst F and Catalyst G produced polymers having polydispersity of 13.3 and 11.9, respectively. The results are shown in Figure 4. Example 3
    [0090] The effect of changing the chromium concentration on the LCB content of the polymers was investigated. Catalyst H was prepared by impregnating SYLOX-SD with chromium acetate to provide a chromium distribution of 3.5 Cr / nm2. The impregnated support was then calcined at 800 ° C as described above. When tested for ethylene polymerization activity, Catalyst H produced an activity of 2.3 kg PE / g / h and polymer having a polydispersity of 10.1, as shown in Figure 5. Referring to Figure 5, the polymer produced from Catalyst H exhibited an LCB content that peaked at over 40 branches per million carbons and over 2.0 branches per chain. Example 4
    [0091] The effect of polymerization in the presence of a cocatalyst on the LCB content of the polymers was investigated. In two different runs, Catalyst A (800 ° C) was tested with either 10 ppm of triethyl aluminum (based on the weight of the isobutane diluent) or with 10 ppm of triethylboro added to the reactor. In both reaction conditions, the catalysts were quite active, producing activities of 1.8 and 3.3 kg PE / g / h, respectively. They produced polymer with a wider MW distribution (polydispersity of 16.1 and 17.5, respectively). The results of SEC-MALS on these polymers are shown in Figure 6. Referring to the upper part of Figure 6, the results demonstrate that both cocatalysts extended the high molecular weight side of the molecular weight distribution. Referring to the upper part of Figure 6, the results indicate that the cocatalysts do not appear to have increased the amount of LCB. However, the LCB peak was changed to higher molecular weight. At the bottom of Figure 6, where LCB is plotted by chain, it was observed that the LCB was brought to a higher molecular weight, demonstrating that the LCB / chain is quite high when cocatalysts are used. For example, the polymer produced using triethylboro exhibits an LCB peak of approximately 2 branches per chain. Also note that the LCB content appears to have been forced to a higher molecular weight by the use of cocatalysts, which produces higher levels of rheological elasticity. Example 5
    [0092] The polymerization effect in the presence of a low monomer concentration in the LCB content of the polymers was investigated. Catalyst F was used to polymerize ethylene under different concentrations of ethylene, including as low as 0.2 mol / L of ethylene. The polymerizations were carried out at 80 ° C, with 0.5 ppm TEA. The results of this experiment are summarized, together with all previous experiments, in Table 1 below. Figure 7 shows the effect of varying the concentration of ethylene monomer on the LCB content. The low ethylene concentration was effective in increasing the level of LCB, but also reduced activity even further. Table 1


    [0093] While the various modalities have been shown and described, modifications of them can be made without deviating from the spirit and teachings of dissemination. The modalities described in this document are only exemplary and are not intended to be limiting. Many variations and modifications of the object disclosed in this document are possible and are within the scope of the disclosure. Where ranges or numerical limitations are expressly indicated, such ranges or expressed limitations should be understood to include iterative ranges or limitations of similar magnitude that are within the ranges or limitations expressly indicated (for example, from about 1 to about 10 includes 2, 3, 4, etc .; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). The use of the term "optionally" with respect to any element of the claim is intended to explain that the element of the subject is required or, alternatively, is not required. Both alternatives are intended to be within the scope of the claim. Use of broader terms, such as comprises, includes, having, etc., is to be understood as providing support for more restricted terms, such as consisting of, consisting essentially of, substantially understood by, etc.
    [0094] In this sense, the scope of protection is not limited by the description defined above, but is limited only by the following claims, this scope including all equivalents of the subject of the claims. Each and every claim is incorporated in the specification as a form of this disclosure. Thus, the claims are an additional description and are an addition to the modalities of the present disclosure. The discussion of a reference in the disclosure is not an admission that it is state of the art of the present disclosure, especially any reference that may have a publication date after the priority date of this request. Disclosures of all patents, patent applications and publications cited in this document are incorporated herein by reference, as they provide exemplary details, procedures or other complementary to those presented in this document.
    权利要求:
    Claims (8)
    [0001]
    1. Polymer having a long chain branch content reaching a peak above 8 long chain branches per million carbon atoms and a polydispersity index greater than 20, characterized by the fact that the long chain branch decreases to approximately zero at a molecular weight greater than 10,000.OOOkg / mol.
    [0002]
    2. Polymer according to claim 1, characterized by the fact that the long chain branch content peaks at 20 long chain branches per one million carbon atoms.
