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    • 专利摘要:
    POLYMER COMPOSITIONS HAVING IMPROVED BARRIER PROPERTIES A unimodal polymer having a melt index of about 0.5 g / 10 min to about 4 g / 10 min, a density equal to or greater than about 0.945 g / cc, which when formed on a film it exhibits a moisture vapor transmission rate of less than about 0.55 g-mil / 100 in2 in 24 hours, as determined in accordance with ASTM F 1249. A unimodal polymer having a melt index of about 0.5 g / 10 min to about 4 g / 10 min, a density equal to or greater than about 0.945 g / cc, which when formed on a film exhibits a moisture vapor transmission rate of less than about 0.44 g-mil / 100 in2 in 24 hours, as determined in accordance with ASTM F 1249.
    公开号:BR112014004956B1
    申请号:R112014004956-4
    申请日:2012-09-04
    公开日:2020-11-10
    发明作者:Qing Yang；Mark L. Hlavinka；Guylaine St Jean；Brooke A Gill
    申请人:Chevron Phillips Chemical Company Lp；
    IPC主号:
    专利说明:

    CROSS REFERENCE TO RELATED ORDERS
    [0001] The object of this application is related to Patent Application Serial No. US61 / 530,711 [Precedent No. 211398US00 (4081-16600)] filed simultaneously therewith and entitled "Polymer Compositions Having Improved Barrier Properties" (" Polymer compositions having improved barrier properties ") and Serial No. 13/224785 [Precedent No. 211432US00 (4081-16900)] deposited simultaneously with this and titled" Multilayer Polymer Films having improved barrier properties "(" Multilayer Polymer Films Having Improved Barrier Properties ”), each of which is hereby incorporated by reference in its entirety for all purposes. FIELD OF THE INVENTION
    [0002] The present disclosure relates to polymeric compositions, more specifically compositions of polyethylene (PE) and articles made of the same. BACKGROUND OF THE INVENTION
    [0003] Polyolefins are plastic materials useful for making a wide variety of valuable products due to their combination of rigidity, ductility, barrier properties, temperature resistance, optical properties, availability and low cost. One of the most valued products is plastic films. In particular, PE is one of the most widely consumed polymers in the world. It is a versatile polymer that offers high performance compared to other polymers and alternative materials such as glass, metal or paper. Plastic films, such as PE films, are mainly used in packaging applications, but also find use in agricultural, medicinal and engineering fields.
    [0004] PE films are manufactured in a variety of types that are generally differentiated by the density of the polymer, so that PE films can be designated, for example, low density polyethylene (LDPE), linear low density polyethylene (LLDPE ), medium density polyethylene (MDPE) and high density polyethylene (HDPE), where each density range has a unique combination of properties, making them suitable for a particular application.
    [0005] Despite many positive attributes of PE, the film product remains permeable to gases, such as oxygen or carbon dioxide and / or moisture (for example, water). Thus, it would be desirable to develop a PE film product exhibiting improved barrier properties. SUMMARY OF THE INVENTION
    [0006] A unimodal polymer is disclosed here, having a melt index of about 0.5 g / 10 min to about 4 g / 10 min, a density equal to or greater than about 0.945 g / cc, which when formed in a film exhibits a moisture vapor transmission rate of less than about 0.55 g-mil / 100 in2 within 24 hours as determined in accordance with ASTM F 1249.
    [0007] A unimodal polymer is also disclosed here, having a melting index of about 0.5 g / 10 min to about 4 g / 10 min, a density equal to or greater than about 0.945 g / cc, which when formed in a film exhibits a moisture vapor transmission rate of less than about 0.44 g-mil / 100 in 24 hours as determined in accordance with ASTM F 1249.
    [0008] A unimodal polymer is also disclosed here, having a melt index of about 0.5 g / 10 min to about 4 g / 10 min, a density equal to or greater than about 0.945 g / cc than when formed in a film exhibits a moisture vapor transmission rate of less than about 0.39 g-mil / 100 in2 within 24 hours as determined in accordance with ASTM F 1249. BRIEF DESCRIPTION OF THE FIGURES
    [0009] Figure 1 is a graphical representation of the molecular weight distribution profiles for the samples in Example 1.
    [0010] Figure 2 is a plot of the dynamic melting viscosity as a function of frequency for the samples in Example 1. DETAILED DESCRIPTION
    [0011] Polymers, polymeric compositions, polymeric articles and methods of doing the same are disclosed here. The polymers and / or polymeric compositions of the present disclosure can comprise polyethylene. The polymers and / or polymeric compositions disclosed herein may comprise a mixture of polymeric components and result in an improved polymer and / or polymeric composition which, interestingly, exhibit barrier properties when compared to a similar polymeric composition, otherwise prepared under conditions many different.
    [0012] 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, but are not limited to, what can be referred to as batch, mud, gas phase, solution, high pressure, tubular, autoclave, or other reactor or reactors. Gas phase reactors can comprise fluidized bed reactors or horizontal stage reactors. Slurry reactors can comprise vertical 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 or continuous product transfer or discharge. Processes may also include partial or complete direct recycling of the unreacted monomer, unreacted comonomer, catalyst and / or cocatalysts, diluents, and / or other materials from the polymerization process.
    [0013] 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 reactors in multiple reactors can include several stages 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 in the second reactor. Alternatively, polymerization in multiple reactors may include the transfer, either manual or automatic, of polymer from one reactor to the subsequent reactor or additional polymerization reactors. 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.
    [0014] The desired polymerization conditions in one of the reactors can be the same or different from the operating conditions of any other reactors involved in the entire polymer production process of the present disclosure. Multiple reactor systems may include any combination that includes, but is not limited to, 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 with cycle and / or gas reactors. The multiple reactors can be operated in series or in parallel. In one embodiment, any arrangement and / or any combination of the reactors can be employed to produce the polymer of the present disclosure.
    [0015] According to one embodiment, the polymerization reactor system may comprise at least one cycle sludge reactor. These 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 this reactor from a suspension comprising the polymer particles and the diluent. Effluent from the reactor can be absorbed abruptly to remove liquids that comprise the solid polymer diluent, monomer and / or comonomer. Various technologies can be used for this separation step including, but not limited to, absorption, which can include any combination of heat addition and pressure reduction; separation by cyclonic action either in a cyclone or hydrocyclone; centrifugation separation; or another appropriate method of separation.
    [0016] Typical sludge polymerization processes (also known as particle shape processes) are disclosed in Patent Nos. US3,248,179, US4,501,885, US5,565,175, US5,575,979, US6,239,235, US6,262,191 and US6,833,415, for example; each of which is incorporated herein by reference in its entirety.
    [0017] Suitable diluents used in sludge polymerization include, but are not limited to: 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 the polymerization of the propylene monomer as disclosed in Patent No. US5,455,314, which is incorporated herein by reference in its entirety.
    [0018] 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 recycled 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, the 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 may comprise a process for the polymerization of multi-stage and gas phase olefins, in which olefins are polymerized in gas phase in at least two independent gas phase polymerization zones, while feeding a polymer containing catalyst formed in a first polymerization zone for a second polymerization zone. A type of gas phase reactor is disclosed in Patent Nos. US4,588,790, US5,352,749 and US5,436,304, each of which is incorporated herein by reference in its entirety.
    [0019] 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. Monomer can be entrained in an inert gas stream and introduced into a reactor zone. Primers, catalysts and / or catalyst components can be entrained in a gaseous flow and introduced into another zone of the reactor. Gas flows can be streaked for polymerization. Heat and pressure can be used appropriately to obtain ideal polymerization reaction conditions.
    [0020] According to yet another modality, the polymerization reactor may comprise a solution polymerization reactor, in which the monomer is contacted 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 contacted in the vapor phase 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. Agitation can be employed to obtain the best temperature control and to maintain uniform polymerization mixes throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat from polymerization.
    [0021] Polymerization reactors suitable for the present disclosure may further comprise any combination of at least one raw material feed system, at least one feed system for the catalyst or catalyst components, and / or at least one feed system. polymer recovery. Reactor systems suitable for the present invention may further comprise systems for purification of raw material, storage and preparation of catalyst, extrusion, reactor refrigeration, polymer recovery, fractionation, recycling, storage, unloading, laboratory analysis and process control.
    [0022] Conditions that are controlled for polymerization efficiency and to provide polymer properties include, but are not limited to, temperature, pressure, type and quantity of the catalyst or cocatalyst and the concentrations of various reagents. Polymerization temperature can affect catalyst productivity, polymer molecular weight and 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.
    [0023] Adequate pressures will also vary according to the reactor and polymerization process. The pressure for liquid phase polymerization in a cycle reactor is usually less than 1000 psig. Pressure for polymerization of the gas phase is generally around 200 - 500 psig. High pressure polymerization in tubular or autoclave reactors is generally performed at about 20,000 to 75,000 psig. Polymerization reactors can also be operated in a supercritical region, generally occurring at higher temperatures and pressures. Operation above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages.
    [0024] The concentration of various reagents can be controlled to produce polymers with certain physical and mechanical properties. The proposed end-use product that will be formed by the polymer and the method for forming that product can be varied to determine the properties of the desired end product. Mechanical properties include, but are not limited to, tensile strength, flexural modulus, impact resistance, creep, stress relaxation and hardness tests. Physical properties include, but are not limited to density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereo-regularity, crack growth, short chain branching, branching long-chain and rheological measurements.
    [0025] The concentrations of monomer, comonomer, hydrogen, cocatalyst, modifiers and electron donors are generally important in the production of specific properties of the polymer. Comonomer can be used to control product density. Hydrogen can be used to control the molecular weight of the product. Cocatalysts can be used to alkylate, eliminate toxins and / or control molecular weight. The concentration of toxicants can be minimized, as toxicants can affect the reactions and / or affect properties of the polymer product in another way. Modifiers can be used to control product properties and electron donors can affect stereo-regularity.
    [0026] In one embodiment, a method of preparing a polymer comprises contacting an olefin and / or alpha-olefin monomer with a catalyst system under conditions suitable for the formation of a polymer of the type described here. In one embodiment, a catalyst composition for producing a polymer of the type disclosed herein can comprise a single metallocene compound; an activator support and an organo-aluminum compound. The term "metallocene" here describes a compound comprising at least a portion of the cycloalkadienyl type η3 to η5, wherein portions of cycloalkadienyl η3 to η5- include cyclopentadienyl linkers, indenyl linkers, fluorenyl linkers and the like, including partially saturated or substituted derivatives, or analogues of any of these. Possible substituents on these binders include hydrogen, so the description "substituted derivatives thereof" in this disclosure comprises partially saturated binders, such as tetrahydroindenyl, tetrahydrofluorenyl, octahidrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, partially saturated substituted indenyl, partially saturated substituted fluorenyl, and others.
    [0027] In one embodiment, the metallocene comprises a tight-bridged loop-metallocene comprising an olefin-containing moiety attached to a cyclopentadienyl-type ligand and at least one aryl group attached to the bridge atom of the bridge ligand. As used here, the term bridge or loop-metallocene simply refers to a metallocene compound, in which the two η5 cycloalkadienyl linkers in the molecule are connected by a bridge portion. Useful ansa-metallocenes are typically "firm-bridged", meaning that two η5 cycloalkadienyl-type ligands are connected by a bridge group in which the shortest link of the bridge portion between η5 cycloalkadienyl-type ligands is a single atom. Thus, the length of the bridge or the current between two ligands of the cycloalcadienyl type η5 is an atom, although this bridge atom is replaced. The disclosure metallocenes are therefore compound- (cycloalkadienyl η5) bridge bis, wherein the η5 cycloalkadienyl moieties include substituted cyclopentadienyl linkers, substituted indenyl linkers, substituted fluorenyl linkers and the like, where a substituent of these cyclopentadienyl type linkers is a bridge group, having the formula ER1R2, where E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and where E is attached to both cyclopentadienyl-type ligands . In this respect, R1 and R2 can be independently selected from an alkyl group or an aryl group, each having up to 12 carbon or hydrogen atoms. A metallocene compound suitable for use in the present disclosure may exhibit a positive hydrogen response. Here, a positive hydrogen response refers to a reduction in molecular weight. Examples of metallocene compounds suitable for use in the present disclosure are described in more detail in Patent Nos. US7,064,225, US7,226,886 and US7,517,939, each of which are incorporated herein by reference in their entirety. In one aspect, the support-activator comprises a chemically treated solid oxide. Alternatively, the support-activator may comprise a clay mineral, a pillared clay, an exfoliated clay, an exfoliated clay gelled in another oxide matrix, a layered silicate mineral, a layered silicate mineral, a silicate mineral layered aluminum, a layered aluminum silicate mineral or any combination thereof.
    [0028] Generally, chemically treated solid oxides have enhanced acidity when compared to the corresponding untreated solid oxide compound. The chemically treated solid oxide also functions as a catalyst activator when compared to the corresponding untreated solid oxide. While the chemically treated solid oxide activates the metallocene (s) in the absence of cocatalysts, it is not necessary to eliminate cocatalysts from the catalyst composition. The activation function of the support-activator is evident in the enhanced activity of the catalyst composition as a whole when compared to a catalyst composition containing the corresponding untreated solid oxide. However, it is believed that the chemically treated solid oxide can function as an activator, even in the absence of an organo-aluminum compound, aluminoxanes, organoboro or organoborate compounds, ionizing ionic compounds and the like.