    [0003]
    3. Polymer according to claim 1, characterized by the fact that the content of long chain branching peaks above 1.0 long chain branching per chain.
    [0004]
    4. Polymer according to claim 1, characterized by the fact that the polymer comprises polyethylene.
    [0005]
    5. Method of polymerization of a monomer, characterized by the fact that it comprises the contact between the monomer and a chromium-supported catalyst, under suitable conditions, for the formation of a polymer; and recovering the polymer in which the chromium-supported catalyst comprises a silica support having a surface area of less than 200 m2 / g and in which the polymer is a polymer as defined in any one of claims 1 to 4.
    [0006]
    6. Method according to claim 5, characterized in that the suitable conditions for the formation of a polymer further comprise a cocatalyst.
    [0007]
    7. Method according to claim 5, characterized by the fact that the chromium-supported catalyst further comprises titanium.
    [0008]
    8. Method according to claim 5, characterized in that the monomer comprises ethylene and the polymer comprises polyethylene.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014013159B1|2020-09-29|POLYMERS WITH LONG BRANCHED CHAIN AND PRODUCTION METHODS OF THE SAME
    ES2745050T3|2020-02-27|Methods for preparing a catalyst
    ES2668368T3|2018-05-17|Quick Activation Catalyst
    BR112019022361A2|2020-02-18|METHODS FOR PREPARING A CATALYST
    ES2837127T3|2021-06-29|Chromium | catalysts with supports-activators
    EP0577761A4|1994-07-13|Mixed chromium catalysts and polymerizations utilizing same
    BR112019010794A2|2019-10-01|methods of preparing a catalyst
    HU205153B|1992-03-30|Process for dimerization of ethylene and simultaneous copolymerization of the dimeric product and ethylene, catalyst compositions for the process, as well as process for producing same
    BR112013016162B1|2020-04-07|method for controlling polymeric composition of ethylene copolymer in process for preparing ethylene copolymer by copolymerization of ethylene and at least one other olefin, process for copolymerizing ethylene and at least one other olefin, method for altering polymeric composition of ethylene copolymer obtained by copolymerization of ethylene and at least one other olefin, and method for transition from one degree of ethylene copolymer to another
    CN108690151B|2020-12-18|Catalyst system for olefin polymerization and olefin polymerization method
    WO2009085101A2|2009-07-09|Methods of preparing a polymerization catalyst
    CN107880163B|2020-07-21|Catalyst component for olefin polymerization and preparation and application thereof
    CN107880169B|2020-07-24|Catalyst component for olefin polymerization and preparation and application thereof
    CN107880178B|2020-07-24|Catalyst component for olefin polymerization and preparation and application thereof
    BR112021005500A2|2021-06-15|methods for producing supported chromium catalysts with increased polymerization activity
    BR112017010521B1|2021-11-30|CHROME-BASED CATALYST COMPOSITIONS FOR OLEFIN POLYMERIZATION, METHOD FOR MANUFACTURING A CHROME-BASED CATALYST COMPOSITION FOR OLEFIN POLYMERIZATION AND OLEFIN POLYMERIZATION METHOD
    同族专利:
    公开号 | 公开日
    EP3246345A1|2017-11-22|
    CN104080823A|2014-10-01|
    CA2857362C|2019-09-24|
    KR20140097319A|2014-08-06|
    BR112014013159A2|2017-06-27|
    SG10201607495SA|2016-10-28|
    MX2014006390A|2015-03-03|
    MX346343B|2017-03-14|
    US20150203614A1|2015-07-23|
    US20170145124A1|2017-05-25|
    EP2785751A1|2014-10-08|
    US9598513B2|2017-03-21|
    CA2857362A1|2013-06-06|
    US10323108B2|2019-06-18|
    EP2785751B1|2018-05-09|
    WO2013081826A1|2013-06-06|
    CA3049594A1|2013-06-06|
    US9023967B2|2015-05-05|
    ES2676664T3|2018-07-23|
    US20170037158A1|2017-02-09|
    CA3049594C|2020-06-30|
    CN104080823B|2017-07-18|
    US9879101B2|2018-01-30|
    SG11201402758XA|2014-06-27|