    [0029] The chemically treated solid oxide may comprise a solid oxide treated with an electron withdrawing anion Although it is not intended to be limited by the following instruction, it is believed that the treatment of solid oxide with an electron withdrawing component increases or reinforces the acidity of the oxide. Thus, the support-activator has both Lewis and Bronsted acidity which is usually greater than the Lewis or Bnansted acid strength of untreated solid oxide, or the support-activator has a greater number of acid sites than untreated solid oxide, or both. One method to quantify the acidity of chemically treated and untreated solid oxide materials is by comparing the polymerization activities of treated and untreated oxides under acid catalyzed reactions.
    [0030] Chemically treated solid oxides of this disclosure are generally formed from an inorganic solid oxide that exhibits Lewis acid or Bronsted acid behavior and has a relatively high porosity. The solid oxide is chemically treated with an electron withdrawing component, usually an electron withdrawing anion to form an activator support.
    [0031] According to one aspect of the present disclosure, the solid oxide used to prepare the chemically treated solid oxide has a pore volume greater than about 0.1 cc / g. According to another aspect of the present disclosure, the solid oxide has a pore volume greater than about 0.5 cc / g. According to one aspect of the present disclosure, solid oxide has a pore volume greater than about 1.0 cc / g.
    [0032] In another aspect, the solid oxide has a surface area of about 100 m2 / g to about 1000 m2 / g. In yet another aspect, the solid oxide has a surface area of about 200 m2 / g to about 800 m2 / g. In yet another aspect of the present disclosure, solid oxide has a surface area of about 250m2 / g to about 600m2 / g.
    [0033] The chemically treated solid oxide may comprise a solid inorganic oxide comprising oxygen and one or more elements selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 of the periodic table, or which comprises oxygen and one or more elements selected from the lanthanide or actinide elements (see: Hawley's Condensed Chemical Dictionary, 11th Ed., John Wiley & Sons, 1995; Cotton, FA, Wilkinson, G., Murillo , CA, and Bochmann, M., Advanced Inorganic Chemistry, 6th Ed., Wiley-Interscience, 1999). For example, inorganic oxide can comprise oxygen and an element or elements selected from Al, B, ser, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn and Zr.
    [0034] Suitable examples of solid oxide materials or compounds that can be used to form chemically treated solid oxide include, but are not limited to, AI2O3, B2O3, BeO, BI2O3, CdO, CO3O4, C ^ Os, CuO, Fβ2θ3 , Ga2θ3, La2θ3, Mn2θs, MoOs, NiO, P2O5, Sb2θ5, SÍO2, Snθ2 SrO, Thθ2, TÍO2, V2O5, WO3, Y2O3, ZnO, Zrθ2, and the like, including mixed oxides thereof and combinations thereof. For example, the solid oxide can comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminum phosphate, heteropolitungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof or any combination thereof. .
    [0035] The solid oxide of this disclosure includes oxide materials such as alumina, compounds of "mixed oxide" thereof, such as silica-alumina, and combinations and mixtures thereof. Mixed oxide compounds, such as silica-alumina, can be single or multiple chemical phases with more than one metal combined with oxygen to form a solid oxide compound. Examples of mixed oxides that can be used in the activator support of the present disclosure include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, zeolites, various clay minerals, Alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminophosphate-silica, titania-zirconia and the like. The solid oxide of this disclosure also encompasses oxide materials, such as silica-coated alumina, as described in U.S. Patent No. 7,884,163, the disclosure of which is incorporated herein by reference in its entirety.
    [0036] The electron withdrawing component used to treat the solid oxide can be any component that increases the Lewis or Bronsted acidity of the solid oxide in the treatment (when compared to the solid oxide that is not treated with at least one electron withdrawing anion. ). According to one aspect of the present disclosure, the electron-withdrawing component is an electron-withdrawing anion derived from a salt, acid or other compound, such as a volatile organic compound, which serves as a source or precursor for the anion. Examples of electron withdrawing anions include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, trilate, fluorotitanate, phosphotungstate and the like, including mixtures and the like, including mixtures themselves. In addition, other ionic or non-ionic compounds that serve as sources for these electron-withdrawing anions can also be employed in the present disclosure. It is envisaged that the electron withdrawing anion may be, or may include, fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate and the like or any combination thereof, in some aspects of this disclosure. In other respects, the electron withdrawing anion can comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate and the like, or any combination thereof.
    [0037] Thus, for example, the support-activator (for example, chemically treated solid oxide) used in the catalyst compositions may be, or may comprise fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, silica -chlorinated alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, silica-coated fluorinated alumina, sulphate-coated alumina , phosphate alumina coated with silica and the like, or combinations thereof. In one aspect, the support-activator may be, or may comprise fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, silica-coated fluorinated alumina, silica-coated sulfated alumina, silica-coated phosphate alumina and the like or any combination of them. In another aspect, the support-activator comprises fluorinated alumina; alternatively, it comprises chlorinated alumina; alternatively, it comprises sulfated alumina; alternatively, it comprises fluorinated silica-alumina; alternatively, it comprises sulfated silica-alumina; alternatively, it comprises fluoridated zirconia silica; alternatively, it comprises chlorinated silica-zirconia; or alternatively, it comprises silica-coated fluorinated alumina.
    [0038] When the electron withdrawing component comprises a salt from an electron withdrawing anion, the counterion or cation of that salt can be selected from any cation that allows the salt to revert or decompose back to acid during calcination. Factors that dictate the suitability of the particular salt to serve as a source for the electron withdrawing anion include, but are not limited to, solubility of the salt in the desired solvent, lack of adverse cation reactivity, ionic pairing effects between the cation and anion, hygroscopic properties communicated to the salt by the cation and the like and thermal stability of the anion. Examples of suitable cations in the electron-withdrawing anion salt include, but are not limited to, ammonium, trialkylammonium, tetraalkylammonium, tetraalkylphosphonium, H +, [H (OEt2) 2] + and the like.
    [0039] Combinations of still one or more different electron withdrawing anions, in varying proportions, can be used to adjust the specific acidity of the activator support to the desired level. Combinations of electron-withdrawing components can be contacted with the oxide material simultaneously or individually, and in any order that grants the desired acidity of chemically treated solid oxide. For example, one aspect of this disclosure is employing two or more electron-withdrawing anion source compounds in two or more contact separation steps.
    [0040] Thus, an example of such a process by which a chemically treated solid oxide is prepared is as follows: a selected solid oxide, or combination of solid oxides is brought into contact with a first electron withdrawer anion source compound for form a first mixture; this first mixture is calcined and then placed in contact with a second electron-withdrawing anion source compound to form a second mixture; the second mixture is then calcined to form a treated solid oxide. In such a process, the first and the second electron-withdrawing anion source compound can be the same or different compounds.
    [0041] According to another aspect of the present disclosure, the chemically treated solid oxide comprises a solid inorganic oxide material, a mixed oxide material or a combination of inorganic oxide materials, which are chemically treated with an electron stripper component, optionally treated with a metal source, including metal salts, metal ions or other compounds containing metal. Examples without limitations of the metal or metal ions include zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium and the like, or combinations thereof. Examples of chemically treated solid oxides that contain a metal or metal ion include, but are not limited to, chlorinated zinc-impregnated alumina, fluorinated titanium-impregnated alumina, fluorinated zinc-impregnated alumina, chlorinated zinc-impregnated silica-alumina, silica- fluorinated zinc impregnated alumina, sulfated zinc impregnated alumina, chlorinated zinc aluminate, fluorinated zinc alumate, sulfated zinc aluminate, silica coated alumina treated with hexafluorotitanic acid, silica coated alumina treated with zinc and then fluorinated and the like. or any combination thereof.
    [0042] Any method of impregnating the solid oxide material with a metal can be used. The method by which the oxide is brought into contact with a metal source, usually a metal-containing salt or compound, may include, but is not limited to, gelation, cogelification, impregnation of one compound to another, and the like. If desired, the metal-containing compound is added or impregnated to the solid oxide in the form of a solution and subsequently converted to metal with support over calcination. In this sense, the inorganic solid oxide can comprise a metal selected from zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum and the like, or combinations of these metals. For example, zinc is often used to impregnate solid oxide because it can provide improved catalyst activity at low cost.
    [0043] The solid oxide can be treated with metallic salts or compounds containing metals before, after or at the same time that the solid oxide is treated with the electron withdrawing anion. Following any contact method, the mixture that was brought into contact with solid compound, electron-withdrawing anion and the metal ion are typically calcined. Alternatively, a solid oxide material, an electron-withdrawing anion source, and the metal or metal-containing metal salt are contacted and calcined simultaneously.
    [0044] Various processes are used to form the chemically treated solid oxide useful in the present disclosure. The chemically treated solid oxide may comprise the contact product of one or more solid oxides with one or more electron-withdrawing anion sources. It is not required that the solid oxide be calcined before being placed in contact with the electron-withdrawing anion source. The contact product is normally calcined either during or after the solid oxide is in contact with the electron-removing anion source. The solid oxide can be calcined or non-calcined. Several processes for preparing solid oxide support-activators that can be employed in this disclosure have been recorded. For example, such methods are described in Patent Nos. US6,107,230; US6,165,929; US6,294,494; US6,300,271; US6,316,553; US6,355,594; US6,376,415; US6,388,017; US6,391,816; US6,395,666; US6,524,987; US6,548,441; US6,548,442; US6,576,583; US6,613,712; US6,632,894; US6,667,274; and US6,750,302; whose disclosures are hereby incorporated by reference in their entirety.
    [0045] In accordance with one aspect of the present disclosure, the solid oxide material is chemically treated by placing it in contact with an electron withdrawing component, usually an electron withdrawing anion source. In addition, the solid oxide material is optionally chemically treated with a metal ion and then calcined to form a chemically treated solid oxide containing metal or impregnated with metal. According to another aspect of the present disclosure, the solid oxide material and an electron-withdrawing anion source are brought into contact and calcined simultaneously.
    [0046] The method by which the oxide is contacted with the electron-withdrawing component, usually a salt or acid from an electron-withdrawing anion, may include, but is not limited to, gelation, cogelification, impregnation of one compound to another , and others. Thus, following any contact method, the mixture placed in contact with solid oxide, electron withdrawing anion and the optional metal ion are calcined.
    [0047] The solid oxide support-activator (ie chemically treated solid oxide) can thus be produced by a process comprising: 1) contacting a solid oxide (or solid oxides) with an anion-removing compound electron (or compounds) to form a first mixture; and 2) calcination of the first mixture to form the solid oxide activator support.
    [0048] According to another aspect of the present disclosure, the solid oxide activator support (i.e., chemically treated solid oxide) is produced by a process comprising: 1) contact of a solid oxide (or solid oxides) with a first electron-withdrawing anion source compound to form a first mixture; 2) calcination of the first mixture to produce a first calcined mixture; 3) contact of the first calcined mixture with a second electron-withdrawing anion source compound to form a second mixture, and 4) calcination of the second mixture to form the solid oxide activator support.
    [0049] In accordance with yet another aspect of the present disclosure, chemically treated solid oxide is produced or formed to bring the solid oxide into contact with the electron-withdrawing anion source compound, where the solid oxide compound is calcined before, during or after contact with the electron-withdrawing anion source, and where there is a substantial absence of aluminoxane, organoboro or organoborate compounds, and ionizing ionic compounds.
    [0050] Calcination of treated solid oxide is generally conducted in an ambient atmosphere, usually in a dry ambient atmosphere, at a temperature of about 200 ° C to about 900 ° C and for a time of about 1 minute to about 100 hours. Calcination can be conducted at a temperature of about 300 ° C to about 800 ° C, or alternatively, at a temperature of about 400 ° C to about 700 ° C. Calcination can be conducted for about 30 minutes to about 50 hours, or for about 1 hour to about 15 hours. Thus, for example, calcination can be conducted for about 1 to about 10 hours at a temperature of about 350 ° C to about 550 ° C. Any suitable ambient atmosphere can be used during calcination. Calcination is usually conducted in an oxidizing atmosphere, such as air. Alternatively, an inert atmosphere, such as nitrogen or argon or a reducing atmosphere, such as hydrogen or carbon monoxide can be used.
    [0051] According to one aspect of the present disclosure, the solid oxide material is treated with a source of halide ion, sulfate ion or a combination of anions, optionally treated with a metal ion and then calcined to provide the treated solid oxide chemically in the form of a particulate solid. For example, the solid oxide material can be treated with a sulfate source (called a "sulfating agent"), a chloride ion source (called a "chloriding agent"), a fluoride ion source (called a "fluoridating agent" ), or a combination thereof, and calcined to provide the solid oxide activator. Useful acid-carrier activators include, but are not limited to, brominated alumina, chlorinated alumina, fluorinated alumina, sulfated alumina, brominated silica-alumina, chlorinated silica-alumina, fluorinated silica-alumina, sulfated silica-alumina, brominated silica-zirconia , chlorinated silica-zirconia, fluorinated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, hexafluorotitanic acid-treated alumina, silica-coated alumina treated with hexafluorotitanic acid, silica-alumina treated with hexafluorozirconic acid, silica-treated alumina , fluorinated boria-alumina, silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, a pillared clay, such as a pillared montmorillonite, optionally treated with fluorine, chloride or sulfate; phosphate alumina or other aluminophosphates, optionally treated with sulfate, fluoride or chloride; or some combination of the above. In addition, any of these activator supports can optionally be treated with a metal ion.