    US20130137839A1|2013-05-30|
    KR101941732B1|2019-04-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2503913A|1944-06-21|1950-04-11|Standard Oil Dev Co|Process of drying inorganic hydrogel particles|
    US3248179A|1962-02-26|1966-04-26|Phillips Petroleum Co|Method and apparatus for the production of solid polymers of olefins|
    US3119569A|1962-03-28|1964-01-28|Baricordi Antonio|Grinding apparatus|
    GB1197069A|1967-06-28|1970-07-01|Du Pont|Catalytic Coatings for Cooking Devices|
    US3622521A|1967-08-21|1971-11-23|Phillips Petroleum Co|Olefin polymerization with chromium and titanium-containing compounds|
    US3900457A|1970-10-08|1975-08-19|Phillips Petroleum Co|Olefin polymerization catalyst|
    US3887494A|1970-11-12|1975-06-03|Phillips Petroleum Co|Olefin polymerization catalyst|
    CA979419A|1970-11-12|1975-12-09|Richard E. Dietz|Olefin polymerization catalyst|
    US3780011A|1971-04-09|1973-12-18|Chemplex Co|Catalyst and catalytic process|
    GB1415649A|1971-12-23|1975-11-26|Bp Chem Int Ltd|Olefin polymerisation process and catalyst for use therein|
    BE793717A|1972-01-07|1973-07-05|Phillips Petroleum Co|LARGE PORES SILICA GEL CATALYSTS|
    US3875079A|1972-07-31|1975-04-01|Phillips Petroleum Co|Large pore silicas|
    US4119569A|1973-05-24|1978-10-10|Phillips Petroleum Company|Olefin polymerization catalyst|
    US3882096A|1973-09-04|1975-05-06|Chemplex Co|Catalyst for and method of preparing ultra high molecular weight polyolefins|
    GB1495265A|1974-03-08|1977-12-14|Bp Chem Int Ltd|Polymerisation of 1-olefins|
    GB1447605A|1974-05-08|1976-08-25|Phillips Petroleum Co|Olefin polymerization catalyst peparation|
    US3976632A|1974-12-04|1976-08-24|Phillips Petroleum Company|Reactivation of organochromium olefin polymerization catalyst in presence of oxygen|
    US4053436A|1975-08-26|1977-10-11|Phillips Petroleum Company|Spray dried titanium-containing catalyst for stress crack resistant polymer|
    US4041224A|1975-11-19|1977-08-09|Chemplex Company|Catalyst, method and polymerization processes|
    US4081407A|1976-03-18|1978-03-28|Phillips Petroleum Company|Catalyst support prepared by alcohol treatment of hydrogels|
    US4169926A|1978-01-16|1979-10-02|Phillips Petroleum Company|Inorganic hydrogels and uses thereof|
    US4190457A|1978-06-09|1980-02-26|Phillips Petroleum Co.|Preparation of inorganic xerogels|
    US4280141A|1978-09-22|1981-07-21|Mccann David H|Time delay and integration detectors using charge transfer devices|
    US4218345A|1979-01-15|1980-08-19|Chemplex Company|Olefin polymerization catalyst of chromium and process of preparing it|
    US4247421A|1979-05-03|1981-01-27|Phillips Petroleum Company|Activation of supported chromium oxide catalysts|
    US4294724A|1980-02-06|1981-10-13|Phillips Petroleum Company|Titanium impregnated silica-chromium catalysts|
    US4345055A|1980-02-06|1982-08-17|Phillips Petroleum Company|Polymerization with titanium impregnated silica-chromium catalysts|
    US4312967A|1980-02-06|1982-01-26|Phillips Petroleum Co.|Polymerization catalyst and process|
    US4296001A|1980-02-06|1981-10-20|Phillips Petroleum Company|Titanium impregnated silica-chromium catalysts|
    US4368303A|1980-02-06|1983-01-11|Phillips Petroleum Company|Titanium impregnated silica-chromium catalysts|
    US4299731A|1980-02-06|1981-11-10|Phillips Petroleum Company|Large pore volume olefin polymerization catalysts|
    US4402864A|1981-08-14|1983-09-06|Phillips Petroleum Company|Catalyst support treated with titanium polymer|
    US4405768A|1981-08-14|1983-09-20|Phillips Petroleum Company|Polymerization process using chromium on a support treated with titanium polymer|
    US4501885A|1981-10-14|1985-02-26|Phillips Petroleum Company|Diluent and inert gas recovery from a polymerization process|
    US4446243A|1981-10-27|1984-05-01|Mobil Oil Corporation|Catalysts for olefin polymerization comprising the reaction product of organotitanium and organochromium with zeolites|