    [0052] The chemically treated solid oxide may comprise a fluorinated solid oxide in the form of a particulate solid. Fluoridated solid oxide can be formed by contacting a solid oxide with a fluoridating agent. The fluoride ion can be added to the oxide by forming an oxide slurry in a suitable solvent such as alcohol or water, including, but not limited to, one to three carbon alcohols due to its volatility and low surface tension. Examples of suitable fluoridating agents include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (NH4BF4), ammonium silicofluoride (hexafluorosilicate) (( ) 2SiF6), Ammonium hexafluorophosphate (NH4PF6), hexafluorotitanic acid (H2TIF6), ammonium hexafluorotitanic acid ((NH4) 2TiFe), hexafluorozironic acid (H2ZrFθ), AIF3, NH4AIF4, analogues of the same. Triflic acid and ammonium ammonium triphylate can also be used. For example, ammonium bifluoride (NH4HF2) can be used as a fluoridating agent, due to its ease of use and availability.
    [0053] If desired, the solid oxide is treated with a fluoridating agent during the calcination step. Any fluoridating agent capable of bringing the solid oxide into contact during the calcination step can be used. For example, in addition to the fluoridating agents described above, volatile organic fluoridating agents can be used. Examples of volatile organic fluoridating agents useful in this aspect of the disclosure include, but are not limited to, freons, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, and the like, and combinations thereof. Calcination temperatures should generally be high enough to decompose the compound and release fluoride Gaseous hydrogen fluoride (HF) or fluorine (F2) itself can also be used with solid oxide if fluoridated during calcination. Silicon tetrafluoride (SiF4) and compounds containing tetrafluoroborate (BF4 ') can also be used. A convenient method of contacting the solid oxide with the fluoridating agent is to vaporize a fluoridating agent in a gas stream used to fluidize the solid oxide during calcination.
    [0054] Similarly, in another aspect of the disclosure, the chemically treated solid oxide comprises a chlorinated solid oxide in the form of a particulate solid. The solid chloride oxide is formed when a solid oxide is brought into contact with a chlorinating agent. The chloride ion can be added to the oxide by forming an oxide slurry in a suitable solvent. The solid oxide can be treated with a chlorinating agent during the calcination step. Any chlorinating agent capable of serving as a chloride source and completely bringing the oxide into contact during the calcination step can be used, such as SiCI4, SiMe2CI2, TiCI4, BCI3 and the like, including mixtures thereof. Volatile organic chlorinating agents can be used. Examples of suitable volatile organic chlorinating agents include, but are not limited to, certain freons, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, and the like or any combination thereof. Hydrogen chloride gas or chlorine itself can also be used with solid oxide during calcination. A convenient method of contacting the oxide with the chlorinating agent is to vaporize a chlorinating agent in a gas stream used to fluidize the solid oxide during calcination.
    [0055] The amount of fluoride or chloride ion present before calcination of the solid oxide is generally about 1 to about 50% by weight, where the weight percentage is based on the weight of the solid oxide, for example, silica -alumina, before calcination. According to another aspect of the disclosure, the amount of fluoride or chloride ion present before calcination of the solid oxide is from about 1 to about 25% by weight, according to another aspect of the disclosure, from about 2 to about 20% by weight. According to yet another aspect of the disclosure, the amount of fluoride or chloride ion present before calcination of the solid oxide is from about 4 to about 10% by weight. Once impregnated with halide, halide oxide can be dried by any suitable method, including, but not limited to, suction filtration followed by evaporation, vacuum drying, vaporization drying, and the like, although it is also possible to start the step calcination immediately without drying the solid oxide.
    [0056] The silica-alumina used to prepare the treated silica-alumina normally has a pore volume greater than about 0.5 cc / g. According to one aspect of the present disclosure, the pore volume is greater than about 0.8 cc / g and according to another aspect of the present disclosure, greater than about 1.0 cc / g. In addition, silica-alumina generally has a surface area greater than about 100 m2 / g. According to another aspect of the disclosure, the surface area is greater than about 250 m2 / g. In addition, in another aspect, the surface area is greater than about 350 m2 / g.
    [0057] The silica-alumina used in the present disclosure normally has an alumina content of about 5 to about 95% by weight. According to a disclosure aspect, the alumina content of silica-alumina is about 5 to about 50%, or about 8% to about 30%, alumina by weight. In another aspect, silica-alumina compounds with a high alumina content can be employed, in which the alumina content of these silica-alumina compounds is typically in the range of about 60% to about 90%, or about 65% to about 80% alumina by weight. According to yet another aspect of the disclosure, the solid oxide component comprises alumina without silica, and according to another aspect of the disclosure, the solid oxide component comprises silica without alumina.
    [0058] The sulfated solid oxide comprises sulfate and a solid oxide component, such as alumina or silica-alumina, in the form of a particulate solid. Optionally, the sulfated oxide is further treated with a metal ion, so that the calcined sulfated oxide comprises a metal. According to one aspect of the present disclosure, the sulfated solid oxide comprises sulfate and alumina. In some cases, sulfated alumina is formed by a process in which the alumina is treated with a sulfate source, for example, sulfuric acid or a sulfate salt, such as ammonium sulfate. This process is usually carried out by forming an alumina slurry in a suitable solvent, such as alcohol or water, in which the desired concentration of the sulfating agent has been added. Suitable organic solvents include, but are not limited to, one to three carbon alcohols due to their volatility and low surface tension.
    [0059] According to a disclosure aspect, the amount of sulfate ions present before calcination is about 0.5 to about 100 parts by weight of sulfate ion of about 100 parts by weight of solid oxide. According to another aspect of the disclosure, the amount of sulfate ion present before calcination is from about 1 to about 50 parts by weight of sulfate ion to about 100 parts by weight of solid oxide, and according to yet another aspect of the disclosure, from about 5 to about 30 parts by weight of sulfate ion to about 100 parts by weight of solid oxide. These weight ratios are based on the weight of the solid oxide before calcination. Once impregnated with sulfate, the sulfated oxide can be dried by any suitable method, including, but not limited to, suction filtration followed by evaporation, vacuum drying, vaporization drying, and the like, although it is also possible to start the drying step. calcination immediately.
    [0060] According to another aspect of the present disclosure, the activator support used in the preparation of the catalyst compositions of this disclosure comprises an exchangeable ion activator support, including, but not limited to silicate and aluminosilicate or mineral compounds, either with layered or layered structures, and combinations thereof. In another aspect of the disclosure, exchangeable ion, layered aluminosilicates, such as pillared clays are used as support-activators. When the acid-activating support comprises an exchangeable ion-activating support, it can optionally be treated with at least one electron-withdrawing anion, such as those disclosed here, although normally the exchangeable ion-activating support is not treated with a electron withdrawing anion.
    [0061] According to another aspect of the present disclosure, the activator-support of this disclosure comprises mineral clays having interchangeable cations and layers capable of expanding. Typical mineral clay activating supports include, but are not limited to, exchangeable ions, layered aluminosilicates, such as pillared clays. Although the term "support" is used, it should not be interpreted as an inert component of the catalyst composition, on the contrary, it should be considered an active part of the catalyst composition, due to its close association with the metallocene component.
    [0062] According to another aspect of this disclosure, the clay materials in this disclosure include materials, either in their natural state or that have been treated with various ions by wetting, ion exchange or pillarization. Typically, the clay material activator support comprises clays that have ion exchanged with large cations, including polynuclear, cations with highly charged metal complexes. However, the clay material activating supports in this disclosure also include clays that have ion exchanged with simple salts, including, but not limited to, Al (lll), Fe (II), Fe (III) and Zn ( ll) with binders, such as halide, acetate, sulfate, nitrate or nitrite.
    [0063] According to another aspect of the present disclosure, the support-activator comprises a pillared clay. The term "pillared clay" is used to refer to clay materials that have had ion exchange with large, normally, highly charged polynuclear metal complex cations. Examples of such ions include, but are not limited to, Keggin ions which can have charges, such as 7 +, various polyoxometalates and other large ions. Thus, the term pilarizing refers to a simple permutation reaction, in which the exchangeable cations of a clay material are replaced with large, highly charged ions, such as Keggin ions. These polymeric cations are then immobilized within the clay interlayer and when calcined are converted into metal oxide "pillars", effectively supporting the clay layers as column-like structures. Thus, once the clay is dried and calcined to produce the supporting pillars between the clay layers, the expanded reticular structure is maintained and the porosity is reinforced. The resulting pores may vary in size and shape depending on the pillar material and the original clay material used. Examples of pillar and pillar clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J.M. Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.)) Ch. 3, pp. 55-99, Academic Press, Inc., (1972); Patent Nos. US4,452,910; US5,376,611; and US 4,060,480; the disclosures of which are incorporated herein by reference in their entirety.
    [0064] The pillarizing process uses clay minerals having interchangeable cations and layers capable of expanding. Any pillarized clay that can enhance the polymerization of olefins in the catalyst composition of the present disclosure can be used. Therefore, clay minerals suitable for pillaring include, but are not limited to, allophanes; smectites, both dioctahedral (Al) and trioctahedral (Mg) and derivatives thereof, such as montmorillonites (bentonites), nontronites, hectorites or laponites; haloisites; vermiculites; micas; fluoromics; chlorites; mixed layer clays; fibrous clays, including but not limited to sepiolites, atapulgites and paligorschites; a serpentine clay; illita; laponite; saponite; and any combination thereof. In one aspect, the pillarized clay support-activator comprises bentonite or montmorillonite. The main component of bentonite is montmorillonite.
    [0065] The pillared clay can be pretreated, if desired. For example, a pillarized bentonite is pre-treated by drying at about 300 ° C under an inert atmosphere, usually dry nitrogen, for about 3 hours, before being added to the polymerization reactor. Although an exemplary pretreatment is described herein, it should be understood that preheating can be carried out at many other temperatures and times, including any combination of temperature and time steps, all of which are encompassed by this disclosure.
    [0066] The activator support used to prepare the catalyst compositions of the present disclosure can be combined with other inorganic support materials, including, but not limited to, zeolites, inorganic oxides, phosphate inorganic oxides and the like. In one aspect, typical support materials used include, but are not limited to, silica, silica-alumina, alumina, titania, zirconia, magnesia, boria, toria, aluminophosphate, aluminum phosphate, silica-titania, coprecipitated silica / titania, mixtures or any combination thereof.
    [0067] The process of making these support-activators can include precipitation, coprecipitation, impregnation, gelation, pore-gelation, calcination (up to 900 ° C), spray drying, instant drying, rotary drying and calcination, crushing, sieving and similar operations.
    [0068] In one embodiment, an organoaluminium compound suitable for use in the present disclosure comprises an alkylaluminum compound. For example, the organoaluminium compound can comprise a trialkylaluminium compound, having the general formula AIR3. Examples of compounds without limitation of trialkylaluminum compounds suitable for use in this disclosure include triisobutylaluminium (TiBA or TiBAI); tri-n-butylaluminium (TNBA); Tri-octli-butylaluminium (TOBA); triethyl aluminum (TEA); and / or other appropriate alkyl-aluminum complexes and combinations thereof. In addition, partially hydrolyzed alkyl aluminum compounds and / or aluminum oxanes can be used. In one embodiment, the organoaluminium compound comprises a compound represented by the general formula:
    where X5 is a halide, hydrocarbiloxide group, hydrocarbilamino group or combinations thereof; X6 is a hydrocarbyl group having up to 18 carbon atoms; p ranges from 0 to 2; eq is 3-p.
    [0069] In one embodiment, catalysts are chosen from compounds such as those represented by the chemical structures MTE-A and MTE-B.

    [0070] In one embodiment, a catalyst system suitable for use in the present disclosure comprises a metallocene compound (for example, MTE-A), an activating support (for example, sulfated alumina); and an organoaluminium compound (for example, TIBA).
    [0071] The polymer may include other additives. Examples of additives include, but are not limited to, antistatic agents, dyes, stabilizers, nucleators, surface modifiers, pigments, glidants, non-stick agents, tachyants, polymer processing aids and combinations thereof. Such additives can be used singly or in combination and can be included in the polymer before, during, or after the preparation of the polymer as described herein. Such additives can be added by any suitable technique, for example, during an extrusion or composition phase, such as during pelletizing or subsequent processing on an end-use article.
    [0072] In one embodiment, a monomer (for example, ethylene) is polymerized using the methodologies disclosed here, to produce a polymer of the type disclosed here. The polymer can comprise a homopolymer. In one embodiment, the polymer is a homopolymer. It should be understood that an insignificant amount of comonomer may be present in the polymers disclosed herein and the polymer is still considered a homopolymer. An insignificant amount of a comonomer refers here to an amount that does not substantially affect the polymer properties disclosed herein. For example, a comonomer can be present in an amount of less than about 0.5% by weight, 0.1% by weight or 0.01% by weight based on the total weight of the polymer.
    [0073] In one embodiment, a polymer of the type described here is characterized by a density equal to or greater than about 0.945 g / cc, alternatively greater than about 0.950 g / cc, alternatively greater than about 0.955 g / cc, or alternatively greater than about 0.960 g / cc, determined according to ASTM D 1505.
    [0074] In one embodiment, a polymer of the type described here is a unimodal resin. "Modality" of a polymer resin refers here to the shape of its molecular weight distribution curve, that is, the appearance of the graph of the polymer's weight fraction as a function of its molecular weight. The weight fraction of the polymer refers to the weight fraction of molecules of a given size. A polymer having a molecular weight distribution curve showing a single peak can be referred to as a unimodal polymer, a polymer having curve showing two distinct peaks can be referred to as a bimodal polymer, a polymer having a curve showing three distinct peaks can be referred to as trimodal polymer, etc. Polymer modality can be determined using any suitable methodology, such as those described here in the example sections.