    US4424320A|1981-11-25|1984-01-03|Phillips Petroleum Company|Polymerization with a silica base catalyst having titanium incorporated through use of peroxide|
    US4405501A|1982-01-20|1983-09-20|Phillips Petroleum Company|Aging of chromium-containing gel at high pH|
    US4434243A|1982-03-09|1984-02-28|Phillips Petroleum Company|Aqueous titanation of catalyst support containing chromium with solubilized Ti4|
    US4442275A|1982-03-09|1984-04-10|Phillips Petroleum Company|Polymerization process using catalyst having aqueous titanation of support with solubilized Ti4|
    US4588790A|1982-03-24|1986-05-13|Union Carbide Corporation|Method for fluidized bed polymerization|
    US4559394A|1983-06-03|1985-12-17|Phillips Petroleum Company|Olefin polymerization using activated chromium catalyst treated with tertiary alcohol|
    US4547557A|1984-07-09|1985-10-15|Phillips Petroleum Company|Silica-titania cogel from two-step hydrolysis|
    SU1563684A1|1986-05-26|1990-05-15|Томский государственный медицинский институт|Cryosurgical scalpel|
    CA1323361C|1987-10-21|1993-10-19|John T. Hsieh|Catalyst composition for polymerizing alpha olefins and alpha olefins polymerization therewith|
    NO891479L|1988-04-12|1989-10-13|Union Carbide Corp|PROCEDURE FOR REDUCING SLEEP FEATURES OF ALFA OLEFINES.|
    NO172242C|1988-04-26|1993-06-23|Showa Denko Kk|PROCEDURE FOR PREPARING ETHYLENE POLYMERS|
    US4981831A|1988-07-25|1991-01-01|Phillips Petroleum Company|Twice-aged porous inorganic oxides, catalysts, and polymerization processes|
    US5115053A|1988-07-25|1992-05-19|Phillips Petroleum Company|Twice-aged porous inorganic oxides, catalysts, and polymerization processes|
    CA2033959A1|1990-01-24|1991-07-25|Levi J. Cottington|Alkoxy-functional silane compositions for unprimed adhesion to polycarbonate|
    EP0455444B1|1990-04-29|1997-10-08|Canon Kabushiki Kaisha|Movement detection device and focus detection apparatus using such device|
    US5565175A|1990-10-01|1996-10-15|Phillips Petroleum Company|Apparatus and method for producing ethylene polymer|
    US5575979A|1991-03-04|1996-11-19|Phillips Petroleum Company|Process and apparatus for separating diluents from solid polymers utilizing a two-stage flash and a cyclone separator|
    US5231066A|1991-09-11|1993-07-27|Quantum Chemical Corporation|Bimodal silica gel, its preparation and use as a catalyst support|
    US5183792A|1991-11-26|1993-02-02|Allied-Signal Inc.|Catalyst for making polyethylene|
    US5352749A|1992-03-19|1994-10-04|Exxon Chemical Patents, Inc.|Process for polymerizing monomers in fluidized beds|
    US5436304A|1992-03-19|1995-07-25|Exxon Chemical Patents Inc.|Process for polymerizing monomers in fluidized beds|
    BE1005795A3|1992-05-13|1994-02-01|Solvay|Olefin polymerization process and polymer blocks derivatives at least olefine.|
    GB9210265D0|1992-05-13|1992-07-01|Unilever Plc|Catalysts and catalyst supports|
    KR950005601B1|1992-09-19|1995-05-27|삼성전자주식회사|Stabilization method and system of digital image|
    US5284926A|1992-09-25|1994-02-08|Phillips Petroleum Company|Catalyst system and process|
    US5576262A|1994-06-02|1996-11-19|W. R. Grace & Co.-Conn.|Glycol ether compounds for the production of polyolefin catalysts and supports|
    US5455314A|1994-07-27|1995-10-03|Phillips Petroleum Company|Method for controlling removal of polymerization reaction effluent|
    DE69633400T2|1995-12-01|2005-02-17|Chevron Phillips Chemical Co. Lp, The Woodlands|Polymerization|
    EP0805164B1|1996-05-01|2002-09-18|INEOS Silicas Limited|Porous inorganic catalyst support|
    EP0882740A1|1997-06-06|1998-12-09|Fina Research S.A.|Titanated chromium-based catalysts to produce polyethylene exhibiting better environmental stress crack resistance|
    EP0882744B1|1997-06-06|2003-07-23|ATOFINA Research|Supported chromium-based catalyst for the production of polyethylene suitable for blow moulding|
    EP0882743B1|1997-06-06|2003-11-12|ATOFINA Research|Titanated chromium-based catalysts to produce polyethylene|