    [0075] In one embodiment, a polymer of the type described here has an average molecular weight (Mw) of about 80 kg / mol to about 200 kg / mol; alternatively from about 90 kg / mol to about 175 kg / mol; or, alternatively from about 100 kg / mol to about 150 kg / mol. The average molecular weight describes the molecular weight distribution of a polymer and is calculated according to equation 1:
    where Ni is the number of molecules in molecular weight Mi.
    [0076] A polymer of the type described here can be characterized by the molecular weight distribution (MWD) of about 2 to about 5; alternatively from about 2 to about 4.5; or alternatively from about 2 to about 4. MWD is the ratio of Mw to the average number of molecular weight (Mn), which is also referred to as the polydispersity index (PDI), or more simply as polydispersity . The average number of molecular weight is the common average of the molecular weights of the individual polymers and can be calculated according to equation (2), where N, is the number of molecules of molecular weight Mi.

    [0077] A polymer of the type described here can be further characterized by a ratio of average molecular weight-z (Mz) to Mw (Mz / Mw) of less than about 4, alternatively of less than about 3, 5, or alternatively less than about 3. The z-average molecular weight is a higher-order average molecular weight that is calculated according to equation (3)
    where Nj is the number of molecules in molecular weight Mi. The Mz / Mw ratio is another indication of the MWD width of a polymer.
    [0078] In one embodiment, a polymer of the type described here has a melt index, Ml, in the range of about 0.5 grams for 10 minutes (g / 10 min) to about 4.0 g / 10 min, alternatively from about 0.7 g / 10 min to about 3.0 g / 10 min, or alternatively from about 0.75 g / 10 min to about 2.75 g / 10 min, or, alternatively, from about 0.8 g / 10 min to about 1.8 g / 10 min. The melt index (Ml) refers to the amount of a polymer that can be forced through a 0.0825 inch diameter melt index hole when subjected to a force of 2160 grams in ten minutes at 190 ° C, as determined according to ASTM D 1238.
    [0079] Polymers of the type disclosed herein can be formed into articles of manufacture or articles of end use using any suitable technique, such as extrusion of blown and molded film, blow molding, injection molding, fiber spinning, thermoforming.
    [0080] In one embodiment, polymers of the types described herein disclosed are manufactured in a film. Promotional films can be produced by any suitable method and under any suitable conditions for film production. In one embodiment, polymers are formed into films through a blown film process. In a blown film process, molten plastic is extruded through an annular die, usually vertically, to form a walled tube. The size of the bubble is a function of the blowing ratio that is controlled by the air introduced into the die. The bubble then moves upward until it passes through pinch rollers where the tube is flattened to create what is known as a lay-flat film. This lay-flat or collapsed tube is then collected on a cardboard roll. Crystallization of the polymer continues in the film until 48 hours after the process. On the highest outlet lines, fresh air is introduced continuously into the bubble, allowing for higher outlet rates. This way of cooling the bubble is known as Internal Bubble Cooling (IBC).
    [0081] Normally, the blowing ratio between die and blown bubble would be 1.5 to 4 times the diameter of the die. The downgrade between the thickness of the melting wall and the thickness of the cooled film occurs in the radial and longitudinal directions and is easily controlled by changing the volume of air inside the bubble and changing the speed of the line start. The films formed from polymer resins of this disclosure (for example, polyethylene) can be of any thickness desired by the user. Alternatively, the polymers of this disclosure can be formed into films having a thickness of about 0.1 mils to about 5 mils, alternatively from about 0.2 mils to about 2 mils, alternatively from about 0.3 mils to about 1.65 mils.
    [0082] In one embodiment, films formed from polymers of this disclosure may exhibit enhanced barrier properties. For example, such films may exhibit reduced moisture vapor transmission rates (MVTR).
    [0083] In one embodiment, monolayer films of 1 thousand produced from polymers of this disclosure have an MVTR of less than, or equal to 0.55 grams-mil per 100 square inches per day (g-mil / 100 in2 / day) , alternatively less than, or equal to about 0.44 g-mil / 100 in2 / day or alternatively less than, or equal to about 0.39 g-mil / 100 in2 / day, measured in accordance with ASTM F 1249. MVTR measures the passage of gaseous H2O through a barrier. MVTR can also be referred to as the water vapor transmission rate (WVTR). Typically, MVTR is measured in a special chamber, vertically divided by the substrate / barrier material. A dry atmosphere is in one chamber, and a wet atmosphere is in the other. A 24-hour test is performed to see how much moisture passes through the substrate / barrier from the "wet" chamber to the "dry" chamber under conditions that can specify any of the five combinations of temperature and humidity in the "wet" chamber. The lower the transmission rate, the better the film is at blocking moisture.
    [0084] In one embodiment, monolayer films formed from polymers of this disclosure may exhibit improved optical properties. For example, such films may exhibit reduced opacity. Generally opacity refers to the cloudy appearance of a material cause by the light scattered from within the material or its surface. The opacity values disclosed here refer to the percentage of transmitted light that disperses or deviates from an incident beam by more than 2.5 ° (degrees of angle). The opacity of a material can be determined in accordance with ASTM D1003 for an opacity percentage of 30% or less. A material having an opacity percentage greater than 30% can be determined in accordance with ASTM E167. In one embodiment, 1000 films produced from polymers of the type described herein have an opacity percentage of less than about 45%, alternatively less than about 35%, or alternatively less than about 25% for a density of 0.949 g / cc or more.
    [0085] The films produced from polymers of this disclosure can be used in the formation of any variety of articles for end use. These end-use items may include, without limitation, merchandise bags, trash can bags, t-shirt bags, grocery bags, product bags, food packaging for content such as cereals, crackers, cheese, meat, etc., Packaging with heat shrink material and other items. Other unrestricted examples of end-use items include containers, cups, trays, pallets, toys or a component of another product. In one embodiment, the polymers disclosed here (for example, polyethylene) can be formed into films that can be useful in food packaging. EXAMPLES
    [0086] Being the object in general described, the following examples are given as particular modalities of disclosure and to demonstrate their practice and advantages. It is understood that the examples are given by way of illustration and are in no way intended to limit the specification of the following claims. The following test procedures were used to evaluate the various polymers and compositions.
    [0087] melt index (Ml, g / 10 min) was determined in accordance with ASTM D 1238, condition E, at 190 ° C with a weight of 2160 grams.
    [0088] Density of the polymer was determined in grams per cubic centimeter (g / cc) in a molded compression sample, refrigerated at about 15 ° C per hour and conditioned for about 40 hours at room temperature in accordance with ASTM D 1505 and ASTM D 1928, procedure C.