    US6239235B1|1997-07-15|2001-05-29|Phillips Petroleum Company|High solids slurry polymerization|
    US6707498B1|1997-11-11|2004-03-16|Fuji Photo Film Co., Ltd.|Charge transfer of solid-state image pickup device|
    KR100531628B1|1998-03-20|2005-11-29|엑손모빌 케미칼 패턴츠 인코포레이티드|Continuous slurry polymerization volatile removal|
    EP0962469A1|1998-06-05|1999-12-08|Fina Research S.A.|Titanated chromium catalyst supported on silica-aluminophosphate|
    US6204346B1|1998-12-17|2001-03-20|Phillips Petroleum Co.|Polymerization process|
    US6262191B1|1999-03-09|2001-07-17|Phillips Petroleum Company|Diluent slip stream to give catalyst wetting agent|
    US6569960B2|1999-07-27|2003-05-27|Phillips Petroleum Company|Process to produce polymers|
    CA2334746A1|2000-02-09|2001-08-09|Sumitomo Chemical Co., Ltd.|Process for producing optically active hemiesters|
    WO2002002652A2|2000-07-05|2002-01-10|Basell Polyolefine Gmbh|Suspended chrome catalyst containing titanium and the use thereof for producing ethylene homopolymers and copolymers|
    AUPR113700A0|2000-10-31|2000-11-23|Australian Nuclear Science & Technology Organisation|Transition metal oxide compositions|
    US7088394B2|2001-07-09|2006-08-08|Micron Technology, Inc.|Charge mode active pixel sensor read-out circuit|
    US8114945B2|2001-10-17|2012-02-14|Ineos Europe Limited|Process control for the -polymerisation of olefins|
    DE60331853D1|2002-12-10|2010-05-06|Basell Polyolefine Gmbh|FOR THE PRODUCTION OF ETHYLENE HOMOPOLYMERS AND COPOLYMERS|
    US6989344B2|2002-12-27|2006-01-24|Univation Technologies, Llc|Supported chromium oxide catalyst for the production of broad molecular weight polyethylene|
    US7384885B2|2003-03-31|2008-06-10|Exxonmobil Chemical Patents Inc.|Catalyst activation and resins therefrom|
    US7041617B2|2004-01-09|2006-05-09|Chevron Phillips Chemical Company, L.P.|Catalyst compositions and polyolefins for extrusion coating applications|
    DE102004020524A1|2004-04-26|2005-11-10|Basell Polyolefine Gmbh|Polyethylene for film, e.g. stretch film, used in carrier bags, contains ethylene homopolymers and/or copolymers of ethylene with 1-alkenes|
    US7615510B2|2004-05-12|2009-11-10|Chevron Phillips Chemical Company Lp|Methods of activating chromium catalysts|
    US7192901B2|2004-10-27|2007-03-20|Exxonmobil Chemical Patents Inc.|Method of preparing a treated support|
    US7390395B2|2005-06-23|2008-06-24|Saleh Elomari|Hydrocarbon conversion using molecular sieve SSZ-56|
    EP1845110A1|2006-04-13|2007-10-17|Total Petrochemicals Research Feluy|Chromium-based catalysts|
    US7879748B2|2006-08-09|2011-02-01|Umicore Ag & Co. Kg|Method for producing a catalyst and the catalyst made therefrom|
    US7375169B1|2007-01-25|2008-05-20|Exxonmobil Chemical Patents Inc.|Method for catalyst preparation and improved polyethylene blow molding resin|
    US7700516B2|2007-09-26|2010-04-20|Chevron Phillips Chemical Company Lp|Methods of preparing a polymerization catalyst|
    US7589044B2|2007-10-02|2009-09-15|Chevron Phillips Chemical Company Lp|Methods of preparing a polymerization catalyst|
    EP2195354B1|2007-10-03|2018-12-05|Chevron Phillips Chemical Company Lp|Methods of preparing a polymerization catalyst|
    US8183173B2|2007-12-21|2012-05-22|Chevron Phillips Chemical Company Lp|Fast activating catalyst|
    US20110217537A1|2008-09-25|2011-09-08|Basell Polyolefine Gmbh|Impact Resistant LLDPE Composition and Films Made Thereof|
    EP2172490A1|2008-10-03|2010-04-07|Ineos Europe Limited|Controlled polymerisation process|
    US8372771B2|2010-02-16|2013-02-12|Chevrton Phillips Chemical Company LP|System and method for catalyst activation|
    US8828529B2|2010-09-24|2014-09-09|Chevron Phillips Chemical Company Lp|Catalyst systems and polymer resins having improved barrier properties|
    EP2447290A1|2010-11-01|2012-05-02|Ineos Commercial Services UK Limited|Chromium catalysed ethylene copolymer powder|
    JP6004528B2|2011-08-29|2016-10-12|地方独立行政法人東京都立産業技術研究センター|Method for producing porous silica-encapsulated particles and porous silica|
    US9023967B2|2011-11-30|2015-05-05|Chevron Phillips Chemical Company Lp|Long chain branched polymers and methods of making same|
    US9096699B2|2011-12-02|2015-08-04|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst|
    US9725530B2|2012-04-20|2017-08-08|East China University Of Science And Technology|Supported metal oxide double active center polyethylene catalyst, process for preparing the same and use thereof|
    US9376511B2|2013-03-13|2016-06-28|Chevron Phillips Chemical Company Lp|Polymerization catalysts and polymers|
    US9587048B2|2015-04-29|2017-03-07|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst|
    US10213766B2|2015-09-18|2019-02-26|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst|
    US9988468B2|2016-09-30|2018-06-05|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst|
    US10654953B2|2016-12-29|2020-05-19|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst|US9023967B2|2011-11-30|2015-05-05|Chevron Phillips Chemical Company Lp|Long chain branched polymers and methods of making same|
    US9096699B2|2011-12-02|2015-08-04|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst|
    US9382349B2|2012-08-03|2016-07-05|Exxonmobil Chemical Patents Inc.|Polyalphaolefins prepared using modified Salan catalyst compounds|
    EP2880096B1|2012-08-03|2018-01-03|ExxonMobil Chemical Patents Inc.|Process for preparing polyalphaolefins using modified salan catalyst compounds and polyalphaolefins prepared therewith|
    EP2880097A4|2012-08-03|2016-07-13|Exxonmobil Chem Patents Inc|Vinyl terminated polyethylene with long chain branching|
    US10155831B2|2013-09-05|2018-12-18|Univation Technologies, Llc|Process control for long chain branching control in polyethylene production|
    US10246528B2|2014-01-09|2019-04-02|Chevron Phillips Chemical Company Lp|Chromiumcatalyst systems with activator-supports|
    US9587048B2|2015-04-29|2017-03-07|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst|
    US10213766B2|2015-09-18|2019-02-26|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst|
    US9988468B2|2016-09-30|2018-06-05|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst|
    US11267914B2|2016-12-29|2022-03-08|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst|
    US10654953B2|2016-12-29|2020-05-19|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst|
    CN108690150B|2017-04-07|2020-11-10|中国石油化工股份有限公司|Catalyst system for olefin polymerization and olefin polymerization method|
    US10550252B2|2017-04-20|2020-02-04|Chevron Phillips Chemical Company Lp|Bimodal PE resins with improved melt strength|
    US10287369B2|2017-04-24|2019-05-14|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst|
    US10323109B2|2017-11-17|2019-06-18|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst utilizing hydrated reagents|
    US10513570B2|2017-11-17|2019-12-24|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst|
    US10543480B2|2018-04-16|2020-01-28|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst utilizing hydrated reagents|
    US11266976B2|2018-04-16|2022-03-08|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst with low HRVOC emissions|
    US10722874B2|2018-04-16|2020-07-28|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst utilizing hydrated reagents|
    WO2021173148A1|2020-02-28|2021-09-02|Ecovyst Catalyst Technologies Llc|Chromium-on-silica catalysts and methods of making the same|
    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-06-16| B09A| Decision: intention to grant|
    2020-09-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/11/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/308.289|2011-11-30|
    US13/308,289|US9023967B2|2011-11-30|2011-11-30|Long chain branched polymers and methods of making same|
    PCT/US2012/064986|WO2013081826A1|2011-11-30|2012-11-14|Long chain branched polymers and methods of making same|
    [返回顶部]