    [0089] Molecular weight and molecular weight distributions were obtained using a PL-GPC 220 system (Polymer Labs, an Agilent Company) equipped with an IR4 detector (PolymerChar, Spain) and three Styragel HMW-6E GPC columns (Waters, MA ) running at 145 ° C mobile phase flow rate 1, 2,4-trichlorobenzene (TCB) containing 0.5 g / L 2,6-di-t-butyl-4-methylphenol (BHT) was fixed at 1 ml / min and the concentration of polymer solutions was generally maintained in the range of 1.0-1.5 mg / ml, depending on the molecular weight. Sample preparation was carried out at 150 ° C for nominally 4 h with occasional and gentle agitation before the solutions were transferred to sample vials for injection. The integral calibration method was used to deduce the molecular weights and molecular weight distributions using polyethylene resin Chevron Phillips Chemicals Company's HDPE, and MARLEX BHB5003, as a broad standard The integral table of the broad standard was predetermined in a separate experiment with SEC-MALS .
    [0090] Rheology measurements were made as follows: Strains were generally kept at a single value during a frequency scan, but higher strain values were used for low viscosity samples to maintain a measurable torque. Smaller strain values were used for high viscosity samples to avoid overloading the torque transducer and to keep within the linear viscoelasticity limits of the sample. The instrument automatically reduces deformation at high frequencies, to keep the torque transducer off overload if necessary. These data were adapted to the Carreau-Yasuda equation to determine shear viscosity (ηo), relaxation time (T) and a measure of the relaxation time distribution width (CY-a). The Carreau- Yasuda (CY) model is represented by equation (4):
    where E = viscosity = (Pas) / = shear rate (1 / s) a = rheological width parameter Tç = relaxation time (s) [describes the site instead of the transition region] Eo = zero shear viscosity ( Pa s) [defines the Newtonian plateau] n = power law constant [defines the final slope of the high shear rate region],
    [0091] To facilitate model adaptation, the power law constant n is retained at a constant value. Details on the meaning and interpretation of the CY model and derived parameters can be found at: C. A. Hieber and H. H. Chiang, Rheol. Acta, 28, 321 (1989); C.A. Hieber and H.H Chiang, Polym. Eng. Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987), each of which is incorporated herein by reference in its entirety.
    [0092] MVTR and opacity were measured in accordance with ASTM F 1249 and ASTM D-1003, respectively. Opacity measurements were determined with a Haze-Gard Plus device from BYK-Gardner or equivalent. EXAMPLE 1
    [0093] Polymers of the type described here were prepared using a catalyst system, consisting of a single metallocene complex (for example, MTE-A or MTE-B), a solid oxide (for example, sulfated alumina) and a compound of organoaluminium (for example, triisobutylaluminium (Tiba)). Specifically 5 samples designated 2-6, of homopolymer polyethylene samples were prepared as disclosed herein. Various properties of the polymer have been evaluated and the results are shown in Table 1. Also shown are the values for a comparative polyethylene resin MARLEX 9659, which is a commercially available high density polyethylene from Chevron Phillips Chemical Company LP. The molecular weight distribution profiles and a plot of the dynamic viscosity of the melt as a function of frequency for the samples are shown in figures 1 and 2, respectively.


    [0094] Although modalities of the invention have been shown and described, modifications of them can be made without abandoning the spirit and teachings of the invention. The modalities and examples described here are exemplary only, and are not intended to be a limiting factor. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Where numerical ranges or limitations are expressly established, such expressed ranges or limitations must be understood to include iterative ranges or limitations such as magnitude covered, express ranges or established limitations (e.g., from about 1 to about 10 includes, 2, 3, 4, etc .; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). Use of the term "optionally" in relation to any element of a claim is intended to mean that the element of the object 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. are to be understood to provide support for stricter terms, such as, consisting of, consisting essentially of, substantially comprises of, etc.
    [0095] In this sense, the scope of protection is not limited by the description set out above, but is limited only by claims that follow that scope including all equivalents of the object of the claims. Each claim is incorporated into the specification as an embodiment of the present invention. Thus, the statements are an additional description and an addition to the detailed description of the present invention. The disclosures of all patents, patent applications and publications cited here by this means are incorporated by reference, insofar as they provide copies, proceedings or other details complementary to those established herein.
    权利要求:
    Claims (9)
    [0001]
    1. Unimodal polymer, characterized by the fact that it has a melting index of 0.8 g / 10 min at 4 g / 10 min, as determined according to ASTM D 1238 condition E at 190 ° C with a weight of 2160 grams, a density equal to or greater than about 0.945 g / cc, as measured according to ASTM D 1505 and ASTM D 1928, procedure C, a molecular weight distribution of 2 to 4, and an average z-molecular weight ratio to at the average molecular weight (Mz / Mw) of less than 4, which when formed in a 1 mil film, exhibits an opacity of less than 35%, measured according to ASTM D-1003 or ASTM E167, and a ratio of moisture vapor transmission of less than about 0.55 g-mil / 100 in2 in 24 hours, as determined in accordance with ASTM F 1249.
    [0002]
    2. Polymer according to claim 1, characterized by the fact that it has an average molecular weight of 80 kg / mol to 200 kg / mol.
    [0003]
    3. Polymer according to claim 1, characterized by the fact that it comprises polyethylene.
    [0004]
    4. Polymer according to claim 1, characterized by the fact that, when formed in a film, it exhibits a moisture vapor transmission rate of less than 0.44 g-mil / 100 in2 in 24 hours, as determined in in accordance with ASTM F 1249.
    [0005]
    5. Polymer according to claim 4, characterized by the fact that it has an average molecular weight of 80 kg / mol to 200 kg / mol.
    [0006]
    6. Polymer according to claim 1, characterized by the fact that it comprises an ethylene polymer.
    [0007]
    7. Polymer, according to claim 1, characterized by the fact that, when formed in a film, it exhibits a moisture vapor transmission rate of less than 0.39 g-mil / 100 in2 in 24 hours, as determined in in accordance with ASTM F 1249.
    [0008]
    8. Polymer according to claim 7, characterized by the fact that it has an average molecular weight of 80 kg / mol to 200 kg / mol.
    [0009]
    9. Food packaging container, characterized by the fact that it comprises a film formed from the polymer, as defined in any one of claims 1 to 8.
    类似技术:
    公开号 | 公开日 | 专利标题
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    BR112014004959B1|2021-01-19|bimodal polymer comprising polyethylene and food packaging container
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-05-26| B09A| Decision: intention to grant|
    2020-11-10| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/09/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/224,775|2011-09-02|
    US13/224,775|US9018329B2|2011-09-02|2011-09-02|Polymer compositions having improved barrier properties|
    PCT/US2012/053606|WO2013033689A1|2011-09-02|2012-09-04|Polymer compositions having improved barrier properties|
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